CN101983098A - Systems and methods for processing CO2 - Google Patents

Abstract

Systems and methods for reducing the levels of carbon dioxide and other atmospheric pollutants are provided. Economically viable systems and methods for removing large quantities of carbon dioxide and other atmospheric pollutants from gaseous waste streams and storing them in a storage-stable form are also discussed.

Description

Systems and methods for processing CO2

cross reference

This application claims the benefit of the following applications, each of which is incorporated herein by reference in its entirety.

U.S. provisional patent application 61/158,992, dated March 10, 2009, titled "Liquid Absorption of Gaseous Pollutants Using a Flat Jet Reactor";

U.S. provisional patent application 61/168,166, filed April 9, 2009, entitled "Apparatus, Systems, and Methods for Treating Industrial Waste Gases";

U.S. provisional patent application 61/178,475, dated May 14, 2009, titled "Apparatus, Systems, and Methods for Treating Industrial Waste Gases";

U.S. Provisional Patent Application 61/228,210, July 24, 2009, entitled "Apparatus, Systems, and Methods for Treating Industrial Waste Gases";

U.S. provisional patent application 61/230,042, dated July 30, 2009, titled "Apparatus, Systems, and Methods for Treating Industrial Waste Gases";

U.S. Provisional Patent Application 61/239,429, September 2, 2009, entitled "Apparatus, Systems, and Methods for Treating Industrial Waste Gases";

U.S. Provisional Patent Application 61/178,360, May 14, 2009, entitled "Methods and Apparatus for Contacting Gas and Liquid";

U.S. provisional patent application 61/221,457, filed on June 29, 2009, entitled "Gas-Liquid-Solid Contactor and Precipitator: Apparatus and Methods";

U.S. provisional patent application 61/221,631, filed on June 30, 2009, entitled "Gas, Liquid, Solid Contacting: Methods and Apparatus";

U.S. Provisional Patent Application 61/223,657, July 7, 2009, entitled "Gas, Liquid, Solid Contacting: Methods and Apparatus";

U.S. provisional patent application 61/289,657, filed on December 23, 2009, entitled "Gas, Liquid, Solid Contacting: Methods and Apparatus";

U.S. Provisional Patent Application 61/306,412, filed February 19, 2010, and entitled "Apparatus, Systems, And Methods For Treating Industrial Waste Gases"; and

U.S. Provisional Patent Application 61/311,275, filed March 5, 2010, entitled "Apparatus, Systems, And Methods For Treating Industrial Waste Gases."

background

The most concentrated point sources of carbon dioxide and many other atmospheric pollutants (such as NOx, SOx, volatile organic compounds ("VOCs"), and particulate matter) are power plants that produce energy, particularly those that produce their electricity by burning carbon-based fuels factories (such as thermal power plants). Considering the projected increase in global energy demand, and despite the continued growth of non-carbon-based energy sources, atmospheric levels of carbon dioxide and other combustion products of carbon-based fuels are projected to increase. Thus, power plants utilizing carbon-based fuels are particularly useful for technologies aimed at reducing carbon dioxide and other atmospheric pollutants.

Attempts to reduce emissions of carbon dioxide and other atmospheric pollutants from power plant waste streams have resulted in many different technologies, most of which require very large energy inputs to account for the energy associated with separating and concentrating diffuse gaseous species. Additionally, current techniques and related equipment are inefficient and costly. Thus, it is important to develop economically viable technologies capable of removing large quantities of carbon dioxide and other atmospheric pollutants from gaseous waste streams by sequestering carbon dioxide and other atmospheric pollutants in a stable form or by converting them into useful commodity products. other air pollutants.

In view of the foregoing, there is a significant need for systems and methods to efficiently and economically sequester carbon dioxide and other atmospheric pollutants.

summary

In some embodiments, the present invention provides a device for transferring a gas component into a liquid, comprising a gas inlet; a chamber configured to contact the liquid and the gas; a first liquid introduction unit at a first location in the chamber; and A second liquid introduction unit at a second position in the chamber, wherein the liquid introduction unit is configured to introduce liquid into the chamber so as to contact the gas; a reservoir configured to contain the liquid after the liquid has contacted the gas; a reservoir for the liquid an outlet after it has been exposed to gas, wherein the inlet, chamber, liquid introduction unit, reservoir and outlet are operably connected; and at least one of the following features: i) at least one array of rows in the chamber, wherein the The rows are configured to redistribute the flow of the gas as it enters the chamber such that the gas flows axially along the chamber over a greater area of the chamber cross-section than the flow of the gas upon entering the chamber prior to interacting with the rows. flow; ii) a defoaming device configured to reduce foam in the reservoir; iii) at least one pump per liquid introduction unit for pumping liquid through the introduction unit; iv) configuring the liquid introduction unit so that the liquid leaves The direction of flow of the first unit is different from the direction of flow of liquid exiting the second unit; v) one or more orifice mechanisms (drain valves) configured to direct the flow of liquid to at least one of the liquid introduction units, to In the gas inlet, or a combination thereof; and vi) changing the area covered by the liquid introduction unit, wherein the liquid introduction unit includes an atomization unit that produces a spray, wherein at least one atomization unit is configured to produce an angle different from that of the other atomization units spray. In some embodiments, the device includes at least two of the features. In some embodiments, the device includes at least three of the features. In some embodiments, the device includes at least four of the features. In some embodiments, the device includes at least five of the features. In some embodiments, the device includes all of the described features. In some embodiments, the gas inlet is configured to accept industrial waste gas, compressed ambient air, compressed carbon dioxide, supercritical carbon dioxide, or any combination thereof. In some embodiments, the gas includes industrial waste gas, carbon dioxide that has been previously separated from the industrial waste gas, or any combination thereof. In some embodiments, the gas includes one or more of carbon dioxide, nitrogen oxides, and sulfur oxides. In some embodiments, the first liquid introduction unit is located at the lowest level above the gas inlet and is oriented to direct liquid flow into the chamber in a direction substantially co-current to the direction of gas flow. In some embodiments, the second liquid introduction unit is oriented to direct liquid flow into the chamber in a direction substantially countercurrent to the direction of gas flow. In some embodiments, the first liquid introduction unit, the second liquid introduction unit, or both include a spout. In some embodiments, the jet comprises a two-fluid jet. In some embodiments, the jets comprise injector-jet jets. In some embodiments, at least one of the pumps is controlled with a variable frequency drive. In some embodiments, the defoaming device includes a cone located on the reservoir. In some embodiments, the defoaming device further includes a liquid sprayer oriented towards the cone. In some embodiments, the device further comprises a liquid recirculation loop configured to direct liquid from the reservoir to one or more of the liquid introduction units. In some embodiments, the apparatus further comprises a demisting level before the gas exits the contacting chamber. In some embodiments, the demisting level includes a wave demister, a flat spray nebulizer, a wet electrostatic precipitator, a packed bed, or any combination thereof. In some embodiments, the liquid provided to the demisting level comprises a different solution than the liquid provided to the liquid introduction unit. In some embodiments, the liquid provided to each liquid introduction unit comprises a different solution. In some embodiments, the liquid provided to the demisting level is clear liquid. In some embodiments, the liquid provided to the liquid introduction unit comprises a slurry. In some embodiments, the apparatus further includes a comminution station configured to accept the slurry from the reservoir and provide processed slurry to the liquid introduction unit. In some embodiments, the recirculation loop includes a comminution station. In some embodiments, the reservoir is located below the spout at the bottom of the contacting chamber. In some embodiments, the apparatus further includes a settling tank operatively connected to the contacting chamber. In some embodiments, the settling tank includes a temperature controller, an inlet for adding a pH adjuster, an agitator, an inlet for a crystal growth agent, an inlet for a crystal seeding agent, an inlet for a settling agent inlet, inlet for flocculant, or any combination thereof. In some embodiments, the device further includes a settling outlet operatively connected to the settling tank. In some embodiments, the precipitation outlet collects the solid precipitate and the supernatant solution. In some embodiments, the precipitation outlet separates solid precipitate from the supernatant solution. In some embodiments, the apparatus further includes a conduit to provide the solid sediment to the building material manufacturing station. In some embodiments, the gas inlet is configured to accept exhaust gas from an industrial facility. In some embodiments, the gas inlet is configured to accept flue gas from a fossil fuel fired facility. In some embodiments, the gas inlet is configured to accept flue gas from a fossil fuel fired facility, further wherein the flue gas has passed through an emission control system before being provided to the gas inlet of the device. In some embodiments, the emission control system includes one or more of: i) electrostatic precipitators for collecting particulate matter; ii) SOx control technology; iii) NOx control technology; iv) physical Filtration technology; or v) Mercury control technology. In some embodiments, the nebulizers of the nebulization unit comprise 60° nebulizers near the walls of the contacting chamber and 90° nebulizers in the inner cross-section of the contacting chamber. In some embodiments, the flow of gas along the rows is vertical. In some embodiments, in the chamber, the apparatus further comprises packing material, trays, packed beds, or any combination thereof. In some embodiments, in said chamber, the device further comprises at least one membrane or one microporous membrane.

In some embodiments, the present invention provides an apparatus comprising an absorber comprising a bubble column; an inlet for an industrial gas operatively connected to the absorber, wherein the industrial gas comprises an amount equal to the time-average Original composition of _CO2 , SOx, NOx, heavy metals, non- _CO2 acid gases and/or fly ash; inlet for absorption solutions including alkaline solutions including brine, particulate material or in absorption slurries Both; outlets for exhaust gases characterized by being depleted in _CO2 and SOx, NOx, heavy metals, non- _CO2 acid gases and/or in fly ash relative to said original composition of said industrial gas At least one of, wherein the outlet is operatively connected to the absorber; an outlet for the absorbing solution that has been contacted with the industrial gas is operatively connected to the absorber; and a processing station is operatively connected to the outlet, wherein The processing station is configured to obtain at least one of the following salable products: building materials including a _CO2 storage component, desalinated water, potable water, a slurry including a _CO2 storage component, or a _CO2 storage component A solution in which the bubble column is configured to produce bubbles of the industrial gas in the absorption solution such that at least 10 wt% of the carbon dioxide in the industrial gas is transferred to the absorption solution. In some embodiments, the present invention provides an apparatus comprising an absorber comprising a sparging vessel; an inlet for an industrial gas operatively connected to the absorber, wherein the industrial gas comprises a quantity CO ₂ , SOx, NOx, heavy metals, non-CO ₂ acid gases and/or fly ash equal to the time-averaged original composition; inlet for absorption solutions including alkaline solutions including brine, particulate material or both in the slurry; an outlet for exhaust gas characterized by its depletion in CO _and SOx, NOx, heavy metals, non- _CO acid gases and/or relative to the original composition of the industrial gas At least one of the fly ash, wherein the outlet is operatively connected to the absorber; an outlet for the absorbing solution that has been contacted with the industrial gas is operably connected to the absorber; and a process operatively connected to the outlet station, wherein the processing station is configured to obtain at least one of the following salable products: building materials including a _CO2 sequestration component, desalinated water, drinking water, a slurry including a _CO2 sequestration component, or a _CO2 sequestration component A solution of a storage component, wherein the dispensing vessel is configured to generate bubbles of the industrial gas in the absorbing solution such that at least 10 wt% of the carbon dioxide in the industrial gas is transferred to the absorbing solution. In some embodiments, the present invention provides an apparatus comprising an absorber comprising a spray tower; an inlet for an industrial gas operatively connected to the absorber, wherein the industrial gas comprises an amount equal to the time-averaged original composition _CO2 , SOx, NOx, heavy metals, non- _CO2 acid gases, and/or fly ash; for inlet of absorption solution, where absorption solution includes alkaline solution, particulate material, or both in the absorption slurry; for discharge an outlet for a gas characterized by being depleted in _CO and at least one of SOx, NOx, heavy metals, non- _CO acid gases and/or fly ash relative to said original composition of said industrial gas, wherein said Said outlet is operatively connected to said absorber; an outlet for absorbing solution that has been contacted with industrial gas is operably connected to the absorber; and a processing station is operatively connected to the outlet, wherein the processing station is configured to obtain At least one of the following salable products: building materials including a _CO2 sequestration component, desalinated water, drinking water, a slurry including a _CO2 sequestration component, or a solution including a _CO2 sequestration component, wherein the spray tower A stream, liquid droplets, or combination thereof configured to produce an absorbing solution in an industrial gas such that at least 10 wt% of the carbon dioxide in the industrial gas is transferred to the absorbing solution, further wherein the spray tower is configured to operate at Operates at a liquid flow rate to gas flow rate ratio (L/G ratio) of 1000 actual cubic feet. In some embodiments, the present invention provides an apparatus comprising an absorber comprising at least one of a spray tower, packing material, packed bed, tray, row, or microporous membrane; operably connected to Inlets to absorbers for industrial gases, where industrial gases include _CO2 , SOx, NOx, heavy metals, non- _CO2 acid gases, and/or fly ash in quantities equal to the time-averaged original composition; inlets for absorption solutions, where Absorbing solution comprising alkaline solution, particulate material or both in the absorbing slurry; outlet for venting gas characterized by being depleted in _CO2 and SOx relative to said original composition of said industrial gas, At least one of NOx, heavy metals, non- _CO2 acid gases and/or fly ash, wherein said outlet is operatively connected to said absorber; an absorption solution for exposed industrial gases operatively connected to absorber and a processing station operatively connected to the outlet, wherein the processing station is configured to obtain at least one of the following salable products: building materials including _CO2 sequestration components, desalinated water, drinking water, including CO ₂ a slurry of a sequestration component or a solution comprising a _CO2 sequestration component, wherein the absorber is configured to produce a stream, droplets, or combination thereof of the absorbing solution in an industrial gas such that at least 10 wt% of the carbon dioxide in the industrial gas is absorbed Transfer to absorption solution, and further wherein the absorber is configured to operate at a liquid flow rate to gas flow rate ratio (L/G ratio) of 50-5,000 gallons per minute per 1000 actual cubic feet. In some embodiments, the present invention provides an apparatus comprising an absorber comprising at least one of a spray tower, packing material, packed bed, tray, row, or microporous membrane; operably connected to Inlets to absorbers for industrial gases, where industrial gases include _CO2 , SOx, NOx, heavy metals, non- _CO2 acid gases, and/or fly ash in quantities equal to the time-averaged original composition; inlets for absorption solutions, where The absorption solution includes an alkaline solution, particulate material, or both in the absorption slurry, wherein the alkaline solution includes saline, clear liquid, or any combination thereof; an outlet for exhausting gases characterized by their relative said raw composition of said industrial gas is depleted in _CO and at least one of SOx, NOx, heavy metals, non- _CO acid gases, and/or fly ash, wherein said outlet is operatively connected to said absorber; an outlet operatively connected to the absorber for the absorption solution that has been contacted with the industrial gas; and a processing station operably connected to the outlet, wherein the processing station is configured to obtain at least one of the following salable products: comprising _CO A construction material of a sequestration component, desalinated water, drinking water, a slurry comprising a _CO2 sequestration component or a solution comprising a _CO2 sequestration component, wherein the absorber is configured to produce a stream of the absorbing solution in an industrial gas, The droplets or combination thereof cause at least 10 wt% of the carbon dioxide in the industrial gas to be transferred to the absorbing solution. In some embodiments, the present invention provides an apparatus comprising an absorber comprising at least one of a spray tower, packing material, packed bed, tray, row, or microporous membrane; operably connected to Inlets to absorbers for industrial gases, where industrial gases include _CO2 , SOx, NOx, heavy metals, non- _CO2 acid gases, and/or fly ash in quantities equal to the time-averaged original composition; inlets for absorption solutions, where an absorption solution comprising an alkaline solution, particulate material, or both in an absorption slurry, wherein the alkaline solution comprises brine; an outlet for exhausting gases characterized by their original Compositionally lean in _CO and at least one of SOx, NOx, heavy metals, non- _CO acid gases, and/or fly ash, wherein the outlet is operatively connected to the absorber; an outlet for the absorption solution that has been contacted with the industrial gas; and a processing station operably connected to the outlet, wherein the processing station is configured to obtain a salable product, wherein the absorber is configured to generate a stream of the absorption solution in the industrial gas, The droplets or combination thereof cause at least 10 wt% of the carbon dioxide in the industrial gas to be transferred to the absorbing solution. In some embodiments, the inlet for industrial gas is configured to accept industrial waste gas, combustion flue gas, cement kiln flue gas, compressed carbon dioxide, supercritical carbon dioxide, or any combination thereof. In some embodiments, the absorbing solution is exposed to the industrial gas such that the absorbing solution exists as liquid droplets, rivulets, liquid columns, jet sprays, liquid films, neutrally buoyant clouds of solution, or any combination thereof. In some embodiments, the device further comprises atomization components in the contacting chamber, including: pressure atomizers (orifices), rotary atomizers, air-assisted atomizers, air-jet atomizers, ultrasonic atomizers , an inkjet atomizer, a MEMS atomizer, an electrostatic atomizer, a two-fluid atomizer, a discharge nozzle, or any combination thereof. In some embodiments, the brine in the absorption solution includes seawater, alkaline brine, cation-rich brine, synthetic brine, industrial wastewater, industrial waste brine, or any combination thereof. In some embodiments, the apparatus further includes a recirculation system. In some embodiments, the recirculation system includes piping and pumps to transfer the industrial gas contacted absorption solution from the outlet for the exposed industrial gas absorption solution, the processing station, or both to the inlet for the absorption solution, the mist components or any combination thereof. In some embodiments, the recirculation system includes piping and pumps to transfer the CO2 _- reduced gas from an outlet for vent gas to an inlet for industrial gas, a bubble column, a spray vessel, or any combination thereof.

In some embodiments, the present invention provides an emission control system operably connected to a power plant that produces energy and industrial exhaust gas comprising carbon dioxide, wherein the emission control system is configured to absorb at least 50% of the carbon dioxide from the exhaust gas and is Configured to use less than 30% of the energy produced by the power plant. In some embodiments, the present invention provides an emission control system operably connected to a power plant, wherein the power plant generates energy and an industrial waste gas comprising sulfur oxides, wherein the emission control system is configured to absorb at least 90% of the sulfur from the waste gas oxide and is configured to use less than 30% of the energy produced by the power plant. In some embodiments, the present invention provides an emission control system operably connected to a power plant, wherein the power plant produces energy and industrial exhaust gases comprising carbon dioxide and sulfur oxides, wherein the emission control system is configured to absorb at least 50% of the emissions from the exhaust gases carbon dioxide and at least 80 percent sulfur oxides, and wherein the emission control system is further configured to use less than 30 percent of the energy produced by the power plant. In some embodiments, the emission control system is configured to accept at least 10% of the industrial exhaust from the power plant. In some embodiments, the emission control system is configured to accept an alkaline solution from an electrochemical system configured to generate a caustic solution. In some embodiments, an electrochemical system includes an anode, a cathode, and at least one ion selective membrane between the anode and the cathode. In some embodiments, the electrochemical system is configured to operate at a voltage of 2.8 V or less applied across the anode and cathode. In some embodiments, the emission control system is configured to accept a pH adjusting agent, wherein the pH adjusting agent comprises industrial waste, naturally occurring pH adjusting agents, produced pH adjusting agents, or any combination thereof. In some embodiments, the emission control system is configured to operate at a liquid flow rate to gas flow rate ratio (L/G) of 5-5,000 gallons per minute per 1000 actual cubic feet per minute. In some embodiments, the system is configured to operate at a liquid flow rate to gas flow rate ratio (L/G) of 100-500 gallons per minute per 1000 actual cubic feet per minute.

Provided herein is a system comprising a precipitation reactor for producing an effluent comprising precipitation products including carbonates, bicarbonates, or combinations thereof, the precipitation reactor being operatively connected to a Liquid-solid separation device for precipitation products from precipitation reactor effluent.

In one version of the liquid-solid separation device, the liquid-solid separation device includes baffles positioned such that in operation the baffles deflect the precipitation reactor effluent so that the precipitated product Descends to the lower region of the liquid-solid separation device and the supernatant rises and leaves the liquid-solid separation device. In another version of the liquid-solid device, the liquid-solid separation device includes a helical channel configured to direct the effluent from the precipitation reactor to flow in the helical channel such that the concentration of the precipitated product is based on size and mass And a supernatant was produced. The liquid-solid separation device of the system described herein includes a precipitated product collector capable of collecting 50%-100%, 75%-100%, or 95%-100% of the precipitated product from the settling table. In addition, the liquid-solid separation device is capable of processing 100L/min-20,000L/min, 5000L/min-20,000L/min, or 10,000L/min-20,000L/min of the effluent from the settling table.

The precipitation reactors of the systems described herein may include a feed reactor and a precipitation table. Addition reactors are capable of removing _CO2 from industrial waste gas streams. Additionally, the feed reactor may be capable of removing one or more of SOx, NOx, heavy metals, particulate matter, VOCs, or combinations thereof from the industrial waste gas stream (steam). The feed reactor includes a flat jet nozzle connected to a water source, wherein the flat jet nozzle is adapted to form a flat jet stream such that a gaseous waste stream including _CO2 is contacted with water from the water source. Gaseous waste streams including _CO2 are waste streams from industrial facilities burning carbon-based fuels, calcined materials, or combinations thereof. The water source The water provided may contain alkaline earth metal ions; in this case the water source may be selected from fresh brackish water, sea water and brine. The settling station is operatively connected to a source of pH-enhancing agent. pH-raising agents may include ash, oxides, hydroxides or carbonates. The precipitation station is suitable for producing precipitation products including carbonates, bicarbonates or combinations thereof.

The systems described herein can further include electrochemical cells. The electrochemical cell can be configured to remove protons from a feeding station, a settling station, or a feeding and settling station.

Also provided is an integrated system comprising a power plant burning a carbon-based fuel to produce an exhaust gas stream comprising carbon dioxide operatively connected to an exhaust gas processing system. The exhaust gas processing system includes a precipitation reactor for producing an effluent comprising precipitation products, including carbonates, bicarbonates, or combinations thereof, operably connected to a precipitation reactor for concentrating the precipitation products from the precipitation reactor effluent Liquid-solid separation device. In one version of the liquid-solid separation device, the liquid-solid separation device includes baffles positioned such that in operation the baffles deflect the precipitation reactor effluent so that the precipitated product Descends to the lower region of the liquid-solid separation device and the supernatant rises and leaves the liquid-solid separation device. In another version of the liquid-solid separation device, the liquid-solid separation device includes a helical channel configured to direct the effluent from the precipitation reactor to flow in the helical channel such that the precipitation product is separated based on size and mass. Concentrate and yield a supernatant. The exhaust gas stream further includes SOx, NOx, heavy metals, VOCs, particulate matter, or combinations thereof.

Also provided is a method comprising diverting part or all of a gaseous waste stream comprising carbon dioxide from an industrial facility to a precipitation facility for producing an effluent comprising precipitation products including carbonates, bicarbonates, or combinations thereof a reactor; and concentrating the precipitation product from the precipitation reactor effluent in a liquid-solid separation device. In one version of the liquid-solid separation device, the effluent is deflected against baffles in the liquid-solid separation device so that the precipitated product descends into the lower region of the liquid-solid separation device and the supernatant rises and exits the liquid-solid separation device device. In another version of the liquid-solid separation device, the effluent is made to flow in a helical channel, allowing concentration of the precipitated product and generation of a supernatant based on size and mass.

The method of sequestering carbon dioxide may be carried out using any system of any one of the preceding claims.

Description of drawings

The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description and accompanying drawings which set forth illustrative embodiments in which the principles of the invention are utilized, in which:

Figure 1 provides a system of the present invention comprising a processor configured to process various gases including carbon dioxide.

Figure 2 provides a system of the present invention comprising a processor and a processing system, wherein the processing system is configured to process a composition from the processor.

Figure 3 provides a system of the present invention comprising a processor and an optional processing system, wherein the processor comprises a contactor and a reactor.

Figure 4 provides a system of the present invention comprising a processor and a treatment system, wherein the supernatant from the treatment system can optionally be recycled to the processor.

Figure 5 provides a system of the present invention comprising a processor, a treatment system, and an electrochemical system, wherein the supernatant from the treatment system can optionally be recycled to the processor, the electrochemical system, or a combination thereof.

Figure 6A provides a schematic diagram of a _CO2 sequestration method according to one embodiment of the present invention.

Figure 6B provides a schematic diagram of a _CO2 storage system according to one embodiment of the present invention.

Figure 6C provides a schematic diagram of an embodiment of this system.

Figure 7 provides a schematic diagram of a _CO2 storage system according to another embodiment of the present invention.

Figure 8 provides a schematic diagram of one embodiment of a low pressure apparatus for the electrochemical production of hydroxides.

Figure 9 provides a schematic diagram of another embodiment of a low pressure apparatus for the electrochemical production of hydroxides.

Figure 10 provides a schematic diagram of another embodiment of a low pressure apparatus for the electrochemical production of hydroxides.

Figure 11 is a schematic diagram of an embodiment of an apparatus for contacting solid material, liquid and gas with a column configuration.

Figure 12 is a schematic illustration of a method for contacting solid materials, liquids and gases.

Figure 13 is a schematic illustration of an embodiment of a device for contacting solid material, liquid and gas with a horizontal configuration as viewed longitudinally in cross section.

Figure 14 is a schematic illustration of an embodiment of a device for contacting solid materials, liquids and gases having a horizontal configuration as viewed in cross-sectional endpoints.

Figure 15 is a schematic illustration of an embodiment of the device.

Figure 16 is a schematic diagram of an embodiment of the entire device.

Figure 17 is a schematic diagram showing a portion of an embodiment of an apparatus for row design.

Figure 18 is a schematic diagram of an embodiment of the device showing a possible arrangement of nebulizers.

Figure 19 is a schematic diagram of an embodiment of the device showing a possible arrangement of nebulizers.

Figure 20 is a schematic illustration of a row configuration that may be used with some embodiments of the devices and systems.

Figure 21A shows a side view of an embodiment of the invention in which droplets and gas follow a long path around a chamber with the gas inlet at the top of the chamber.

Figure 21B shows a top-down cross-sectional view of an embodiment of the invention in which droplets and gas follow a long path around a chamber with the gas inlet at the top of the chamber.

Figure 22A shows a side view of an embodiment of the invention in which droplets and gas follow a long path around a chamber with the gas inlet at the bottom of the chamber.

Figure 22B shows a top-down cross-sectional view of an embodiment of the invention in which the liquid droplets and gas follow a long path around the chamber with the gas inlet at the bottom of the chamber.

Figure 23 provides a schematic diagram of a gas-liquid or gas-liquid-solid contactor.

FIG. 24 provides a schematic diagram of another view of the gas-liquid or gas-liquid-solid contactor of FIG. 23 .

Figure 25 provides a simplified diagram of the online monitor.

Figure 26 is a schematic diagram of an embodiment of a device showing longitudinally and horizontally oriented segments.

Figure 27 is a schematic diagram of an embodiment of a device showing longitudinally and horizontally oriented segments.

Figure 28 is a schematic diagram of an embodiment of a device showing longitudinal and horizontal oriented sections with countercurrent solution circulation with respect to gas flow in the horizontally oriented sections suing pumps.

Figure 29 is a schematic illustration of an embodiment of a device and system, where the system is a series of devices.

Figure 30 is a schematic diagram of an embodiment of a system showing an array of devices.

Figure 31 is a schematic diagram of an embodiment of a system showing an array of devices.

Figure 32 is a schematic diagram of an embodiment of the system.

Figure 33 provides a schematic diagram of a power plant integrating a _CO2 storage system according to an embodiment of the present invention.

Figure 34 provides a schematic diagram of a Portland cement plant.

Figure 35 provides a schematic diagram of a cement plant co-located with a settling unit according to one embodiment of the present invention.

Figure 36 provides a schematic diagram of a cement plant that does not require mined limestone raw material according to one embodiment of the present invention.

Figure 37 provides a schematic diagram of a system according to one embodiment of the invention.

Figures 38, 39 and 40 provide schematic illustrations of a system according to one embodiment of the invention.

Figures 41 and 42 provide photographs of precipitates of the present invention.

Figure 43 provides a photograph of the amorphous precipitate of the present invention.

Figure 44 provides graphical results from the _CO2 absorption experiments reported in the Examples section below.

Figure 45 shows an embodiment of the invention in which droplet formation and contact of the droplet with the gas of interest are performed in separate chambers.

Figure 46 shows an embodiment in which droplet formation and gas contact are performed in a chamber designed to separate the coalescing droplets from the droplet-forming liquid.

Figure 47 is a schematic diagram showing an embodiment of a device using a defoaming cone and a nebulizer.

Detailed description

Systems, devices, and methods related to efficiently contacting solid materials, liquids, and gases are described herein. Embodiments presented herein represent methods and apparatus for introducing gases into liquids or slurries or both. In some embodiments where a slurry is introduced, the slurry includes liquid and solid material components such that the solid material is present throughout the contact of the liquid with the gas. Introducing means dissolving and/or absorbing a gas into a liquid or adsorbing and/or chemisorbing a gas onto the surface of a liquid. The introduction of gas into the liquid is achieved by optimizing the contact conditions. Conditions varied and optimized in embodiments herein include: solution chemistry of the liquid; surface area to volume ratio of the liquid; flow rate ratio of the liquid or slurry and gas (L/G); and contact time between the liquid and gas. Introducing a gas into a liquid is desirable for a number of reasons, some of which are contemplated in embodiments herein, including but not limited to removing components of the gas stream (e.g., scrubbing flue gas) and Effective in precipitating material in reactions between liquids (e.g. formation of fine solid particles).

The methods, devices and systems of the invention may utilize gas-liquid or gas-liquid-solid technology as further described herein. Contacting methods may be utilized wherein a liquid or slurry (ie, absorption solution) is introduced into the gas, wherein the liquid and/or slurry is introduced in the form of droplets, a stream, or a combination thereof. Contacting methods may be utilized in which a gas is introduced into a liquid or slurry (ie, an absorption solution) in which the gas generates bubbles or foam. In either case, parameters can be optimized to introduce carbon dioxide and at least one of SOx, NOx, heavy metals, non- _CO2 acid gases, or fly ash into the liquid or slurry making up the absorption solution. To facilitate such incorporation, structural features such as packing materials, packed beds, trays, rows or membranes, including microporous membranes, may be used in the methods, devices and systems of the invention. Once the desired components of the gas have been introduced into the absorbing solution by contact between the solution and the gas, the contacted solution may be treated by suitable means that do not allow the components removed from the gas to be released into the Earth's atmosphere middle. Alternatively, the contacted solution may be subjected to precipitation conditions such that a solid precipitate is formed, and such precipitate and effluent liquid may be further processed for recovery of salable products (e.g. potable water, building materials including _CO2 -storage components ).

The method, apparatus and system of the present invention can be adapted for contacting gas and absorbing solution in an emission control system operably connected to a power plant such that flue gas (i.e. industrial waste gas) from the power plant contains carbon dioxide, SOx, NOx , heavy metals, non-carbon dioxide acid gases and sometimes fly ash. It is desirable to remove carbon dioxide and at least one of SOx, NOx, heavy metals, non-carbon dioxide acid gases, and sometimes fly ash while using very little, such as 30%, of the energy produced by a power plant, to power the emission control system. Emission control systems include actions and components such as, but not limited to, pumping and recirculating absorption solution, regenerating or recharging absorption solution, circulating flue gas, removing particulate matter including fly ash and sediment, and treating carbon dioxide and SOx Any liquid, solid or slurry of at least one of , NOx, heavy metals, non-carbon dioxide acid gases and sometimes fly ash (removed from flue gas). The methods, apparatus and systems of the present invention may replace other emission control systems or may be used with existing systems that power plants may have in place, however, in some embodiments it is not necessary to have separate _CO2 and SOx emissions Control System.

Some embodiments utilize simultaneous pulverization, particle size reduction, and mixing of the solid component of the slurry and the liquid component of the slurry. Some embodiments include contacting with a gas while mixing and reducing the size of the solid particulate matter. Comminution, or particle size reduction, can be used to improve the reactivity of the solid components of the slurry by increasing the surface area of solids that may participate in the reaction and by exposing new solid material with each pass of the slurry through the comminution step. Comminution may be accomplished using any suitable device for reducing the size of the solid particles, including but not limited to jet mills, screw conveyors, high shear mixers, wet mills, attritors, colloid mills, or any combination thereof . In some embodiments, pulverization occurs prior to the first contact of the slurry with the gas. In some embodiments, comminution occurs after the slurry is first contacted with the gas during recirculation. In some embodiments, comminution is performed in a pipeline with a screw conveyor while the slurry is also in contact with a gas before reaching the contact chamber.

Some embodiments utilize high-efficiency gas-liquid contacting methods or devices. High-efficiency gas-liquid contact methods or devices have additional advantages of optimized contact parameters, such as: higher surface area, whereby gas introduction into liquid can be carried out; solution chemistry is conducive to the kinetics of gas introduction into liquid; while gas is introduced into liquid, Sufficient residence time is provided by slowing fluid flow or increasing the path length of liquid and gas travel.

One of the uses of efficient gas-liquid contacting methods and apparatus is to optimize precipitation reactions. Changes in the solution chemistry of a liquid in a gas-liquid contactor affect the ability of the liquid to introduce gas. In some embodiments, the chemistry of the liquid (eg, absorption solution, contact mixture) is influenced to introduce the gas more efficiently. In some embodiments, the pH of the liquid (eg, absorption solution, contacting mixture) allows simultaneous removal of _CO2 and _SO2 and/or SOx from the gas. In some embodiments, the chemistry of the liquid (eg, absorption solution, contacting mixture) does not require a separate (ie, distinct from the method or step of removing CO ₂ ) SO ₂ and/or SOx removal steps. In some embodiments, the pH of the liquid is between pH 4 and pH 13.5. In some embodiments, the pH of the liquid is between pH 4 and pH 11. In some embodiments, the pH of the liquid is between pH 5 and pH 10. In some embodiments, the pH of the liquid is between pH 5.5 and pH 9.5. In some embodiments, the pH of the liquid is affected by reagents added to the solution from which the droplets were made. Agents that alter the pH of a liquid include, but are not limited to, naturally occurring pH raising agents, microorganisms and fungi, synthetic chemical pH raising agents, recycled man-made waste streams, and alkaline solutions produced by electrochemical means.

Before the present invention is described in greater detail, it is to be understood that this invention is not limited to particular embodiments described herein, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

Where a range of values is provided, it is understood that each intervening value between the upper and lower limits of the stated range, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, and within the stated range Any other stated or intervening values are encompassed by the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.

Certain ranges are given herein with the term "about" preceding the numerical value. The term "about" is used herein to provide literal support for the exact number that it precedes as well as a number near or approximately the number that the term precedes. In determining whether a number is around or approximate to a specifically stated number, an adjacent or approximately unrecited number may be a number which, in the range in which it is expressed, provides a substantial equivalent of the specifically stated number things.

All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference. In addition, each cited publication, patent, or patent application is incorporated herein by reference to disclose and describe the subject matter to which the publication is cited. Citation of any publication is for its disclosure prior to the filing date and should not be construed as an admission that the inventions described herein are not entitled to such publication by virtue of prior invention. Further, the dates of publication provided may be different from the actual publication dates, which may need to be independently confirmed.

Note that as used herein, and in the appended claims, the singular forms "a", "an" and "the" include plural recited items unless the context clearly dictates otherwise. It is further noted that the claims may be drafted to exclude any optional elements. Accordingly, this statement is intended to be used as a prior basis for the use of such exclusive terminology, such as "merely" etc., or for the use of a "negative" limitation with respect to the recitation of claim elements.

It will be apparent to those skilled in the art upon reading this disclosure that each individual embodiment described and illustrated herein has discrete components and features that can be readily separated from the features of any other multiple embodiments and incorporated without departing from the scope or spirit of the invention. Any described method may be performed in the order of events described or in any other logically feasible order. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, representative illustrative methods and materials are now described.

The methods and systems of the present invention may utilize a process summarized by the following chemical reactions:

Combustion of carbonaceous fuel sources in the liquid, gaseous or solid phase forms gaseous carbon dioxide:

C+O ₂ (g)→CO ₂ (g)

(2) The contact between the carbon dioxide source and the water source makes carbon dioxide into a solvate to obtain an aqueous solution of carbon dioxide:

CO ₂ (g) CO ₂ (aq)

(3) The formation of carbon dioxide dissolved in water and the equilibrium of carbonic acid aqueous solution:

CO ₂ (aq)+H ₂ O H ₂ CO ₃ (aq)

(4) Carbonic acid is a weak acid that dissociates in two steps, where the equilibrium balance is determined in part by the pH of the solution, where typically pHs below 8-9 favor bicarbonate formation and pHs above 9-10 favor conducive to the formation of carbonates. In a second step, a hydroxide source can be added to increase the alkalinity:

H ₂ CO ₃ +2H ₂ O H ₃ O ⁺ (aq)+HCO ₃ ^- (aq)

HCO ₃ ^- (aq)+OH ^- (aq) H ₂ O+CO ₃ ^2- (aq)

The reaction of an elemental metal cation from group IIA with a carbonate anion forms a metal carbonate precipitate:

mX(aq)+nCO ₃ ^2- X _m (CO ₃ ) _n (s)

wherein X is any element or combination of elements capable of chemically binding to one or more carbonate groups, and m and n are stoichiometric positive integers.

In further describing the subject invention, a _CO2 sequestration method according to an embodiment of the present invention is first described in detail. Systems that can be used to practice various embodiments of the methods of the invention are then described, followed by compositions that can be produced using the methods and systems of the invention.

Methods of _CO2 storage

In some embodiments, the present invention provides methods for _CO2 sequestration. In such an embodiment, an amount of _CO2 may be removed or sequestered from the environment, such as the Earth's atmosphere or a gaseous waste stream produced by an industrial facility, so that some or all of the _CO2 is no longer present in it. CO removal ₂ environment. For example, _CO2 sequestration removes _CO2 from fuel combustion or prevents _CO2 from fuel combustion from being released into the atmosphere. In some embodiments, the form of _CO2 that is sequestered is a form that includes carbonate, bicarbonate, or a combination of carbonate and bicarbonate. Such compositions may include solutions, slurries including precipitation materials, or precipitation materials alone or in combination with one or more additional materials used in or as building materials. For example, compositions of the present invention may include precipitation materials that include carbonate compounds (eg, amorphous calcium carbonate, calcite, aragonite, vaterite, etc.). Thus, in some embodiments, _CO2 sequestration according to aspects of the invention results in a composition (e.g., a precipitation material comprising carbonate compounds) wherein at least a portion of the carbon in the composition is derived from fuels used by humans (e.g., Fossil fuels). The CO ₂ -storage method according to the invention produces a storage-stable product from an amount of CO ₂ such that the CO ₂ in which the product was generated is then sequestered in the product. A storage-stable CO ₂ -storage product is a storage-stable composition that introduces an amount of CO ₂ into a storage-stable form, such as aboveground, underwater, or underground, such that the CO ₂ is no longer available in the atmosphere gaseous form or _CO2 is no longer available to the gas in the atmosphere. Thus, the sequestration of CO ₂ according to the method of the invention prevents CO ₂ gas from entering the atmosphere and allows long-term storage of CO ₂ in such a way that CO ₂ does not become part of the atmosphere.

Embodiments of the methods of the present invention include small-, neutral- or negative-carbon footprint methods. Carbon neutral methods of the present invention include methods with negligible or no carbon footprint. In a negative-carbon footprint approach, the weight of _CO2 that is stored (e.g. by converting _CO2 to carbonate) through the implementation of the process is greater than that produced by the implementation of the process (e.g. by electricity production, alkali production, etc.) weight of _CO2 . In some cases, the _CO2 stored by the practical method exceeds the _CO2 produced by the practical method by 1 to 100%, such as 5 to 100%, including 10 to 95%, 10 to 90%, 10 to 80%, 10 to 70%, 10 to 60%, 10 to 50%, 10 to 40%, 10 to 30%, 10 to 20%, 20 to 95%, 20 to 90%, 20 to 80%, 20 to 70%, 20 to 60%, 20 to 50%, 20 to 40%, 20 to 30%, 30 to 95%, 30 to 90%, 30 to 80%, 30 to 70%, 30 to 60%, 30 to 50%, 30 to 40%, 40 to 95%, 40 to 90%, 40 to 80%, 40 to 70%, 40 to 60%, 40 to 50%, 50 to 95%, 50 to 90%, 50 to 80%, 50 to 70%, 50 to 60%, 60 to 95%, 60 to 90%, 60 to 80%, 60 to 70%, 70 to 95%, 70 to 90%, 70 to 80%, 80 to 95%, 80 to 90%, and 90 to 95%. In some cases, the weight of _CO stored by the practical method exceeds the weight of _{the CO} generated by the practical method by 5% or more, by 10% or more, by 15% or more, by 20% % or more, up to 30% or more, up to 40% or more, up to 50% or more, up to 60% or more, up to 70% or more, up to 80% or more, up to 90% or above or up to 95% or more.

Referring to the system of FIG. 1 , the present invention provides an aqueous-based method for processing a carbon dioxide source (130) and producing a composition comprising carbonates, bicarbonates, or carbonates and bicarbonates, wherein the carbon dioxide source comprises one or more other components besides carbon dioxide. In such an embodiment, an industrial source of carbon dioxide can be sourced, a proton-removing agent source (140) can be sourced, and each can be provided to processor 110 to be processed (i.e., subjected to suitable conditions to produce salts, bicarbonates, or combinations of carbonates and bicarbonates). In some embodiments, processing an industrial source of carbon dioxide includes contacting a proton-removing agent source in a contactor (such as, but not limited to, a gas-liquid contactor or a gas-liquid-solid contactor) to produce carbon dioxide from an initial aqueous solution or slurry- The composition to be fed, which may be a solution or a slurry. In some embodiments, compositions comprising carbonates, bicarbonates, or carbonates and bicarbonates can be produced in a contactor from a carbon dioxide-fed solution or slurry. In some embodiments, the carbon dioxide-fed solution or slurry can be provided to a reactor where a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate can be produced. In some embodiments, the compositions are produced in contactors and reactors. For example, in some embodiments, the contactor can produce an initial composition comprising bicarbonate and the reactor can produce a composition comprising carbonate, bicarbonate, or both carbonate and bicarbonate from the initial composition. In some embodiments, the methods of the invention may further comprise sourcing a source of divalent cations, such as a source of alkaline earth metals (eg, Ca2+, Mg2+). In such embodiments, the source of divalent cations may be provided to the proton-removing agent source or directly to the processor. Compositions comprising carbonates, bicarbonates, or carbonates and bicarbonates may include separable Precipitating material (eg, CaCO ₃ , MgCO ₃ , or combinations thereof). Whether or not the processor-derived composition includes isolatable precipitation material, the processor-derived composition can be used directly (optionally with minimal post-processing) in the manufacture of building materials. In some embodiments, compositions comprising carbonates, bicarbonates, or carbonates and bicarbonates directly from a processor (optionally with minimal post-processing) can be injected into subterranean locations such as the U.S. Described in Provisional Patent Application 61/232,401 (filed August 7, 2009, which application is incorporated herein by reference in its entirety).

Referring to the systems of Figures 2-5, the present invention provides an aqueous-based method for processing a carbon dioxide source (130) and producing a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate, wherein the carbon dioxide source comprises a or more additional components other than carbon dioxide. In addition to producing compositions as described with reference to Figure 1, the present invention further provides methods of treating compositions comprising carbonates, bicarbonates, or carbonates and bicarbonates. Thus, in some embodiments, the present invention provides an aqueous-based method for treating a carbon dioxide source (130) to produce a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate and treating the resulting composition. method. Whether or not the composition produced by the processor of the invention includes separable precipitation material, the composition can be provided directly to the treatment system of the invention for processing (eg, concentration, filtration, etc.). In some embodiments, the composition may be provided directly to the treatment system from the contactor, reactor, or clarifier of the processor. For example, a processor-produced composition that does not contain separable precipitation material can be provided directly to a processing system to concentrate the composition and produce a supernatant. In another non-limiting example, a processor-generated composition comprising separable precipitation material can be provided directly to a processing system for liquid-solid separation. Processor-produced compositions may be provided to any of a number of treatment system subsystems, including but not limited to dewatering systems, filtration systems, or dewatering systems in combination with filtration systems, wherein the treatment system or its subsystems, The supernatant is separated from the composition to produce a concentrated composition (eg, the concentrated composition is more concentrated with respect to carbonate, bicarbonate, or carbonate and carbonate).

Referring to the system of FIG. 3 , in some embodiments, the present invention provides a method for feeding a solution with _CO from an industrial waste gas stream to produce a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate . In such an embodiment, the pH of the solution may be 6.5-14.0 prior to feeding the solution with _CO2 . In some embodiments, the pH of the solution may be at least 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5 prior to feeding the solution with _CO or 14.0. The pH of the solution may be increased using any suitable method, including, but not limited to, the use of proton-removing agents and electrochemical methods for effecting proton removal. In some embodiments, a proton-removing agent may be used to increase the pH of the solution prior to feeding the solution with CO ₂ . Such proton-removing agents include, but are not limited to, hydroxides (eg NaOH, KOH) and carbonates (eg _Na2CO3 , _K2CO3 ). In some embodiments, sodium hydroxide is used to increase the pH of the solution. Thus, in some embodiments, the present invention provides methods for feeding an alkaline solution (e.g., pH greater than 7.0) with _CO from an industrial waste gas stream to produce Composition of hydrogen salts.

In some embodiments, the composition produced by feeding an alkaline solution with _CO from an industrial waste source (i.e., a solution comprising carbonate, bicarbonate, or carbonate and bicarbonate) can be a slurry or substantially A clear solution (ie, substantially free of precipitated material, such as at least 95% or more free), depending on the cations available in the solution when the solution is fed with _CO2 . As described herein, when the solution is fed with _CO2 , the solution may, in some embodiments, include divalent cations such as Ca2+, Mg2+ or combinations thereof. In such embodiments, the resulting composition may include carbonate, bicarbonate, or both carbonate and bicarbonate salts of divalent cations forming a slurry (eg, precipitation material). Such a slurry, for example, may include CaCO ₃ , MgCO ₃ or combinations thereof. In some embodiments, the solution may include insufficient divalent cations to form a slurry including carbonates, bicarbonates, or carbonates and bicarbonates of divalent cations when the solution is fed with CO ₂ . In such embodiments, _when the solution is fed with CO, the resulting composition may include carbonates, carbonates, Bicarbonate or carbonate and bicarbonate. In some embodiments, for example, monovalent cations such as Na+, K+ or combinations thereof (optionally by addition of NaOH and/or KOH) may be present in a substantially clear solution when the solution is fed with _CO2 . Compositions resulting from feeding such solutions with _CO2 may include, for example, carbonates, bicarbonates, or both carbonates and bicarbonates of monovalent cations.

Thus, in some embodiments, the present invention provides for feeding an alkaline solution (e.g., pH greater than 7.0) to _CO from an industrial waste gas stream to produce a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate The method, wherein the composition is substantially clear (ie, substantially free of precipitated material, such as at least 95% or more free). The substantially clear composition can then be contacted with a source of divalent cations (e.g., Ca2+, Mg2+, or combinations thereof) to produce a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate of divalent cations, which form slurry. As above, such a slurry may include CaCO ₃ , MgCO ₃ or combinations thereof, which may be processed as described herein. In a non-limiting example, an alkaline solution comprising NaOH (such as NaOH dissolved in fresh water lacking significant divalent cations) can be contacted with _CO from an industrial waste gas stream in a gas-liquid contactor to produce , bicarbonate, or a combination of carbonate and bicarbonate, wherein the composition is substantially clear due to the absence of precipitating material which in turn is due to the absence of significant divalent cations. Depending on the amount of _CO2 (and make-up NaOH, if any) added, the substantially clear composition may include NaOH, _NaHCO3 and/or _Na2CO3 . The substantially clear composition can then be contacted with a source of divalent cations (e.g., Ca2+, Mg2+, Sr2+, etc.) in a reactor outside the gas-liquid contactor to produce carbonate, bicarbonate, or carbon containing divalent cations. A combination of acid salts and bicarbonates (eg, precipitation material), which forms a slurry. Thus, the composition may include _CaCO3 and/or _MgCO3 , and the composition may be processed as described herein. For example, the composition can undergo liquid-solid separation and the solids can be made into cement, secondary binding material, fine aggregate, mortar, coarse aggregate, concrete, pozzolan cement, or combinations thereof.

Referring to the systems of Figures 4 and 5, the present invention also provides an aqueous based method of processing a carbon dioxide source (130) and producing a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate, wherein the carbon dioxide source comprises One or more additional components other than carbon dioxide, and wherein at least a portion of the treatment system supernatant is recycled. For example, in some embodiments, the present invention provides for treating a waste gas stream comprising CO _and , optionally, SOx, NOx, and/or Hg in a processor to produce a treated waste gas stream (e.g., a pure gas stream suitable for for release into the environment), including carbonates, bicarbonates, or combinations of carbonates and bicarbonates, and effluents in which at least a portion of the effluents are recycled to the processor. As shown in Figures 4 and 5, the supernatant from the treatment system (which may include a dewatering system and a filtration system) can be recycled in various ways. Thus, in some embodiments, at least a portion of the supernatant from a dehydration system, a filtration system, or a combination of a dehydration system and a filtration system can be used to treat carbon dioxide. The supernatant can be provided to a carbon dioxide-treatment system processor. In such embodiments, the supernatant may be provided to a contactor (e.g., a gas-liquid contactor, a gas-liquid-solid contactor), a reactor, a combination of a contactor and a reactor, or used to treat carbon dioxide any other unit or combination of units. Additionally, in some embodiments, at least a portion of the supernatant from the treatment system can be provided to the wash system. In such embodiments, the supernatant may be used to wash compositions of the invention (eg, precipitation materials comprising CaCO ₃ , MgCO ₃ , or combinations thereof). For example, the supernatant can be used to wash chloride from the carbonate-based precipitation material. Referring to Figure 5, at least a portion of the treatment system supernatant may be provided to the electrochemical system. Thus, the treatment system supernatant can be used to generate proton-removing agents or to perform proton removal for the treatment of carbon dioxide. In some embodiments, at least a portion of the supernatant from the treatment system can be provided to a different system or process. For example, at least a portion of the treatment system supernatant may be provided to a desalination unit or desalination process such that the treatment system supernatant, which after being used to treat carbon dioxide, is generally more concentrated than other available feeds (e.g., seawater, brine, etc.) Softened (ie, lower concentrations of Ca2+ and/or Mg2+), can be desalinated for drinking water.

Recirculation of the supernatant of the treatment system is beneficial because the recirculation provides efficient use of available resources; minimal disturbance of the surrounding environment; and reduced energy requirements that provide the benefits of the systems and methods of the present invention. Lower carbon footprint. When the carbon dioxide-processing system of the present invention is operably connected to an industrial facility (e.g., a fossil fuel-fired power plant such as a coal-fired power plant) and uses electricity generated at the industrial facility, the recirculation of supernatant liquid from the treatment system The provided reduced energy requirement provides a reduced energy requirement. When expressed as a percentage, the energy requirement for a given process, plant or system is the energy consumed by the process, plant or system relative to the total output of the power plant to which the process, plant or system is connected or used. A carbon dioxide-processing system not configured for recirculation (i.e., a carbon dioxide processing system configured for a single-pass process) such as that shown in Figure 2 can have at least 10% of the energy requirements of an industrial plant, which can be attributed to continuous A fresh source of alkalinity (eg, seawater, brine) is pumped into the system. In such an example, a 100 MW power plant (eg, a coal-fired power plant) would need to provide 10 MW of power to the carbon dioxide-processing system for continuously pumping a fresh source of alkalinity into the system. In contrast, a system configured for recirculation such as that shown in Figure 4 or Figure 5 may have a Energy requirements of industrial plants, which may be attributable to pumping make-up water and recirculating supernatant. A carbon dioxide-processing system configured for recirculation may exhibit at least 2%, such as at least 5%, including at least 10%, for example, at least 25% or at least 50% energy when compared to a system designed for a single pass process drop in need. For example, if a CO2-treatment system configured for recirculation consumes 9 MW of electricity to pump the make-up water and recirculate the supernatant and a CO2-treatment system designed for the single-pass process consumes 10 MW of electricity attributable to pumping , then a carbon dioxide-treatment system configured for recirculation shows a 10% drop in energy requirements. For systems such as those shown in Figures 4 and 5 (i.e., carbon dioxide-processing systems configured for recirculation), the reduction in energy requirements attributable to pumping and recirculation can also provide a reduction in the total energy requirements. decline, especially when compared to carbon dioxide-processing systems configured for single-pass processes. In some embodiments, recycling provides a reduction in the total energy requirement of the carbon dioxide-processing system, wherein the reduction is at least 2%, such as at least 4%, including at least 6%, such as at least 8% or at least 10%, when compared to At the total energy demand of a carbon dioxide-treatment system configured for a single-pass process. For example, if a CO2-treatment system configured for recirculation has an energy requirement of 15% and a CO2-treatment system designed for a one-pass process has a 20% energy requirement, then a CO2-treatment system configured for recirculation shows an overall energy requirement of 5%. Decreased energy requirements. For example, a carbon dioxide-processing system configured for recirculation, wherein recirculation includes filtration through a filtration unit such as a nanofiltration unit (e.g., to concentrate divalent cations in the retentate and reduce divalent cations in the permeate), There may be a reduction in total energy requirement of at least 2%, such as at least 4%, including at least 6%, such as at least 8% or at least 10%, when compared to a carbon dioxide-processing system configured for a single pass process.

The energy requirements of the carbon dioxide-processing method, apparatus and system of the present invention can be further reduced by efficient use of other resources. In some embodiments, the energy requirements of the carbon dioxide-processing systems of the present invention can be further reduced by efficient use of heat from industrial sources. In some embodiments, for example, heat from an industrial source of carbon dioxide (e.g., flue gas heat from a coal-fired power plant) can be used to dry salts and bicarbonates). In such embodiments, a spray dryer may be used to spray dry the composition. For example, low grade (eg, 150-200° C.) waste heat can be utilized by a heat exchanger to evaporatively spray dry compositions including precipitation material. In addition, drying the compositions of the present invention using heat from an industrial source of carbon dioxide allows simultaneous cooling of an industrial source of carbon dioxide (e.g., flue gas from a coal-fired power plant), which enhances the dissolution of carbon dioxide, a temperature-dependent inverse process. In some embodiments, the energy requirements of the carbon dioxide-processing systems of the present invention can be further reduced through efficient use of pressure. For example, in some embodiments, the carbon dioxide-processing system of the present invention is configured with an energy recovery system. Such energy recovery systems are known, for example, in the field of desalination and operate by pressure exchange. In some embodiments, when capturing and processing 70-90% of the carbon dioxide emitted from industrial facilities (e.g., coal-fired power plants), the total energy requirement of the carbon dioxide-processing system can be less than 99.9%, 90%, 80% , 70%, 60%, 50%, 40%, 30%, 20%, 15%, 10%, 5%, or 3%. For example, in some embodiments, when capturing and treating 70-90% of the carbon dioxide emitted from industrial facilities (e.g., coal-fired power plants), the total energy requirement of the carbon dioxide-processing system may be less than 30%, such as less than 20% , including less than 15%, eg, less than 10%, less than 5% or less than 3%. Thus, a carbon dioxide-processing system of the present invention configured for recirculation, heat exchange, and/or pressure exchange can reduce the parasitic load on industrial equipment providing power while maintaining carbon dioxide processing capacity.

Inevitably, the recycling and other methods described herein consume water as it may become part of the compositions of the present invention (e.g., precipitation materials include, e.g., amorphous calcium carbonate CaCO ₃ ·H ₂ O; three Hydromagnesite MgCO ₃ ·2H ₂ O; etc.), may be evaporated by drying (eg, spray drying) the composition of the invention, or lost in some other part of the process. Thus, make-up water can be provided to account for the water lost to process carbon dioxide to produce compositions of the invention (eg, spray-dried precipitation material). For example, a total of less than 700,000 gallons/day of make-up water could be replaced by water lost from producing, for example, spray-dried precipitation material from the flue gas of a 35 MW coal-fired power plant. A method requiring only make-up water may be considered a zero process water discharge method (ie, a zero liquid waste method). In methods where additional water is used in addition to make-up water, the water can be derived from any of the water sources described herein (eg, seawater, brine, etc.). In some embodiments, for example, water may be sourced from a power plant cooling stream and returned to this stream in a closed loop system. Processes that require make-up water and additional process water are considered low process water discharge processes because the systems and methods of the present invention are designed to use resources efficiently.

In some embodiments, the present invention provides contacting a volume of an aqueous solution with a carbon dioxide source to produce a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate, wherein the composition is a solution or a slurry. To produce precipitation material comprising carbonates, bicarbonates, or carbonates and bicarbonates, the method of the invention comprises contacting a volume of an aqueous solution containing secondary cations with a source _of CO and subjecting the resulting solution to facilitated precipitation conditions of. The divalent cations can come from any of a number of different sources of divalent cations, depending on availability at a particular location. Such sources include industrial waste, seawater, brine, hard water, rocks and minerals (eg, lime, periclase, materials including metal silicates such as serpentine and olivine), and any other suitable source.

In some locations, waste streams from various industrial processes (ie, industrial waste streams) provide suitable sources of divalent cations (as well as proton-removing agents such as metal hydroxides). Such waste streams include, but are not limited to, mining waste; ash (e.g., coal ash such as fly ash, bottom ash, boiler slag); slag (e.g., iron slag, phosphorus slag); cement kiln waste (e.g., cement kiln dust); refinery/petrochemical refinery waste (e.g. oil field and biogas layer brine); coal seam waste (e.g. gas extraction brine and coal seam brine); paper processing waste; water softening waste brine (e.g. ion exchange effluent); Processing waste; agricultural waste; metal polishing waste; high pH textile waste; Ash, cement kiln dust, and slag, in general, waste sources of metal oxides, which are further described in U.S. Patent Application 12/486,692 (filed June 17, 2009, which is incorporated herein by reference in its entirety), can be Use in any combination with materials including metallosilicates, which are further described in US Patent Application 12/501,217 (filed July 10, 2009, which is also incorporated herein by reference in its entirety). To practice the present invention, any of the sources of divalent cations described herein may be mixed and matched. To practice the invention, for example, materials including metal silicates (eg, magnesium silicate minerals such as olivine, serpentine, etc.) can be combined with any of the sources of divalent cations described herein.

In some locations, a suitable source of divalent cations for use in preparing compositions of the invention (e.g., comprising carbonate, bicarbonate, or precipitation material of carbonate and bicarbonate) is water (e.g., comprising divalent Aqueous solutions of cations such as seawater or brine), the latter can vary depending on the particular location in which the invention is practiced. Suitable aqueous solutions of divalent cations that may be used include solutions containing one or more divalent cations (eg, alkaline earth metal cations such as Ca2+ and Mg2+). In some embodiments, the aqueous source of divalent cations includes alkaline earth metal cations. In some embodiments, the alkaline earth metal cations include calcium, magnesium, or mixtures thereof. In some embodiments, the aqueous solution of divalent cations includes calcium in an amount of 50 to 50,000 ppm, 50 to 40,000 ppm, 50 to 20,000 ppm, 100 to 10,000 ppm, 200 to 5000 ppm, or 400 to 1000 ppm. In some embodiments, the aqueous solution of divalent cations includes magnesium in an amount of 50 to 40,000 ppm, 50 to 20,000 ppm, 100 to 10,000 ppm, 200 to 10,000 ppm, 500 to 5000 ppm, or 500 to 2500 ppm. In some embodiments, the ratio of Ca2+ to Mg2+ (i.e., Ca2+:Mg2+) in the aqueous solution of divalent cations in the presence of both Ca2+ and Mg2+ is 1:1 to 1:2.5; 1:2.5 to 1 :5; 1:5 to 1:10; 1:10 to 1:25; 1:25 to 1:50; 1:50 to 1:100; 1:100 to 1:150; 1:150 to 1:200 ; 1:200 to 1:250; 1:250 to 1:500; 1:500 to 1:1000 or a range thereof. For example, in some embodiments, the ratio of Ca2+ to Mg2+ in an aqueous solution of divalent cations is between 1:1 and 1:10; 1:5 and 1:25; 1:10 and 1:50; 1:25 and 1 :100; between 1:50 and 1:500; or between 1:100 and 1:1000. In some embodiments, the ratio of Mg2+ to Ca2+ (i.e., Mg2+:Ca2+) in the aqueous solution of divalent cations is 1:1 to 1:2.5; 1:2.5 to 1:5; 1:5 to 1:10; 1:10 to 1:25; 1:25 to 1:50; 1:50 to 1:100; 1:100 to 1:150; 1:150 to 1:200; 1:200 to 1:250; 1: 250 to 1:500; 1:500 to 1:1000 or the range thereof. For example, in some embodiments, the ratio of Mg2+ to Ca2+ in an aqueous solution of divalent cations is between 1:1 and 1:10; 1:5 and 1:25; 1:10 and 1:50; 1:25 and 1 :100; between 1:50 and 1:500; or between 1:100 and 1:1000.

One or more components present in the source of divalent cations from which the compositions of the invention (eg, precipitation material) are prepared can be used to identify the source of divalent cations used. These identifying components and their quantities may be referred to as "source identifiers" or "markers". For example, if the source of divalent cations is seawater, source identifiers or labels that may be present in compositions of the invention (e.g., precipitation material) include, but are not limited to, chlorine, sodium, sulfur, potassium, bromine, silicon, strontium, etc. . Such elements may be present in the composition at any known valency. Any such source identifiers or indicia may be present in small amounts, for example, 20,000 ppm or less, 2000 ppm or less, 200 ppm or less or 20 ppm or less. In some embodiments, for example, the label is strontium. In the precipitation material of the present invention, strontium may be incorporated into the aragonite lattice and constitute 10,000 ppm or less of the aragonite lattice, in certain embodiments, 3 to 10,000 ppm, such as 5 to 5000 ppm, including 5 to 1000ppm, eg, 5 to 500ppm or 5 to 100ppm. The source identifier can vary depending on the particular source of divalent cations (eg, saline) used to produce the compositions of the invention. In some embodiments, due at least in part to the source of divalent cations, the calcium carbonate content of the compositions (e.g., precipitation materials) of the invention may be 25% w/w or higher, such as 40% w/w or higher , including 50% w/w or higher, eg, 60% w/w or higher. In some embodiments, such compositions have a calcium:magnesium ratio that is influenced by, and thus reflects, the source of divalent cations from which the composition is derived. In some embodiments, the calcium:magnesium molar ratio is 10:1 to 1:5 Ca:Mg, such as 5:1 to 1:3 Ca:Mg. In some embodiments, the composition is characterized as having a source-identifying carbonate:hydroxide compound ratio, wherein the ratio is, for example, 100 to 1, 10 to 1, or 1 to 1.

Aqueous solutions of divalent cations may include those derived from fresh water, brackish water, sea water, or brine (e.g., naturally occurring brines or anthropogenic brines such as geothermal plant effluents, desalination plant effluents, synthetic brines, including those containing dissolved minerals), and divalent cations of other aqueous solutions (either of which may be naturally occurring or anthropogenic) of greater salinity than fresh water. For convenience, in describing the present invention, fresh water may be considered to have a salinity of less than 0.5 ppt (parts per thousand). Brackish water can include more salt than fresh water, but not as much salt as seawater. Brackish water can be considered to have a salinity of about 0.5 to about 35 ppt. Seawater may be water from the sea, ocean, or any other body of water with a salinity in the range of about 35 to about 50 ppt. The brine may have a salinity of about 50 ppt or more. Thus, brine may be water saturated or nearly saturated with salt. In some embodiments, the water source from which the divalent cations are derived is a mineral-rich (eg, calcium-rich and/or magnesium-rich) freshwater source. In some embodiments, the water source from which the divalent cations are derived is a naturally occurring brine source selected from seas, oceans, lakes, swamps, estuaries, lagoons, surface brines, deep brines, soda lakes, inland seas, and the like. In some embodiments, the water source from which the divalent cations are derived is surface brine. In some embodiments, the water source from which the divalent cations are derived is subterranean brine. In some embodiments, the water source from which the divalent cations are derived is deep brine. In some embodiments, the water source from which the divalent cations are derived is Ca-Mg-Na-(K)-Cl; Na-(Ca) _-SO4 -Cl; Mg-Na-(Ca) _-SO4 -Cl ; Na-CO ₃ -Cl; or Na-CO ₃ -SO ₄ -Cl brine. In some embodiments, the water source from which the divalent cations are derived is an anthropogenic brine selected from geothermal plant wastewater or desalination wastewater. In some embodiments, the water source may also contain boron in the form of borates, including but not limited to, inter alia, BO ₃ ^3- , B ₂ O ₅ ^4- , B ₃ O ₇ ^5- , and B ₄ O ₉ ^{6 -} .

Fresh water is often a suitable source of divalent cations (eg, cations of alkaline earth metals such as Ca2+ and Mg2+). Any of a number of suitable freshwater sources may be used, including freshwater sources ranging from relatively mineral-free sources to relatively mineral-rich sources. Mineral-rich freshwater sources may be naturally occurring and include any of a number of hard water sources, lakes or inland seas. Some mineral-rich freshwater sources such as soda lakes or inland seas (for example, Lake Van in Turkey) also provide a source of pH-altering agents. Mineral-rich freshwater sources can also be anthropogenic. For example, mineral-poor (soft) water can be contacted with a source of divalent cations such as alkaline earth metal cations (e.g., Ca2+, Mg2+, etc.) to produce mineral-rich water, which is suitable for the methods and systems described herein . Divalent cations or precursors thereof (eg salts, minerals) may be added to fresh water (or any other type of water described herein) using any suitable procedure (eg, addition of solids, suspensions or solutions). In some embodiments, divalent cations selected from Ca2+ and Mg2+ are added to fresh water. In some embodiments, monovalent cations selected from Na+ and K+ are added to fresh water. In some embodiments, fresh water comprising Ca2+ is combined with materials comprising metal silicates, ash (e.g., fly ash, bottom ash, boiler slag), or products or processed forms thereof, including combinations thereof, which form A solution comprising calcium and magnesium cations.

Thus, some methods include preparing a source of divalent cations by adding one or more divalent cations (eg, Ca2+, Mg2+, combinations thereof, etc.) to a water source. Sources of magnesium cations include, but are not limited to, magnesium hydroxide, magnesium oxide, and the like. Sources of calcium cations include, but are not limited to, calcium hydroxide, calcium oxide, and the like. Naturally occurring or man-made sources of such cations may be used. Naturally occurring sources of such cations include, but are not limited to, mafic minerals (eg, olivine, serpentine, olivine, talc, etc.) and the like. Adding additional magnesium cations to the water source (e.g., seawater) prior to producing the compositions of the present invention increases production (e.g., production of precipitation material) as well as affects the composition of such compositions (e.g., precipitation material), which provides A way to increase _CO2 sequestration by utilizing minerals such as but not limited to olivine, serpentine and Mg(OH)2 (brucite). The source of a particular cation (e.g., Ca2+, Mg2+, combinations thereof, etc.) can be naturally occurring or anthropogenic, and can be pure or impure relative to the mineral (e.g., derived from the mineral of interest and other Compositions of minerals and components).

The method of the present invention comprises introducing magnesium cations in a manner sufficient to produce a magnesium to calcium ratio in water of 3 or higher, for example, 4 or higher, such as 5 or higher, for example 6 or higher, including 7 or higher source added to the initial water. In certain embodiments, the water has a desired magnesium to calcium cation ratio of 3-10, such as 4-8. Any suitable source of magnesium cations may be added to the water to provide the desired ratio of magnesium to calcium cations, where the particular source of magnesium cations of interest includes, but is not limited to, Mg(OH)2, serpentine, olivine, magnesium Iron and ultramafic minerals. The amount of source of magnesium cations added to the water can vary, eg, depending on the particular source of magnesium cations and the initial water from which the CO ₂ -feed water is generated. In certain embodiments, the amount of magnesium cation added to the water is 0.01 to 100.0 g/L, such as 1 to 100 g/L of water, including 5 to 100 g/L of water, such as 5 to 80 g/L of water, including 5 to 50 g/l of water. In certain embodiments, the amount of magnesium cations added to the water is sufficient to produce water with a hardness reading of 0.06 g/L or more, such as 0.08 g/L or more, including 0.1 g/L or more, as determined by A Metrohm titrator (Metrohm AG, Switzerland) was determined according to the manufacturer's instructions. The source of magnesium cations can be combined with water using any suitable procedure, such as stirring, mixing, etc.

In embodiments where a source of magnesium, calcium, or a combination of magnesium and calcium is added to the water, the source may be in solid form, such as large, hard and often crystallized particles or a collection of particles that are difficult to get into solution. in block form. For example, Mg(OH) in the form of brucite may be in the form of many minerals useful in embodiments of the present invention, such as serpentine, olivine, and other magnesium silicate minerals, as well as cement waste, among others. Divalent cations from such sources, such as magnesium cations, may be introduced into an aqueous solution in the form of carbonate suitable for reaction with the carbonate to form the divalent cation using any suitable method. Increasing surface area by reducing particle size is one such method, which can be achieved by methods well known in the art such as ball milling and jet milling. Jet milling has the further advantage of destroying much of the crystalline structure of the substance, which increases solubility. Also contemplated is sonochemistry, where intense sonication can be used to increase reaction rates by a desired amount, eg 106 times or more. Particles, with or without size reduction, may be exposed to aqueous-promoting conditions, such as exposure to acids such as HCl, _{H2SO4 ,} etc.; mild acids or bases may also be used in some embodiments. See, eg, U.S. Patent Application Publication Nos. 2005/0022847; 2004/0213705; 2005/0018910; 2008/0031801; and 2007/0217981; European Patent Application Publication Nos. EP1379469 and EP1554031; 061305, each of which is incorporated herein by reference in its entirety.

In some embodiments, the methods and systems of the present invention use serpentine as the mineral source. Serpentine is a naturally occurring abundant mineral and may generally be described by the general formula X2-3Si2O5(OH)4, where X is selected from the group consisting of: Mg, Ca, Fe2 ⁺ , Fe3 ⁺ , Ni, Al, Zn, and Mn, the serpentine material is a heterogeneous mixture mainly composed of magnesium hydroxide and silica. In some embodiments of the present invention, serpentine is used not only as a magnesium source, but also as a hydroxide source. Thus, in some embodiments of the invention, hydroxide is provided to remove protons from water and/or to adjust pH by dissolving serpentine; in these embodiments acid dissolution is not ideal for accelerated dissolution, And using other means, such as jet milling and/or sonication. It should be understood that in a batch or continuous process, the duration of dissolution of the serpentine or other mineral is not critical, since once the process has started on the desired scale and sufficient time has elapsed to achieve a suitable level of dissolution, the A continuous flow of molten material can be maintained indefinitely. Thus, even if dissolution to the desired level takes days, weeks, months or even years, once the process has reached the first point in time when the desired dissolution has occurred, it can be maintained indefinitely. Other methods may be used to provide some or all of the magnesium and/or hydroxide to the method prior to the point in time when the desired dissolution has occurred. Serpentine is also a source of iron, which is a useful component for precipitates such as cement, where an iron component is often desired.

Other examples of silicate-type minerals useful for the present invention include, but are not limited to, olivine, the natural magnesium-iron silicate ((Mg, Fe) _2SiO4 ), which may generally be represented by the general formula X2( _SiO4 )n Described, wherein X is selected from Mg, Ca, Fe2+, Fe3+, Ni, Al, Zn and Mn, and n=2 or 3; and calcium silicate, such as wollastonite. Minerals may be used alone or in combination with each other as described in US Patent Application (Publication No.) 2009/0301352 (published December 10, 2009), which is incorporated herein by reference in its entirety. In addition, materials can occur naturally or can be manufactured. Examples of industrial by-products include, but are not limited to, waste cement, calcium-rich fly ash, and cement kiln dust (CKD), as disclosed in U.S. Patent Application (Publication No.) 2010/0000444 (published January 7, 2010). , which is incorporated herein by reference in its entirety.

In some embodiments, the aqueous solution of divalent cations can be obtained from an industrial facility that is also providing a waste gas stream (eg, a combustion gas stream). For example, in water-cooled industrial plants, such as seawater-cooled industrial plants, the water that has been used by the industrial plant for cooling can then be used as water for generating precipitation material. If desired, the water can be cooled before entering the precipitation system of the present invention. Such an approach may be used, for example, with a flow-through cooling system. For example, a municipal or agricultural water supply can be used as a flow-through cooling system for industrial equipment. The water from the industrial facility can then be used to produce precipitation material with the output water having reduced hardness and greater purity.

Aqueous solutions of divalent cations may further provide proton-removing agents, which may be expressed as alkalinity or the ability of a solution containing divalent cations to neutralize acids to the equivalent point of carbonate or bicarbonate. Alkalinity (AT) can be expressed by the following formula:

A _T ＝[HCO ₃ ^- ] _T +2[CO ₃ ^2- ] _T +[B(OH) ₄ ^- ] _T +[OH ^- ] _T +2[PO ₄ ^3- ] _T +[HPO ₄ ^2- ] _T + [SiO(OH) ₃ ^- ] T - [H ⁺ ] _sws - [HSO ₄ ^- ],

where "T" represents the total concentration of the species in solution as measured. Other substances, depending on the source, can also contribute to alkalinity. The total concentration of species in solution differs from the free concentration, which takes into account the significant amount of ion-pair interactions that exist, for example, in seawater. According to this formula, the aqueous divalent cation source can have various concentrations of bicarbonate, carbonate, borate, hydroxide, phosphate, hydrogen phosphate and/or silicate, which can contribute to Alkalinity of an aqueous divalent cation source. Any type of alkalinity is suitable for the present invention. For example, in some embodiments, a source of divalent cations of high borate alkalinity is suitable for the present invention. In such embodiments, the source of divalent cations may comprise boron in the form of borates including, but not limited to, BO ₃ ^3- , B ₂ O ₅ ^4- , B ₃ O ₇ ^5- , and B ₄ O ₉ ^6- . In such embodiments, the borate concentration may exceed the concentration of any other species in the solution, including, for example, carbonate and/or bicarbonate. In some embodiments, the source of divalent cations has an alkalinity of at least 10, 100, 500, 1000, 1500, 3000, 5000, or greater than 5000 milliequivalents. For example, in some embodiments, the source of divalent cations has a basicity of 500 to 1000 milliequivalents.

In some methods of the invention, water (such as brine or mineral-rich water) is not exposed to a source of _CO2 prior to subjecting the water to precipitation conditions. In these methods, the water will have associated with it an amount of _CO2 , for example in the form of bicarbonate ions, which have been obtained from the environment to which the water was exposed before carrying out the method. Subjecting the water to the precipitation conditions of the present invention results in the conversion of this CO ₂ into a storage stable precipitate and thus sequesters the CO ₂ . When the water subjected to the method of the present invention is again exposed to its natural environment such as the atmosphere, more _CO from the atmosphere will be absorbed by the water, which results in a net removal of _CO from the atmosphere and a corresponding amount of _CO introduced into the In storage-stable products, a source of mineral-rich freshwater may be exposed to a source of CO ₂ , for example, as described in more detail below. Embodiments of these methods can be viewed as methods for sequestering _CO2 gas directly from the Earth's atmosphere. Embodiments of the method effectively remove _CO2 from the Earth's atmosphere. For example, embodiments of the method are configured to remove _CO2 from brine at a rate of 0.025M or more, such as 0.05M or more, including 0.1M or more per gallon of brine.

In some embodiments, the invention provides for contacting a volume of an absorption solution (e.g., an aqueous solution) with a source of carbon dioxide to produce a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate, wherein the composition is a solution or slurry. In some embodiments, the solution is a slurry comprising precipitation material comprising carbonates, bicarbonates, or carbonates and bicarbonates. In some embodiments, the precipitating material is produced by subjecting the volume of aqueous solution to precipitating conditions before, during, or after contacting with the carbon dioxide source. There may be sufficient carbon dioxide in an aqueous solution to generate significant amounts of carbonate, bicarbonate, or both (eg, from brine or seawater); however, additional carbon dioxide is typically used. The source of _CO2 can be any suitable source of _CO2 . The source of _CO2 can be gas, liquid, solid (eg, dry ice), supercritical fluid, or _CO2 dissolved in a liquid. In some embodiments, the _CO2 source is a gaseous _CO2 source such as a waste gas stream. The source of gaseous _CO2 can be substantially pure _CO2 , or, as described in more detail below, include one or more components other than _CO2 , wherein one or more components include one or Various additional gases such as SOx (eg, SO, SO ₂ , SO ₃ ), NOx (eg, NO, NO ₂ ), etc., non-gas components, or combinations thereof. The waste stream may further include VOCs (volatile organic compounds), metals (eg, mercury, arsenic, cadmium, selenium), and particulate matter, including particles of solids (eg, fly ash) or liquids suspended in a gas. In some embodiments, the source of gaseous _CO2 can be an exhaust stream (eg, exhaust) produced by an active process of an industrial facility. The nature of industrial facilities can vary, and industrial facilities include, but are not limited to, power plants, chemical processing plants, mechanical processing plants, oil refineries, cement plants, steel plants, and others that generate _CO2 for combustion as fuel or another process step (e.g., Industrial equipment for by-products of calcination in cement plants. In some embodiments, for example, the source of gaseous _CO2 can be flue gas from a coal-fired power plant.

Exhaust gas streams that include _CO include streams in a reduced state (eg, syngas, shifted syngas, natural gas, hydrogen, etc.) and streams in an oxidized state (eg, flue gas resulting from combustion). Specific exhaust gas streams that may be suitable for use in the present invention include oxygenated flue gas produced by combustion (e.g., from coal or another carbon-based fuel with little or no flue gas pretreatment), turbocharged Boiler product gas, coal gasification product gas, pre-combustion synthesis gas (eg, as formed during coal gasification in power plants), shifted coal gasification product gas, anaerobic digester product gas, wellhead natural gas Logistics, reforming natural gas or methane hydrate, etc. Combustion gases from any suitable source may be used in the methods and systems of the present invention. In some embodiments, combustion gases from post-combustion effluent stacks of industrial facilities such as power plants, cement plants, and coal processing plants are used.

Thus, waste gas streams can be produced by various different types of industrial equipment. Suitable waste gas streams of the present invention include those produced by burning fossil fuels (e.g., coal, oil, natural gas, propane, diesel), biomass, and/or naturally occurring organic fuel reserves (e.g., tar sands, heavy oil, oil shale). , etc.) anthropogenic fuel products of industrial plant waste streams. In some embodiments, exhaust gas streams suitable for use in the systems and methods of the present invention originate from coal fired power plants, such as pulverized coal power plants, supercritical coal power plants, bulk coal fired power plants, fluidized bed coal power plants. In some embodiments, the exhaust gas stream originates from a gas or oil boiler and steam turbine power plant, a gas or oil boiler simple cycle gas turbine power plant, or a gas or oil boiler combined cycle gas turbine power plant. In some embodiments, an exhaust gas stream produced by a power plant burning syngas (ie, gas produced by the gasification of organic matter, eg, coal, biomass, etc.) is used. In some embodiments, a waste gas stream from an integrated gasification combined cycle (IGCC) unit is used. In some embodiments, systems and methods in accordance with the present invention utilize an exhaust gas stream produced by a heat recovery steam generator (HRSG) unit.

Waste gas streams including _CO2 may also result from other industrial processes. Waste gas streams produced by cement plants are also suitable for use in the systems and methods of the present invention. Cement plant off-gas streams include off-gas streams from wet and dry plants, which may use shaft kilns or rotary kilns, and may include precalciners. These industrial devices may each burn a single fuel, or may burn two or more fuels sequentially or simultaneously. Other industrial facilities such as furnaces and refineries are also useful sources of waste gas streams that include carbon dioxide.

The gaseous waste stream may be provided to the _CO2 -treatment system of the present invention by an industrial facility in any suitable manner for conveying the gaseous waste stream. In some embodiments, the waste gas stream is provided by a gas transport device (e.g., pipes, pipes, etc.) from an industrial plant flue or a similar structure (e.g., industrial plant flue and chimney) to the _CO2 -processing One or more locations in the system. In such an embodiment, a line (e.g., pipe, pipe, etc.) may be connected to the flue of the industrial facility so that the gas exiting through _the device or its components, such as gas-liquid contactor or gas-liquid-solid contactor). Depending on the particular configuration of the _CO2 -processing system, the location of the gas delivery means on the industrial plant may be varied, for example, in order to provide a desired temperature of the off-gas stream. Thus, in some embodiments, where the desired temperature is in the range of 0°C to 2000°C, such as 0°C to 1800°C, including 60°C to 700°C, e.g. Flue gas can be obtained at the exit point of the furnace, or at any point in the power plant that provides the desired temperature. The gas delivery device may be configured to maintain the temperature of the flue gas above the dew point (eg, 125°C) to avoid condensation and related complications. Other steps can be taken to reduce the adverse effects of condensation and other deleterious effects, such as using stainless steel or fluorocarbon (eg poly(tetrafluoroethylene)) lined tubing so that the tubing does not quickly fail.

Carbon dioxide can be the major non-air source component in the exhaust stream. In some embodiments, the exhaust gas stream may include carbon dioxide in an amount from 200 ppm to 1,000,000 ppm, such as from 1000 ppm to 200,000 ppm, including from 2000 ppm to 200,000 ppm, for example, from 2000 ppm to 180,000 ppm, or from 2000 ppm to 130,000 ppm. In some embodiments, the exhaust stream may include carbon dioxide in an amount from 350 ppm to 400,000 ppm. Such quantities of carbon dioxide can be considered as time-averaged quantities. For example, in some embodiments, the exhaust stream may include carbon dioxide in an amount of 40,000 ppm (4%) to 100,000 ppm (10%), depending on the exhaust stream (e.g., from a natural gas fired power plant, furnace, small boiler, etc. of CO ₂ ). For example, in some embodiments, the exhaust stream may include carbon dioxide in amounts ranging from 100,000 ppm (10%) to 150,000 ppm (15%), depending on the exhaust stream (e.g., from a coal-fired power plant, oil-fired generator, diesel CO ₂ for generators, etc.). For example, in some embodiments, the waste gas stream may include carbon dioxide in an amount from 200,000 ppm (20%) to 400,000 ppm (40%) depending on the waste gas stream (e.g., _CO2 from cement plant calcination, chemical plant, etc.) . For example, in some embodiments, the waste gas stream may include carbon dioxide in amounts ranging from 900,000 ppm (90%) to 1,000,000 ppm (100%) depending on the waste gas stream (e.g., _CO2 from ethanol fermenters, in refineries, Ammonia plants, _CO2 from steam reforming at substitute natural gas (SNG) plants, _CO2 from acid gas separation, etc.). The concentration of _CO in the exhaust stream can be reduced by 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or More, 80% or more, 90% or more, 95% or more, 99% or more, 99.9% or more, or 99.99%. In other words, at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, 99.9%, or 99.99% of the carbon dioxide can be removed from the waste gas stream.

A portion of the waste gas stream (ie, not the entire gaseous waste stream) from an industrial facility can be used to produce a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate. In such embodiments, the waste gas stream used to generate the portion of the composition may be 75% or less, such as 60% or less, and includes 50% and less of the waste gas stream. In other embodiments, a majority (eg, 80% or more) of the entire waste gas stream produced by the industrial facility is used to produce the composition. In such embodiments, 80% or more, such as 90% or more, including 95% or more, up to 100% of the waste gas stream (e.g., flue gas) produced by the source may be used to generate Compositions of the invention.

In _some embodiments of the invention, substantially 100% of the CO contained in the flue gas or a portion of the flue gas (from a power plant) may be sequestered as a composition of the invention (e.g., comprising one or Precipitation material of various stable or metastable inorganic substances). Such sequestration can be performed in a single step or in multiple steps, and can further _include other methods for sequestering _CO2 (e.g., for removal of More energy-intensive methods may become feasible in removing final _CO2 from the gas where the energy consumption of all initial _CO2 is too high). Thus, in some embodiments, the gas entering the power plant (regular atmospheric air) may contain a concentration of _CO2 that is greater than the concentration of _CO2 in the flue gas leaving the power plant that has been produced by the present Inventive method and system process. Accordingly, in some embodiments, the methods and systems of the present invention include methods comprising: providing a gas (e.g., atmospheric air) to a power plant, wherein the gas includes CO ₂ ; processing the gas in the power plant (e.g., Consuming _O2 by burning fossil fuels to produce _CO2 , then treating exhaust gas to remove _CO2 ; and releasing gas from a power plant, where the gas released from the power plant has lower CO than the gas supplied to the power plant ₂ content. In some embodiments, the gas released from the power plant contains at least 10% less _CO2 , or at least 20% less _CO2 , or at least 30% less _CO2 , or at least 40% less CO2 than the gas entering the power plant CO ₂ , or at least 50% less CO ₂ , or at least 60% less CO ₂ , or at least 70% less CO ₂ , or at least 80% less CO ₂ , or at least 90% less CO ₂ , or At least 95% less _CO2 , or at least 99% less _CO2 , or at least 99.5% less _CO2 , or at least 99.9% less _CO2 . In some embodiments, the gas entering the power plant is atmospheric air and the gas leaving the power plant is treated flue gas.

Although exhaust streams from industrial facilities provide relatively concentrated sources of _CO and/or additional components produced by fossil fuel combustion, the methods and systems of the present invention are also applicable to the removal of combustion gases from less concentrated sources Components (eg, atmospheric air) that contain much lower concentrations of pollutants than, for example, flue gases. Accordingly, in some embodiments, methods and systems involve reducing the concentration of _CO2 and/or additional components in atmospheric air by producing compositions of the invention. As with the exhaust stream, the concentration of _CO2 in a portion of the atmospheric air can be reduced by 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more More, 70% or more, 80% or more, 90% or more, 95% or more, 99% or more, 99.9% or more, or 99.99%. Such reduction of _CO2 can be achieved at the yields described herein, or at higher or lower yields, and can be achieved in one process step or in a series of process steps.

In certain embodiments, the oxidizing conditions include subjecting the gas stream to hydrogen peroxide (H ₂ O ₂ ) or a H ₂ O ₂ /CH ₃ OH mixture. An exemplary description of a system and method for oxidizing a CO2 _- containing gas stream using hydrogen peroxide can be found in US Patent No. 5,670,122, which is incorporated herein by reference in its entirety. As described in the '122 patent, the gas stream can be treated with hydrogen peroxide for a time sufficient to oxidize the components therein, for example, to convert nitrogen monoxide (NO), sulfur trioxide (SO ₃ ), light hydrocarbons ( One or more of C1-C4), carbon monoxide (CO) and mercury are converted to _NO2 , _SO2 , _CO2 and HgO. The gas stream can be treated with hydrogen peroxide or a _H2O2 / _{CH3OH mixture} , and the gas stream can then be contacted with water (e.g., water containing alkaline earth metal ions, in the form of flat jets, sprays or droplets, fumes or combination). In some embodiments, a recovered gas stream, which is recovered after contacting the gas stream with water (e.g., alkaline earth metal-containing water), is treated with a H ₂ O ₂ /CH ₃ OH mixture and reprocessed ( i.e., second exposure to water).

The reaction time of hydrogen peroxide or H ₂ O ₂ /CH ₃ OH mixture may be 0.01-5 seconds, for example 0.1-2 seconds. _NO2 , _SO2 , _CO2 and HgO (and other components of the gas stream) can then be removed by adsorption to water, eg water containing alkaline earth metal ions. In certain embodiments, the gas-fed water is then subjected to precipitation conditions to form a precipitate that includes one or more chemical components from the gas stream (eg, _NO2 , _SO2 , _CO2 , HgO, etc.). Thus, the present invention provides a rapid and efficient method for removing chemical components (e.g., _CO2 , important pollutants, and/or other toxic or environmentally harmful components) of a wide variety of gas sources such that These components are not emitted into the atmosphere in dangerously high concentrations. For example, the present invention may be used to remove these compounds from flue gases emitted from boilers, furnaces, incinerators, stationary engines and other systems involved in the combustion of various types of fuels.

The total amount of hydrogen peroxide and methanol used in combination with the gas stream will generally be in a molar ratio of 0.5 to 2.0, in most applications 0.9 to 1.5, relative to the total number of components. Hydrogen peroxide may be sparged (eg, as an aqueous solution) at a concentration of 1%-50%, eg, 10-30%. Hydrogen peroxide can also be sparged as _a mixture of _H2O2 solution and methanol. Using a mixture of _H2O2 and _methanol is desirable because the cost of methanol is very low. The ratio of methanol to _H2O2 should be as high as possible in order to reduce the cost _of additives, but to meet emission requirements.

The use of hydrogen peroxide in the present invention has many advantages. Aqueous hydrogen peroxide solution is stable if stored properly. The use of hydrogen peroxide does not create any environmental concerns because hydrogen peroxide itself is not a source of pollution and the only by-products of the reaction are water and oxygen. Therefore, hydrogen peroxide can be safely used in the present invention.

The pH of the water in contact with the _CO2 source can vary. In some cases, the pH of the water in contact with the _CO2 source is acidic such that the pH is below 7, such as 6.5 or less, 6 or less, 5.5 or less, 5 or less, 4.5 or more Low or 4 or lower. In other embodiments, the pH of the water may be neutral to slightly alkaline, which means the pH of the water may be from pH 7 to pH 9, such as from pH 7 to pH 8.5, including from pH 7.5 to pH 8.5.

In some cases, water, such as alkaline earth metal ion-containing water (including alkaline solutions or naturally saline waters), is alkaline when contacted with a source of _CO2 , such as a carbon dioxide-containing gas stream. In this case, although alkaline, the pH of the water is generally insufficient to cause precipitation of storage-stable carbon dioxide sequestration products. Thus, the pH may be 9.5 or lower, such as 9.3 or lower, including 9 or lower.

In some cases, the pH as described above may be maintained at a substantially constant value when contacted with the carbon dioxide-containing gas stream, or the pH may be manipulated to maximize _CO2 absorption while minimizing base consumption or other means of removing protons , such as by starting at a certain pH and gradually raising the pH as _CO2 continues to be introduced. In embodiments wherein the pH is maintained substantially constant, wherein "substantially constant" means that during certain stages of contact with carbon dioxide the pH varies by 0.75 or less, such as 0.50 or less, including 0.25 or more Less, like 0.10 or less. The pH can be maintained at a substantially constant value, or manipulated so as to maximize _CO2 absorption, but prevent precipitation of hydroxides, no precipitate, using any suitable method. In some cases, during _CO2 dosing of water, the pH is maintained at a substantially constant value, or is manipulated without precipitation to maximize _CO2 absorption, in a manner that provides a substantially constant pH This is accomplished by adding a sufficient amount of alkali to the water. Sometimes it is desirable to control the pH to maximize carbon _dioxide and other components from the gas stream (e.g. SOx, NOx , heavy metals, other acid gases) absorption. Any suitable base or combination of bases may be added, including but not limited to oxides and hydroxides such as magnesium hydroxide, with further examples of suitable bases being reviewed below. In other cases, the pH may be maintained at a substantially constant value, or manipulated to maximize _CO2 absorption, by using an electrochemical process, such as the one described below, so that the pH of the water is measured electrochemically The method remains basically constant. Surprisingly, as shown in Example IV, it has been found that by simple seawater spraying, with simultaneous addition of alkali (removal of protons), it is possible to absorb, for _example , greater than 50% of the of CO ₂ .

In some embodiments, the methods and systems of the present _invention are capable of absorbing 5% or _more , 10%, or More, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more , 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, 95 % or more, or 99% or more _CO2 . In some embodiments, the methods and systems of the present invention are capable of absorbing 50% or more of _{the CO2} in a gaseous source of CO2 such as an industrial source of _CO2 such as flue gas from a power plant or waste gas from a cement plant.

In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 20 tons/hour of carbon dioxide into the absorption solution, averaged over 72 hours of continuous operation. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 40 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 60 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 70 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 80 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 90 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 100 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 110 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 120 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 130 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 140 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 150 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 160 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 170 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 180 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 190 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the methods and systems of the present invention are capable of absorbing greater than 200 tons/hour of carbon dioxide into the absorption solution.

In some embodiments, the present invention provides contacting a volume of an aqueous solution with a carbon dioxide source to produce a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate, wherein the composition is a solution or a slurry. Contacting the aqueous solution with a source of carbon dioxide promotes the dissolution of _CO2 into the aqueous solution, which produces carbonic acid, a species in equilibrium with bicarbonate and carbonate. To produce the compositions of the present invention (e.g., precipitation material comprising carbonates, bicarbonates, or carbonates and bicarbonates), various species (e.g., ) to shift the equilibrium toward bicarbonate, carbonate, or somewhere in between. When the protons are removed, more _CO2 goes into solution. In some embodiments, a proton-removing agent and/or method is used while contacting an aqueous solution with _CO to enhance _CO uptake in a single phase of the reaction, where the pH can be held constant, increased, or even decreased, followed by rapid removal of protons (eg, by adding a base), which in some embodiments can cause rapid precipitation of the precipitation material. Protons can be removed from the Various substances are removed (such as carbonic acid, bicarbonate, hydronium ion, etc.).

Naturally occurring proton-removing agents include any proton-removing agent that occurs in a wide variety of environments that may generate or have a basic local environment. Some embodiments provide naturally occurring proton-removing agents, including minerals that create a basic environment when added to a solution. Such minerals include, but are not limited to, lime (CaO); periclase (MgO); iron hydroxide minerals (eg, goethite and limonite); and pozzolans. Methods of digestion of such minerals and rocks comprising such minerals are described in US Patent Application No. 12/501,217, filed July 10, 2009, which is incorporated herein by reference in its entirety. Some embodiments provide for the use of a naturally occurring water body comprising carbonate, borate, sulfate, or nitrate alkalinity, or some combination thereof, as a source of proton-removing agent. Any alkaline brine (eg, surface brine, subterranean brine, deep brine, etc.) is suitable for use in the present invention. In some embodiments, surface brines including carbonate alkalinity provide a source of proton-removing agents. In some embodiments, surface brines including borate alkalinity provide a source of proton-removing agents. In some embodiments, subsurface brines including carbonate alkalinity provide a source of proton-removing agents. In some embodiments, subsurface brines including borate alkalinity provide a source of proton-removing agents. In some embodiments, deep brines including carbonate alkalinity provide a source of proton-removing agents. In some embodiments, deep brines including borate alkalinity provide a source of proton-removing agents. Examples of naturally alkaline water bodies include, but are not limited to, surface water sources (eg, alkaline lakes such as Lake Mono in California) and groundwater sources (eg, alkaline aquifers such as the deep geological alkaline aquifers of Lake Searles in California). Other embodiments provide for the use of sediment from dry alkaline water bodies such as the scabs of Lake Natron in the Great Rift Valley along Africa. For additional sources of brine and evaporated salt, see US Provisional Patent Application No. 61/264,564, filed November 25, 2009, which is incorporated herein by reference in its entirety. In some embodiments, organisms that secrete basic molecules or solutions as part of their normal metabolism are used as proton-removing agents. Examples of such organisms are fungi that produce alkaline proteases (e.g., the deep-sea fungus Aspergillus subtilis, with an optimum pH of 9) and bacteria that produce alkaline molecules (e.g., cyanobacteria such as the sp. Atlin wetlands in Colombia, which increases pH from photosynthesis by-products). In some embodiments, an organism is used to produce a proton-removing agent, wherein the organism (e.g., Bacillus pasteuria, which hydrolyzes urea to ammonia) metabolizes a pollutant (e.g., urea) to produce a proton-removing agent or Solutions including proton-removing agents (eg, ammonia, ammonium hydroxide). In some embodiments, the organism is cultured alone from the precipitation reaction mixture, wherein the proton-removing agent or a solution comprising the proton-removing agent is used to add to the precipitation reaction mixture. In some embodiments, naturally occurring or produced enzymes are used in combination with proton-removing agents to cause precipitation of precipitation material. Carbonic anhydrase, an enzyme produced by plants and animals, accelerates the conversion of carbonic acid to bicarbonate in aqueous solution. Thus, carbonic anhydrase can be used to increase the dissolution of _CO2 and accelerate the precipitation of precipitation material, as described in more detail herein.

Chemicals used to perform proton removal generally refer to synthetic chemicals, which are produced in large quantities and are commercially available. For example, chemicals used to remove protons include, but are not limited to, hydroxides, organic bases, superbases, oxides, ammonia, and carbonates. Hydroxides include chemical species that provide hydroxide anions in solution, including, for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2) or magnesium hydroxide (Mg (OH)2). Organic bases are carbon-containing molecules that are usually nitrogen-containing bases and include primary amines such as methylamine, secondary amines such as diisopropylamine, tertiary amines such as diisopropylethylamine, aromatic amines such as aniline, and heteroaromatics such as pyridine , imidazole and benzimidazole and various forms thereof. In some embodiments, an organic base selected from the group consisting of pyridine, methylamine, imidazole, benzimidazole, histidine, and phosphazene is used to decompose various substances (e.g., carbonic acid, bicarbonate, hydronium ion, etc.) Compositions of the present invention are prepared by removing protons from . In some embodiments, ammonia is used to raise the pH to a level sufficient to prepare the compositions of the present invention. Superbases suitable for use as proton-removing agents include sodium ethoxide, sodium amide (NaNH ₂ ), sodium hydride (NaH), butyllithium, lithium diisopropylamide, lithium diethylamide and bis( Lithium trimethylsilyl)amide. Oxides including, for example, calcium oxide (CaO), magnesium oxide (MgO), strontium oxide (SrO), beryllium oxide (BeO) and barium oxide (BaO) are also suitable usable proton-removing agents. Carbonates for use in the present invention include, but are not limited to, sodium carbonate.

Waste streams from various industrial processes (ie, industrial waste streams) can provide proton-removing agents, in addition to including cations (eg, Ca2+, Mg2+, etc.) and other suitable metal forms suitable for use in the present invention. Such waste streams include, but are not limited to, mining waste; ash (e.g., coal ash such as fly ash, bottom ash, boiler slag); slag (e.g., iron slag, phosphorus slag); cement kiln waste (e.g., cement kiln dust (CKD)); refinery/petrochemical refinery waste (e.g. oil field and biogas layer brine); coal seam waste (e.g. gas extraction brine and coal seam brine); paper processing waste; water softening waste brine (e.g. ion exchange effluent ); silicon processing waste; agricultural waste; metal polishing waste; high pH textile waste; and alkaline slag. Mining waste includes any waste that results from the extraction of a metal or another valuable or useful mineral from the earth. In some embodiments, waste from mining is used to alter the pH, wherein the waste is selected from red mud from Bayer's aluminum extraction process; waste from extraction of magnesium from seawater (e.g., Mg(OH)2 as found in Moss Landing); and waste from mining methods including leaching. For example, red mud can be used to alter pH as described in U.S. Provisional Patent Application No. 61/161369, filed March 18, 2009, and entitled "Gas Stream Multi- PCT Application PCT/US10/25970 for Pollutants Control Systems And Methods" and U.S. Patent Application No. 12/716,235, filed March 2, 2010, entitled "Gas Stream Multi-Pollutants Control Systems And Methods," which are incorporated in their entirety by This article serves as a reference. Red mud, depending on processing conditions and source material (for example, bauxite) can include Fe2O3 _{, Al2O3} , SiO2, _Na2O , CaO, _TiO2 , K2O, MgO, _CO2 , S2O, _MnO2 , P2O5, all Each of the species is listed in a loose order from most abundant to less abundant, and each of the species is represented as an oxide for convenience. Coal ash, cement kiln dust and slag, collectively waste sources of metal oxides, are further described in U.S. Patent Application No. 12/486692 (filed June 17, 2009, published as US 2010-0000444A1, Published on January 7, 2010, entitled "Methods And Systems For Utilizing Waste Sources Of Metal Oxides."), the disclosure of which is incorporated herein in its entirety, may be used alone or in combination with other proton-removing agents to provide in the proton-removing agent of the present invention. Agricultural waste, through animal waste or excessive fertilizer use, can contain potassium hydroxide (KOH) or ammonia (NH ₃ ) or both. Thus, agricultural waste can be used as a proton-removing agent in some embodiments of the invention. This agricultural waste is often collected in ponds, but it can also percolate into aquifers where it can be harvested and used.

In some embodiments of the invention, the ash can be used as a proton-removing agent, for example, to raise the pH of _CO2 -fed water. Ash can be used as the sole pH altering agent or with one or more additional pH altering agents. Contemplated in certain embodiments is the use of coal ash as ash. Coal ash as used in the present invention refers to the residue resulting from the combustion of pulverized anthracite, lignite, bituminous or sub-bituminous coal in power plant boilers or coal-fired smelters such as chain screen boilers, cyclone boilers and fluidized bed boilers . Such coal ash includes fly ash, which is finely divided coal ash carried over from the furnace by exhaust or flue gas, and bottom ash, which collects in agglomerated form at the bottom of the furnace.

Fly ashes are generally highly heterogeneous and include a mixture of glassy particles with various identifiable crystalline phases such as quartz, mullite, and various iron oxides. Fly ashes considered include Type F and Type C fly ash. The aforementioned Types F and C fly ash are defined by CSA Standard A23.5 and ASTM C618. The main difference between these categories is the amount of calcium, silica, alumina and iron content in the ash. The chemical properties of fly ash are mainly influenced by the chemical content of the coal being burned (ie, anthracite, bituminous and lignite). Fly ashes considered include large amounts of silica (silica, _SiO2 ) (both amorphous and crystalline) and lime (calcium oxide, CaO, magnesium oxide, MgO).

Table 3 below provides the chemical composition of various types of fly ash used in embodiments of the present invention.

Table 3. Chemical composition of various types of fly ash.

component bituminous coal Subbituminous coal lignite SiO ₂ (%) 20-60 40-60 15-45 Al ₂ O ₃ (%) 5-35 20-30 20-25 Fe ₂ O ₃ (%) 10-40 4-10 4-15 CaO(%) 1-12 5-30 15-40

Combustion of harder, older anthracite and bituminous coals generally produces Class F fly ash. Class F fly ash is pozzolanic in nature and contains less than 10% lime (CaO). Fly ash produced by burning younger lignite or sub-bituminous coals has some self-binding properties in addition to pozzolanic properties. In the presence of water, Class C fly ash will harden and gain strength over time. Class C fly ash typically contains greater than 20% lime (CaO). The alkali and sulfate (SO ₄ ) content is generally higher in Class C fly ash.

The fly ash material solidifies while suspended in the exhaust gas and is collected using various methods, such as by electrostatic precipitators or filter bags. Fly ash particles are generally spherical and have a size of 0.5 μm-100 μm as the particles solidify while being suspended in the exhaust gas. Fly ashes contemplated include those in which at least 80% by weight comprise particles smaller than 45 microns. In certain embodiments of the present invention, the use of highly alkaline fluidized bed combustor (FBC) fly ash is also contemplated.

Also contemplated in embodiments of the present invention is the use of bottom ash. Bottom ash from coal combustion is formed in the form of agglomerates in coal fired boilers. Such fired boilers may be liquid slagging boilers or solid slagging boilers. Bottom ash is water quenched when produced in liquid or solid slagging boilers. Quenching yielded agglomerates with a size where 90% fell within the 0.1 mm-20 mm particle size range, with bottom ash agglomerates having a broad distribution of agglomerate sizes within this range. The main chemical components of bottom ash are silica and alumina, with smaller amounts of Fe, Ca, Mg, Mn, Na and K, and oxides of sulfur and carbon.

Also contemplated in certain embodiments is the use of pozzolans as ash. Volcanic ash consists of small pyroclastics (ie, shavings of crushed rock and glass produced by volcanic eruptions, less than 2 millimeters (0.079 in) in diameter).

In one embodiment of the invention, cement kiln dust (CKD) is added to the reaction vessel as a means of changing the pH. The nature of the fuel from which the ash and/or CKD is produced and the manner in which the fuel is burned will affect the chemical composition of the resulting ash and/or CKD. Thus, ash and/or CKD may be used as part of, or the only means of adjusting pH, and various other components may be used along with a particular ash and/or CKD, based on the chemical composition of the ash and/or CKD .

In an embodiment of the invention, ash is added to the reaction as a source of these additional reactants to produce a carbonate mineral precipitate comprising one or more components such as amorphous silica, crystalline di Silica, calcium silicate, calcium aluminum silicate, or any other moiety that may be produced by the reaction of ash during carbonate mineral precipitation.

The ash used in the present invention can be contacted with water to obtain the desired pH change using any suitable procedure, for example, by placing an amount of ash in a water-filled reactor where the amount of ash added is sufficient to raise the pH to the desired pH. Horizontally, by passing water through a volume of ash, for example, in the form of towers or beds, etc.

In certain embodiments, where the pH is not raised to a level of 12 or higher, the fly ash used in the process, such as described below, will not necessarily dissolve, but instead will remain in the form of a particulate composition. This undissolved ash can be separated from the rest of the reaction product, eg filtered off, for subsequent use. Alternatively, the water may flow through a volume of ash provided in a fixed arrangement, such as in a tower or co-function structure, which provides liquid flow through the ash but does not allow the ash solids to flow out of the structure with the liquid. This embodiment does not require separation of undissolved ash from product liquid. In other embodiments, where the pH exceeds 12, the ash dissolves and provides a pozzolanic product, eg, as described in detail elsewhere.

In embodiments of the present invention, where the ash is utilized in the precipitation process, firstly, the ash can be removed from the flue gas by means such as electrostatic precipitation, or can be utilized directly through the flue gas. The use of ash in embodiments of the invention may provide reactants such as alumina or silica, in addition to raising the pH.

In certain embodiments of the invention, slag is used as a pH altering agent, eg, to increase the pH of _CO fed water. Slag can be used as the sole pH changing agent or with one or more additional pH changing agents such as ash or the like. Slag is produced by working metal and can contain calcium and magnesium oxides as well as iron, silicon and aluminum compounds. In certain embodiments, the use of slag as a pH changing material provides additional benefits by introducing reactive silica and alumina to the precipitated product. Slags considered include, but are not limited to, blast furnace slags from pig iron smelting, slags from electric arc or blast furnace processing of steel, copper slags, nickel slags, and phosphorus slags.

By removing protons from solutes (e.g., deprotonation of carbonic acid or bicarbonate) or from solvents (e.g., deprotonation of hydronium ions or water), electrochemical methods provide a method for removing protons from various substances in solution. Another means of removing protons. For example, deprotonation of the solvent can form if the proton matching produced by _CO2 dissolution exceeds or exceeds the electrochemical proton removal from the solute molecule. In some embodiments, low-voltage electrochemical methods are used to remove protons, for example, when _CO is dissolved in the precipitation reaction mixture or a precursor solution (ie, a solution that may or may not contain divalent cations) of the precipitation reaction mixture. In some embodiments, _CO dissolved in an aqueous solution that does not contain divalent cations is processed by low-pressure electrochemical methods to generate carbonic acid, bicarbonate, hydronium ions, or any species or combinations thereof that result from the dissolution of _CO . remove protons. Low voltage electrochemical method at 2, 1.9, 1.8, 1.7, or 1.6V or less, such as 1.5, 1.4, 1.3, 1.2, 1.1V or less, such as 1V or less, such as 0.9V or less, 0.8V or less, 0.7V or less, 0.6V or less, 0.5V or less, 0.4V or less, 0.3V or less, 0.2V or less, or 0.1V or less under the average voltage operate. Low pressure electrochemical methods that do not generate chlorine gas are convenient for use in the systems and methods of the present invention. Low pressure electrochemical methods for removing protons that do not generate oxygen are also convenient for use in the systems and methods of the present invention. In some embodiments, no gas is produced at the anode low pressure process. In some embodiments, hydrogen gas is produced electrochemically at a low pressure at the cathode and delivered to the anode where it is converted to protons. Electrochemical methods that do not generate hydrogen may also be suitable. In some cases, the electrochemical methods used to remove protons did not produce any gaseous by-products. Electrochemical methods for proton removal are further described in: US Patent Application 12/344,019 (filed December 24, 2008); US Patent Application 12/375,632 (filed December 23, 2008); International Patent Application PCT/US08/088242 (dated December 23, 2008); International Patent Application PCT/US09/32301 (dated January 28, 2009); and International Patent Application PCT/US09/48511 ( filed June 24, 2009), each of which is incorporated herein by reference in its entirety.

Alternatively, alkaline molecules (eg, hydroxides) can be generated electrochemically, eg, by the chlor-alkali process or variations thereof (eg, low pressure variants). Electrodes (ie, cathode and anode) can be present in a device containing an aqueous or exhaust-fed (eg, _CO2 -fed) solution, and a selective barrier, such as a membrane, can separate the electrodes. Electrochemical systems and methods for removing protons can produce by-products (eg, hydrogen gas), which can be collected and used for other purposes. Additional electrochemical methods that may be used in the systems and methods of the present invention include, but are not limited to, those described in U.S. Provisional Patent Application 61/081,299 (filed July 16, 2008) and U.S. Provisional Patent Application 61/091,729, the disclosure of which is incorporated herein by reference. Combinations of the proton-removing agent sources and methods of performing the proton removal described above may be used.

In embodiments where electrochemical methods are used to remove protons and/or generate bases, an acid stream, such as an HCl stream, is typically also produced, and this stream, alone or any other suitable source of acid, or combination thereof, can be For enhancing the dissolution of, for example, magnesium-containing inorganics such as olivine or serpentine, or calcium sources such as cement waste. Dissolution can be further enhanced by sonication methods, which can create pockets of localized extremes of temperature and pressure, increasing reaction rates by a factor of one hundred to over a million. Such methods are known in the art.

In some embodiments, the methods of the invention allow large amounts of magnesium and, sometimes, calcium to be added to the water used in some embodiments of the invention, which increases the precipitate that can be formed per unit of water in a single precipitation step This amount, when combined with a method of dissolving _CO2 from industrial water sources, eg, seawater or other brine sources, allows for surprisingly high yields of carbonate-containing precipitates. In some embodiments, the method of the invention comprises removing _CO from a gas source, e.g., an industrial gas source such as a flue from a power plant, _by subjecting the _CO to water into which the CO has been dissolved from the gas source. gas, or as a method of removing _CO2 from waste gas from a cement plant, where the precipitation step provides an amount of precipitate: 10 g/L or more in a single precipitation step, 15 g/L or more in a single precipitation step , 20 g/L or more in a single precipitation step, 25 g/L or more in a single precipitation step, 30 g/L or more in a single precipitation step, 40 g/L or more in a single precipitation step, in 50g/L or more in a single precipitation step, 60g/L or more in a single precipitation step, 70g/L or more in a single precipitation step, 80g/L or more in a single precipitation step, in a single precipitation step 90 g/L or more in a step, 100 g/L or more in a single precipitation step, 125 g/L or more in a single precipitation step, or 150 g/L or more in a single precipitation step.

In some embodiments, the method of the present invention comprises removing _CO from _a gas source by subjecting water (e.g., seawater, brine, absorption solution) into which CO has been dissolved from a gas source of CO (e.g., an industrial source of carbon dioxide) to precipitation conditions. , for example, an industrial gas source of _CO2 such as flue gas from a power plant, or exhaust gas such as from a cement plant, a process for removing _CO2 , wherein the precipitation conditions provide a deposit of the following amount: During 72 hours of continuous application of the precipitation conditions An average of 136 tons/hour to 445 tons/hour during the period of time.

In some embodiments, the methods of the present invention comprise removing _CO from _a gas source by subjecting water (e.g., seawater, brine, absorption solution) into which CO has been dissolved from a gas source of CO (e.g., an industrial source of carbon dioxide) to precipitation conditions. , for example, an industrial gas source of _CO2 such as flue gas from a power plant, or exhaust gas such as from a cement plant, a process for removing _CO2 , wherein the precipitation conditions provide a deposit of the following amount: During 72 hours of continuous application of the precipitation conditions The time period averaged from 2.6 grams of sediment/liter of absorption solution to 26.11 grams of sediment/liter of absorption solution. In some embodiments, the precipitation conditions provide an amount of precipitate ranging from an average of 5.2 grams of precipitate per liter of absorption solution to 26.11 grams of precipitate per liter of absorption solution over a period of 72 hours of continuous application of the precipitation condition. In some embodiments, the precipitation conditions provide an amount of precipitate ranging from an average of 7.83 grams of precipitate per liter of absorption solution to 26.11 grams of precipitate per liter of absorption solution over a 72 hour period of continuous application of the precipitation conditions, Such as 9.14 to 26.11, such as 10.44 to 26.11, such as 11.75 to 26.11, such as 13.05 to 26.11, such as 14.36 to 26.11, such as 15.66 to 26.11, such as 16.97 to 26.11, such as 18.27 to 26.11, such as 19.58 to 26.11, such as 20.88 to 26. Such as 22.19 to 26.11, such as 23.5 to 26.11, such as 24.8 to 26.11 grams of precipitate per liter of absorption solution.

In some embodiments, the precipitate includes magnesium carbonate; in some embodiments, the precipitate includes calcium carbonate; in some embodiments, the precipitate includes magnesium carbonate and calcium carbonate and/or magnesium carbonate/calcium carbonate. In some embodiments, the ratio of magnesium to calcium in the precipitation material produced in a single precipitation step is at least 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, or at least 4:1. 1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1. In some embodiments, the ratio of magnesium to calcium in the precipitation material produced in a single precipitation step is at least 2:1. In some embodiments, the ratio of magnesium to calcium in the precipitation material produced in a single precipitation step is at least 4:1. In some embodiments, the ratio of magnesium to calcium in the precipitation material produced in a single precipitation step is at least 6:1. In some embodiments, the precipitate comprises calcium carbonate and magnesium carbonate, and comprises a component that allows at least a portion of the carbon in the carbonate to be traced back to a fossil fuel source.

In some embodiments, the precipitate includes magnesium carbonate; in some embodiments, the precipitate includes calcium carbonate; in some embodiments, the precipitate includes magnesium carbonate and calcium carbonate and/or magnesium carbonate/calcium carbonate. In some embodiments, the ratio of magnesium to calcium in the precipitation material produced on average within 72 hours of applying the precipitation conditions is at least 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, Or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1. In some embodiments, the ratio of magnesium to calcium in the precipitation material produced is, on average, at least 2:1 within 72 hours of applying the precipitation conditions. In some embodiments, the precipitation material produced has a ratio of magnesium to calcium of at least 4:1 on average within 72 hours of applying the precipitation conditions. In some embodiments, the precipitation material produced has a ratio of magnesium to calcium of at least 6:1 on average within 72 hours of applying the precipitation conditions. In some embodiments, the precipitate comprises calcium carbonate and magnesium carbonate, and comprises a component that allows at least a portion of the carbon in the carbonate to be traced back to a fossil fuel source.

As noted above, the method of the present invention involves subjecting water (which may or may not be fed with _CO2 in a feed reactor, as described above) to precipitation conditions sufficient to produce a storage-stable precipitated carbon dioxide sequestration product. Any suitable precipitation conditions that result in the desired sequestered product may be used.

Precipitation conditions of interest include those that adjust the physical environment of the water to produce the desired precipitation product. For example, the temperature of the water can be adjusted to a level suitable for the desired precipitation of the product to occur. In such embodiments, the temperature of the water may be adjusted to values from 0°C to 90°C, such as 20°C to 50°C and inclusive. Thus, while a given set of precipitation conditions may have temperatures ranging from 0°C to 100°C, in certain embodiments the temperature may be adjusted to produce the desired precipitate. The temperature of the water can be adjusted using any suitable procedure. In some cases, the use of low or zero carbon dioxide emission sources, such as solar energy resources, wind energy resources, hydroelectric energy resources, geothermal energy resources, waste heat from flue gases (which can be as high as 500 ° C when heating is required), etc., energy to regulate temperature.

Although the pH of the water may range from 7 to 14 during a given precipitation process, in some cases the pH is raised to alkaline levels in order to produce the desired precipitation product. In such embodiments, the pH is raised to a level sufficient to cause precipitation of the desired _CO2 -storage product, as described above. Thus, the pH may be raised to 9.5 or higher, such as 10 or higher, including 10.5 or higher. Where desired, the pH can be raised to a level that minimizes, if not eliminates, _CO2 production during precipitation. For example, the pH may be raised to a value of 10 or higher, such as 11 or higher. In certain embodiments, the pH is increased to 7-11, such as 8-11, including 9-11, such as 10-11. In this step, the pH can be raised to and maintained at the desired alkaline level such that the pH is maintained at a constant alkaline level, or the pH can be varied between two or more different Shift or cycle between alkaline levels, depending on desired requirements.

In normal seawater, 93% of the dissolved _CO2 is in the form of bicarbonate ions ( _HCO3- ) and 6% is in the form of carbonate ions ( _CO32- ). When calcium carbonate precipitates from normal seawater, _CO2 is released. In fresh water, above pH 10.33, more than 90% of the carbonate is in the form of carbonate ions, and no _CO2 is released during calcium carbonate precipitation. In seawater, this transition occurs at a slightly lower pH, closer to a pH of 9.7. While the pH of the water used in the process may range from 5 to 14 during a given precipitation process, in some embodiments the pH is raised to alkaline levels in order to drive the precipitation of carbonate compounds as well as other compounds such as , depending on expectations. In some of these embodiments, the pH is raised to a level that minimizes, if not eliminates, the production of _CO2 during precipitation, which causes dissolved _CO2 , for example in the form of carbonates and bicarbonates , are trapped in carbonate compound precipitates. In such embodiments, the pH may be raised to 9 or higher, such as 10 or higher, including 11 or higher.

As noted above, the pH of the water source (eg, alkaline earth metal ion-containing water) is raised using any suitable method. In certain embodiments, pH increasing agents may be used, where examples of such agents include oxides (calcium oxide, magnesium oxide), hydroxides (e.g., potassium hydroxide, sodium hydroxide, brucite (Mg( OH)2, etc.), carbonates (for example, sodium carbonate) and the like.

As noted above, ash (or slag, in some embodiments) is used in some embodiments as the only means of changing the pH of the water to a desired level. In other embodiments, ash is used along with one or more additional pH changing procedures.

Alternatively, or in conjunction with the use of a pH raising agent (as described above), the pH of a source of water (eg, alkaline earth metal ion-containing water) can be raised to a desired level by electrolysis of water, using electrolytic or electrochemical processes. Contemplated electrochemical processes include, but are not limited to, those described above as well as those described in U.S. Provisional Patent Application 61/081,299, filed July 16, 2008, and U.S. Provisional Patent Application 61/091,729, application dated August 25, 2008, each of which is incorporated herein by reference in its entirety. Also contemplated are the electrolytic processes described in U.S. Patent Application (Publication No.) 2006/0185985, published August 24, 2006, U.S. Patent Application (Publication No.) 2008/0248350, published October 9, 2008, and International Patent Application Publication No. WO 2008/018928, published February 14, 2008, each of which is incorporated herein by reference in its entirety.

Where desired, additives other than the pH raising agent may also be introduced into the water in order to influence the properties of the precipitate produced. Thus, certain embodiments of the method include providing the additive in the water before or during the time the water is subjected to the precipitation conditions. Certain calcium carbonate polymorphs may benefit from trace amounts of certain additives. For example, vaterite, a highly unstable polymorph of _CaCO3 that precipitates in a number of different forms and rapidly converts to calcite, can be formed by including trace amounts of lanthanum chloride in calcium carbonate supersaturated solutions Lanthanum was obtained in very high yields. Contemplated additives other than lanthanum include, but are not limited to, transition metals and the like. For example, addition of ferrous or ferric iron is known to favor the formation of disordered dolomite (protodolomite) where it would not otherwise form.

The properties of the precipitate may also be influenced by the choice of an appropriate major ion ratio. The major ion ratio also has a strong influence on polymorph formation. For example, as the magnesium:calcium ratio in water increases, aragonite becomes a favorable polymorph of calcium carbonate compared to low-magnesium calcite. At low magnesium: calcium ratios, low-magnesium calcite is the preferred polymorph.

Precipitation velocity also has a large influence on compound phase formation. The fastest precipitation can be achieved by using the desired crystallization solution. Without crystallization, rapid precipitation can be obtained by rapidly increasing the pH of seawater, which results in a more amorphous component. When silica is present, the faster the reaction rate, the more silica is bound to the carbonate precipitate. The higher the pH, the faster the precipitation and the more amorphous the precipitate.

Thus, a set of precipitation conditions for producing the desired precipitate from water includes, in certain embodiments, the temperature of the water, and the pH, and in some cases the concentration of additives and ionic species in the water. Precipitation conditions may also include factors such as rate of mixing, form of agitation such as sonication, presence of seeds, catalysts, membranes or substrates. In some embodiments, precipitation conditions include supersaturation conditions, temperature, pH, and/or concentration gradients, or cycling or varying any of these parameters. The process used to prepare the carbonate compound precipitate of the present invention may be a batch or continuous process. It should be understood that precipitation conditions may be different to produce a given precipitate in a continuous flow system as compared to a batch system.

In certain embodiments, the contact between water (e.g., alkaline earth metal ion-containing water) and _CO can be achieved using any suitable process (e.g., spray gun, staged flow tube reactor) to control sediment particles size range. In the method and system of the claimed invention, one or more additives may be added to the water source containing metal ions, for example, flocculants, dispersants, surfactants, antiscalants, crystal growth retardants, buried Preservatives, etc., in order to control the size range of sediment particles.

The pH of the water may be raised using any suitable means. Contemplated approaches as described in more detail herein include, but are not limited to: use of pH raising agents, electrochemical methods, use of naturally alkaline water, such as from soda lakes, and the like. In some cases, a pH-raising agent may be used, where examples of such agents include oxides (such as calcium oxide, magnesium oxide, etc.), hydroxides (such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide) , carbonates (such as sodium carbonate), etc. The amount of pH raising agent added to the water will depend on the particular nature of the agent and the volume of water being altered, and will be sufficient to raise the pH of the water to the desired value.

Electrochemical methods and systems that may be used in embodiments of the invention are described below. The method and system use one or more ion selective membranes (low voltage systems for hydroxide generation). These methods and systems are further described in the following documents: International Patent Application PCT/US08/88242, filed December 23, 2008, titled "Low-Energy Electrochemical Hydroxide System and Method," and International Patent Application PCT/US08/88246, Application date on December 23, 2008, title "Low-Energy Electrochemical Proton Transfer System and Method," each of which is fully incorporated herein as a reference.

Low voltage system for the production of hydroxides

A second group of methods and systems for proton removal/hydroxide generation from aqueous solutions involves low energy methods of electrochemically preparing ionic solutions utilizing ion exchange membranes in electrochemical cells. In one embodiment, the system includes an electrochemical system wherein the ion exchange membrane separates a first electrolyte and a second electrolyte, the first electrolyte contacts the anode and the second electrolyte contacts the cathode. In this system, when a voltage is applied across the anode and cathode, hydroxide ions are formed at the cathode and no gas is formed at the anode.

In another embodiment, the system comprises an electrochemical system comprising a first electrolysis cell comprising an anode in contact with a first electrolyte and an anion exchange membrane separating the first electrolyte and a third electrolyte; and Two electrolytic cells comprising a second electrolyte in contact with the cathode and a cation exchange membrane separating the first and third electrolytes; wherein hydroxide ions are formed at the cathode and no gas is formed at the anode when a voltage is applied across the anode and cathode.

In one embodiment, the method includes placing an ion exchange membrane between a first electrolyte and a second electrolyte, the first electrolyte contacting the anode and the second electrolyte contacting the cathode; The ion exchange membrane migrates to form hydroxide ions at the cathode without gas formation at the anode.

In another embodiment, the method includes placing a third electrolyte between the anion exchange membrane and the cation exchange membrane; placing the first electrolyte between the anion exchange membrane and the anode; and placing the second electrolyte between the cation exchange membrane and the cathode; and hydroxide ions are formed at the cathode by applying a voltage to the anode and cathode to cause ions to migrate across the cation exchange membrane and the anion exchange membrane without gas formation at the anode.

By the described methods and systems, low-voltage electrochemical transfer of ionic species from one solution to another provides anionic solutions for various applications, including the preparation of sodium hydroxide solutions for storage Carbon dioxide, as described herein. In one embodiment, a solution comprising OH- is obtained from brine and used for _CO2 sequestration by precipitating calcium and magnesium carbonates and bicarbonates from a salt solution comprising alkaline earth metal ions.

Methods and systems in various embodiments relate to low voltage electrochemical systems and methods for producing sodium hydroxide solutions in aqueous solutions utilizing one or more ion exchange membranes wherein no gas is formed at the anode, And wherein hydroxide ions are formed at the cathode. Thus, in some embodiments, hydroxide ions are formed during the electrochemical process, but no oxygen or chlorine gas is formed. In some embodiments, hydroxide ions are formed in an electrochemical process wherein the voltage applied across the anode and cathode is less than 2.8V, 2.7V, 2.5V, 2.4V, 2.3V, 2.2V, 2.1V, 2.0V , 1.9V, 1.8V, 1.7V, 1.6V, 1.5V, 1.4V, 1.3V, 1.2V, 1.1V, 1.0V, 0.9V, 0.8V, 0.7V, 0.6V, 0.5V, 0.4V, 0.3 V, 0.2V, or 0.1V. In various embodiments, an ionic membrane is utilized to separate the brine in contact with the anode from the solution, such as sodium chloride, in contact with the cathode. When a low voltage is applied across the cathode and anode, a solution such as sodium hydroxide solution is formed in the solution surrounding the cathode; at the same time, an acidified solution including hydrochloric acid is formed in the solution surrounding the anode. In various embodiments, gases such as chlorine or oxygen are not formed at the anode.

In various embodiments, a sodium hydroxide solution can be used to sequester _CO2 , as described herein, and an acidic solution can be used to dissolve calcium and magnesium containing inorganics to provide calcium and magnesium ions for _CO2 sequestration , also as described in this article.

Turning to Figures 8-10, in various embodiments, the system can be adapted for both batch and continuous processes, as described herein. Referring to Figures 8-9, in one embodiment, the system includes an electrochemical cell in which an ion exchange membrane (802, 824) is positioned to separate a first electrolyte (804) from a second electrolyte (806), the first electrolyte contacting the anode (808) and the second electrolyte contacts the cathode (810). As illustrated in Figure 8, an anion exchange membrane (802) is used; in Figure 9, a cation exchange membrane (824) is used.

In various embodiments, as illustrated in Figures 8 and 9, the first electrolyte (804) includes a brine solution, which includes seawater, freshwater, brine, or brackish water, etc.; and the second electrolyte includes substantially chlorinated sodium solution. In various embodiments, the second (806) electrolyte may include seawater or a concentrated solution of sodium chloride. In various embodiments, the anion exchange membrane (802) and cation exchange membrane (824) comprise conventional ion exchange membranes suitable for use in acidic and/or basic solutions at operating temperatures of up to 100°C in aqueous solution. As illustrated in Figures 8 and 9, the first and second electrolytes contact the anode and cathode to complete an electrical circuit including a voltage or current regulator (812). Current/voltage regulators are adapted to increase or decrease the current or voltage across the cathode and anode in the system as required.

Referring to Figures 8 and 9, in various embodiments, the electrochemical cell includes a first electrolyte inlet aperture (814), which can be adapted to feed the first electrolyte (804) into the system and contact the anode (808). Likewise, the cell includes a second electrolyte inlet port (816) for feeding the second electrolyte (806) into the system and in contact with the cathode (810). In addition, the cell includes an outlet aperture (818) for draining the first electrolyte from the cell, and an outlet aperture (820) for draining the second electrolyte from the cell. As will be appreciated by those skilled in the art, the inlet and outlet holes can accommodate various flow regimes, including intermittent, semi-intermittent, or continuous flow. In alternative embodiments, the system includes a tube (822) for directing gas to the anode; in various embodiments, the gas includes hydrogen formed at the cathode (810).

Referring to Figure 8, where an anion membrane (802) is utilized, when a low voltage is applied across the cathode (810) and anode (808), hydroxide ions are formed at the cathode (810) and no gas is formed at the anode (808) . Further, wherein the second electrolyte (806) includes sodium chloride, chloride ions migrate from the second electrolyte (806) to the first electrolyte (804) through the anion exchange membrane (802); form protons at the anode (808); and The cathode (810) forms hydrogen gas. As noted above, gases such as oxygen or chlorine are not formed at the anode (808).

Referring to Figure 9, where a cationic membrane (824) is utilized, when a low voltage is applied across the cathode (810) and anode (808), hydroxide ions are formed at the cathode (810) and no gas is formed at the anode (808) . In various embodiments, the cation exchange membrane (824) comprises a conventional ion exchange membrane suitable for acidic and basic solutions in aqueous solution at operating temperatures up to 100°C. As illustrated in Figure 9, the first and second electrolytes contact the anode and cathode to complete the electrical circuit including voltage and/or current regulators (812). A voltage/current regulator is adapted to increase or decrease the current or voltage across the cathode and anode in the system as required. In a system as illustrated in Figure 9, wherein the second electrolyte (804) comprises sodium chloride, sodium ions migrate from the first electrolyte (804) through the cation exchange membrane (824) to the second electrolyte (806); in Protons are formed at the anode (808); and hydrogen is formed at the cathode (810). As noted above, gases such as oxygen or chlorine are not formed at the anode (808).

As can be understood by those skilled in the art, and with reference to FIG. , an aqueous sodium hydroxide solution will form in the second electrolyte (806). Thus, depending on the voltage applied to the system and the flow rate of the second electrolyte (806) through the system, the pH of the second electrolyte is adjusted. In one embodiment, when 0.1 V or less, 0.2 V or less, 0.3 V or less, 0.4 V or less, 0.5 V or less, 0.6 V or less, 0.7V or less, 0.8V or less, 0.9V or less, 1.0V or less, 1.1V or less, 1.2V or less, 1.3V or less, 01.4V or less, 1.5V or less, 1.6V or less, 1.7V or less, 1.8V or less, 1.9V or less, or 2.0V or less potential, the pH of the second electrolyte solution increases; in another implementation In one embodiment, when a voltage of 0.1V to 2.0V is applied across the anode and cathode, the pH of the second electrolyte increases; in yet another embodiment, when a voltage of 0.1V to 1V is applied across the anode and cathode , the pH of the second electrolyte solution increases. Similar results can be achieved with voltages of 0.1 V to 0.8 V; 0.1 V to 0.7 V; 0.1 V to 0.6 V; 0.1 V to 0.5 V; 0.1 V to 0.4 V; and 0.1 V to 0.3 V across the electrodes. Exemplary results obtained with this system are summarized in Table 2.

Table 2. Low energy electrochemical methods and systems.

The voltage across the electrodes time (seconds) Initial pH at the anode Endpoint pH at the anode Initial pH at the cathode Endpoint pH at the cathode 0.6 2000 6.7 3.8 6.8 10.8 1.0 2000 6.6 3.5 6.8 11.1

In this example, both the anode and cathode included platinum, and the first and second electrolytes included sodium chloride solution.

Likewise, referring to FIG. 9, in the second electrolyte (806), when hydroxide ions enter the solution from the anode (810) while sodium ions migrate from the first electrolyte to the second electrolyte, in the second electrolyte (806) Gradually an aqueous solution of sodium hydroxide will form. Depending on the voltage applied across the system and the flow rate of the second electrolyte through the system, the pH of the solution will be adjusted. In one embodiment, when 0.1 V or less, 0.2 V or less, 0.3 V or less, 0.4 V or less, 0.5 V or less, 0.6 V or less, 0.7V or less, 0.8V or less, 0.9V or less, 1.0V or less, 1.1V or less, 1.2V or less, 1.3V or less, 1.4V or less, 1.5V or less, 1.6V or less, 1.7V or less, 1.8V or less, 1.9V or less, or 2.0V or less voltage, the pH of the second electrolyte solution increases; in another implementation In one embodiment, when a voltage of 0.1V to 2.0V is applied across the anode and cathode, the pH of the second electrolyte increases; in yet another embodiment, when a voltage of 0.1V to 1V is applied across the anode and cathode , the pH of the second electrolyte solution increases. Similar results can be achieved with voltages of 0.1 V to 0.8 V; 0.1 V to 0.7 V; 0.1 V to 0.6 V; 0.1 V to 0.5 V; 0.1 V to 0.4 V; and 0.1 V to 0.3 V across the electrodes. In one embodiment, a voltage of 0.6V or less is applied across the anode and cathode; in another embodiment, a voltage of 0.1V to 0.6V or less is applied across the anode and cathode; in yet another embodiment In the scheme, a voltage of 0.1 to 1 V or less is applied across the anode and cathode.

In various embodiments and with reference to Figures 8-10, hydrogen gas formed at the cathode (810) is passed to the anode (808), where, without being bound by any theory, it is believed that the gas adsorbs and/or absorbs to the anode and subsequently form protons at the anode. Thus, as can be appreciated, where protons are formed at the anode and chloride ions migrate to the first electrolyte (804) such as in FIG. 8 or sodium ions migrate out of the first electrolyte such as in FIG. Next, an acidic solution comprising eg hydrochloric acid is obtained in the first electrolyte (804).

In another embodiment, as illustrated in Figure 10, the system includes an electrochemical cell comprising an anode (808) in contact with a first electrolyte (804) and an anion exchange (830) separating the first and third electrolytes (830). a membrane (802); and a second electrolytic cell comprising a second electrolyte (806) contacting the cathode (880) and a cation exchange membrane (824) separating the first and third electrolytes, wherein applied across the anode and cathode When the voltage is high, hydrogen ions are formed at the cathode and gas is formed at the anode. Like the systems of Figures 8 and 9, the system of Figure 10 is adaptable to both batch and continuous processes.

In various embodiments, as illustrated in FIG. 10, the first electrolyte (804) and the second electrolyte (806) include a saline solution, the latter including seawater, fresh water, salt water, or brackish water, etc.; and the second electrolyte A solution consisting essentially of sodium chloride. In various embodiments, the first (804) and second (806) electrolytes can include seawater. In the embodiment illustrated in Figure 10, the third electrolyte (830) comprises a substantially sodium chloride solution.

In various embodiments, the anion exchange membrane (802) comprises any suitable anion exchange membrane suitable for use in acidic and basic solutions in aqueous solution at operating temperatures up to 100°C. Likewise, the cation exchange membrane (824) includes any suitable cation exchange membrane suitable for use in acidic and basic solutions in aqueous solution at operating temperatures up to 100°C.

As illustrated in Figure 10, in various embodiments, the first electrolyte (804) contacts the anode (808) and the second electrolyte (806) contacts the cathode (810). A third electrolyte (830) in contact with the anion and cation exchange membranes completes the circuit including a voltage or current regulator (812). Current/voltage regulators are adapted to increase or decrease the current or voltage across the cathode and anode in the system as required.

Referring to FIG. 10, in various embodiments, the electrochemical cell includes a first electrolyte inlet port (814) adaptable for introducing a first electrolyte 804 into the system; a second electrolyte port (806) for introducing a second electrolyte (806) into the system; an inlet port (816); and a third inlet port (826) for introducing a third electrolyte into the system. In addition, the cell includes an outlet hole (818) for discharging the first electrolyte; an outlet hole (820) for discharging the second electrolyte; and an outlet hole (828) for discharging the third electrolyte. As will be appreciated by those skilled in the art, the inlet and outlet holes can accommodate various flow regimes, including intermittent, semi-intermittent, or continuous flow. In alternative embodiments, the system includes a tube (822) for directing gas to the anode; in various embodiments, the gas is hydrogen formed at the cathode (810).

Referring to Figure 10, when a low voltage is applied across the cathode (810) and anode (808), hydroxide ions are formed at the cathode (810), and no gas is formed at the anode (808). Further, when the third electrolyte (830) includes sodium chloride, chloride ions migrate from the third electrolyte (830) to the first electrolyte (804) through the anion exchange membrane (802); sodium ions migrate from the third electrolyte (802) to the first electrolyte (804); 830) migrates to the second electrolyte (806); protons are formed at the anode; and hydrogen is formed at the cathode. As noted above, gases such as oxygen or chlorine are not formed at the anode (808).

As can be understood by those skilled in the art, and with reference to FIG. 10, in the second electrolyte (806), when hydroxide ions enter the solution from the cathode (810) while chloride ions migrate out of the third electrolyte, gradually in An aqueous sodium hydroxide solution will form in the second electrolyte (806). Depending on the voltage applied across the system and the flow rate of the second electrolyte through the system, the pH of the solution will be adjusted. In one embodiment, when 0.1 V or less, 0.2 V or less, 0.3 V or less, 0.4 V or less, 0.5 V or less, 0.6 V or less, 0.7V or less, 0.8V or less, 0.9V or less, 1.0V or less, 1.1V or less, 1.2V or less, 1.3V or less, 01.4V or less, 1.5V or less, 1.6V or less, 1.7V or less, 1.8V or less, 1.9V or less, or 2.0V or less or less, the pH value of the second electrolyte solution increases; In another embodiment, when a voltage of 0.1 V to 2.0 V is applied across the anode and cathode, the pH of the second electrolyte increases; in yet another embodiment, when a voltage of 0.1 V to 1 V is applied across the anode and cathode When the voltage is increased, the pH value of the second electrolyte solution increases. Similar results can be achieved with voltages of 0.1 V to 0.8 V; 0.1 V to 0.7 V; 0.1 V to 0.6 V; 0.1 V to 0.5 V; 0.1 V to 0.4 V; and 0.1 V to 0.3 V across the electrodes. In one embodiment, a voltage of 0.6V or less is applied across the anode and cathode; in another embodiment, a voltage of 0.1V to 0.6V or less is applied across the anode and cathode; in yet another embodiment In the scheme, a voltage of 0.1V to 1V or less is applied across the anode and cathode.

Also, referring to Figure 10, in the first electrolyte (804), when protons are formed at the anode (808) and go into solution while chloride ions migrate from the third electrolyte to the first electrolyte, in the first electrolyte (804) Gradually an acidic solution will form. Depending on the voltage applied across the system and the flow rate of the second electrolyte through the system, the pH of the solution will be adjusted. In one embodiment, when 0.1 V or less, 0.2 V or less, 0.3 V or less, 0.4 V or less, 0.5 V or less, 0.6 V or less, 0.7V or less, 0.8V or less, 0.9V or less, 1.0V or less, 1.1V or less, 1.2V or less, 1.3V or less, 1.4V or less, 1.5V or less, 1.6V or less, 1.7V or less, 1.8V or less, 1.9V or less, or 2.0V or less voltage, the pH of the second electrolyte solution increases; in another implementation In one embodiment, when a voltage of 0.1V to 2.0V is applied across the anode and cathode, the pH of the second electrolyte increases; in yet another embodiment, when a voltage of 0.1V to 1V is applied across the anode and cathode , the pH of the second electrolyte solution increases. Similar results can be achieved with voltages of 0.1 V to 0.8 V; 0.1 V to 0.7 V; 0.1 V to 0.6 V; 0.1 V to 0.5 V; 0.1 V to 0.4 V; and 0.1 V to 0.3 V across the electrodes. In one embodiment, a voltage of 0.6V or less is applied across the anode and cathode; in another embodiment, a voltage of 0.1V to 0.6V or less is applied across the anode and cathode; in yet another embodiment In the scheme, a voltage of 0.1 V to 1 V or less was applied across the anode and cathode, as shown in Table 2.

As illustrated in Figure 10, the hydrogen gas formed at the cathode (810) is passed to the anode (808), where, without being bound by any theory, it is believed that the hydrogen gas is adsorbed and/or absorbed into the anode and subsequently the protons in An anode is formed and enters the first electrolyte (804). Furthermore, in various embodiments as illustrated in Figures 8-10, gases such as oxygen or chlorine are not formed at the anode (808). Thus, as can be appreciated, hydrochloric acid is obtained in the first electrolyte (804) with the formation of protons at the anode and the migration of chlorine gas to the first electrolyte.

As can be understood by those skilled in the art, and with reference to FIG. , an aqueous sodium hydroxide solution will form in the second electrolyte (806). Thus, depending on the voltage applied to the system and the flow rate of the second electrolyte (806) through the system, the pH of the second electrolyte is adjusted. In one embodiment, when 0.1 V or less, 0.2 V or less, 0.3 V or less, 0.4 V or less, 0.5 V or less, 0.6 V or less, 0.7V or less, 0.8V or less, 0.9V or less, 1.0V or less, 1.1V or less, 1.2V or less, 1.3V or less, 1.4V or less, 1.5V or less, 1.6V or less, 1.7V or less, 1.8V or less, 1.9V or less, or 2.0V or less voltage, the pH of the second electrolyte solution increases; in another implementation In one embodiment, when a voltage of 0.1V to 2.0V is applied across the anode and cathode, the pH of the second electrolyte increases; in yet another embodiment, when a voltage of 0.1V to 1V is applied across the anode and cathode , the pH of the second electrolyte solution increases. Similar results can be achieved with voltages of 0.1 V to 0.8 V; 0.1 V to 0.7 V; 0.1 V to 0.6 V; 0.1 V to 0.5 V; 0.1 V to 0.4 V; and 0.1 V to 0.3 V across the electrodes. In one embodiment, when a voltage of 0.6 V or less is applied across the anode and cathode, the pH of the second electrolyte solution increases; in another embodiment, when a voltage of 0.1 V to At a voltage of 0.6 V, the pH of the second electrolyte increases; in yet another embodiment, the pH of the second electrolyte solution increases when a voltage of 0.1 V to 1 V or less is applied across the anode and cathode.

Optionally, by bubbling the gas into the second electrolyte solution 806, gas including _CO2 is dissolved into the second electrolyte solution as described above. In an optional step, the resulting second electrolyte solution is used to precipitate carbonate and/or bicarbonate compounds such as calcium or magnesium carbonate and/or their bicarbonate salts, as described herein. Precipitated carbonate compounds can be used as cement and building materials, as described herein.

In another optional step, the acidified first electrolyte solution 804 is utilized to dissolve calcium and/or magnesium rich minerals, such as mafic minerals, including serpentine or olivine, for use as precipitated carbonates and A solution of bicarbonate, as described herein. In various embodiments, the resulting solution can be used as a second electrolyte solution. Likewise, in embodiments where hydrochloric acid is generated in the first electrolyte 804, hydrochloric acid may be used instead of, or in addition to, the acidified second electrolyte solution.

The embodiments described above produce an electrolyte solution enriched in bicarbonate ions and carbonate ions, or a combination thereof, and an acidified stream. Acidified streams can also be used in various chemical processes. For example, an acidifying stream may be used to dissolve calcium and/or magnesium rich minerals such as serpentine and olivine to produce an electrolyte solution for reservoir 816 (or 832 ). Such an electrolyte solution may be dosed with bicarbonate ions and subsequently made basic enough to precipitate carbonate compounds as described herein.

In some embodiments, a first electrochemical process can be used to remove protons from solution to facilitate _CO2 absorption without concomitant generation of hydroxides, while a second electrochemical process can be used to generate hydroxides for further removal of protons Instead, the equilibrium shifts towards the carbonate and causes the precipitation of the carbonate. The two processes may have different voltage requirements, for example, the first process may require a lower voltage than the second process, thereby minimizing the total voltage used in the method. For example, the first process may be a two-electrode method as described in U.S. Patent Application 12/344,019 (December 24, 2008, which is incorporated herein by reference in its entirety), at 1.0 V or less, or 0.9 V or less, or 0.8V or less, or 0.7V or less, or 0.6V or less, or 0.5V or less, or 0.4V or less, or 0.3V or less, or 0.2V or less, or 0.1V or less operation, while the second process may be a low pressure hydroxide production method as described above, at 1.5V or less, or 1.4V or less, or 1.3V or less, or 1.2V or less Small, or 1.1V or less, 1.0V or less, or 0.9V or less, or 0.8V or less, or 0.7V or less, or 0.6V or less, or 0.5V or less, Or 0.4V or less, or 0.3V or less, or 0.2V or less, or 0.1V or less operation. For example, in some embodiments the first process is a two electrode process operating at 0.6V or less, while the second process is a low pressure hydroxide production process operating at 1.2V or less.

The electrochemical methods described in the following documents are also considered: U.S. Patent Application (Publication No.) 2006/0185985, published August 24, 2006; U.S. Patent Application (Publication No.) 2008/0248350, published 2008 October 9, 2008; International Patent Application (publication number) WO 2008/018928, published on February 14, 2008; and International Patent Application (publication number) WO 2009/086460, published on July 7, 2009 , each of which is incorporated herein by reference in its entirety.

Stoichiometry dictates _that producing the carbonate to be precipitated in order to sequester CO from _a CO source requires the removal of two protons from the original carbonic acid formed when _CO is dissolved in water (see Eq. 1-5). Removal of the first proton produces bicarbonate and removal of the second produces carbonate, which can precipitate, for example, in the form of a carbonate of a secondary cation, such as magnesium carbonate or calcium carbonate. Removing two protons requires some method or combination of methods, and these usually require energy. For example, if protons are removed by adding NaOH, the renewable NaOH source is usually the chloralkali method, which uses electrochemical methods and requires at least 2.8 V and a fixed amount of electrons per mole of NaOH . This energy requirement can be expressed in terms of a carbon footprint, ie the amount of carbon produced to provide the energy to drive the process.

A suitable way to express the carbon footprint of a given method of proton removal is as a percentage of _CO2 withdrawn from the _CO2 source. That is, the energy required to remove protons can be expressed in terms of _CO2 emissions from conventional power generation methods that generate this energy, which in turn can be expressed as a percentage of _CO2 withdrawn from the _CO2 source. For convenience, and as a definition in this aspect of the invention, " _CO2 produced" in the process will be considered to provide enough energy to remove two protons in a conventional coal/steam power plant CO ₂ will be produced. For such power plants of the last few years, data are publicly available which show tons of _CO2 are produced per total MWh of energy produced. See, eg, a website with an address generated by combining "http://carma." and "org/api/". For the purposes of the definitions here, a value of 1 tonne of CO ₂ /MWh will be used, which corresponds closely to a typical coal-fired power plant; for example the WA Parish plant produced 18,200,000 MWh of energy in 2000 while producing approximately 19,500,000 tonnes of CO ₂ , and currently produces 21,300,00 MWh of energy, while producing 20,900,000 tons of CO ₂ , which on average is very close to the defined 1 ton of CO ₂ /MWh, which will be used in this invention. These values can thus be used to calculate the _CO2 production necessary to remove enough protons to remove _CO2 from the gas stream and compare it to the _CO2 removed. For example, in a process utilizing the chlor-alkali process, which operates at 2.8V to provide alkali and is used to sequester _CO2 from a coal/steam power plant, using a ratio of 1 ton _CO2 /1MWh for supplying energy The amount of _CO2 produced by the power plant with the removal of two protons from the production of the base by the chlor-alkali process is much higher than 200% of the amount of _CO2 sequestered by the removal of the two protons and the precipitation of the _CO2 in a stable form. As a further proviso to the definition of " _CO2 produced" in this aspect of the invention, in all " _CO2 produced" no energy load is included, for example, attributable to reusing the by-products of the process in order to remove protons Theoretical or practical calculations of the reduction (for example, in the case of the chlor-alkali process, the use of the hydrogen produced in the process in a fuel cell or by direct combustion to generate energy). In addition, theoretical or practical supplementation of electricity supplied by power plants using renewable energy sources, such as energy sources that generate little or no carbon dioxide, such as wind energy, solar energy, tidal energy, hydroelectric energy, etc., is not considered. If the method of proton removal involves the use of hydroxide or other bases, including naturally occurring or stored bases, the amount of _CO2 produced will be the amount stoichiometrically calculated based on the method by which the base was produced, e.g. for industrial For bases produced, the standard chlor-alkali method or other method by which bases are produced, and for trona, the best theoretical model for the natural production of bases.

Using this definition of " _CO2 produced" in some embodiments, the invention includes the formation of stable _CO2 -containing precipitates from gaseous sources of anthropogenic _CO2 , wherein the precipitates are formed using A process for the deprotonation of an aqueous solution of _CO2 in which part or all of the gaseous source of _CO2 is dissolved, and wherein the _CO2 produced by the process for deprotonation is less than 100, 90, 80, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5% of the _CO2 removed from the _CO2 gas source by the formation of the precipitate. In some embodiments, the invention includes forming a stable _CO2 -containing precipitate from a gas source of anthropogenic _CO2 , wherein the precipitate is formed using a gas source from which some or all of the _CO2 is dissolved. A method for the deprotonation of an aqueous solution of _CO2 , and wherein the _CO2 produced by the deprotonation method is less than 70% of the _CO2 removed from the _CO2 gas source by the formation of precipitates. In some embodiments, the invention includes forming a stable _CO2 -containing precipitate from a gas source of anthropogenic _CO2 , wherein the precipitate is formed using a gas source from which some or all of the _CO2 is dissolved. A method for the deprotonation of an aqueous solution of _CO2 , and wherein the _CO2 produced by the deprotonation method is less than 50% of the _CO2 removed from the _CO2 gas source by the formation of precipitates. In some embodiments, the invention includes forming a stable _CO2 -containing precipitate from a gas source of anthropogenic _CO2 , wherein the precipitate is formed using a gas source from which some or all of the _CO2 is dissolved. A method for the deprotonation of an aqueous solution of _CO2 , and wherein the _CO2 produced by the deprotonation method is less than 30% of the _CO2 removed from the _CO2 gas source by the formation of precipitates. In some embodiments, the method of removing protons is a method, such as an electrochemical method, as described herein, that removes protons without generating a base, eg, hydroxide. In some embodiments, the method of removing protons is a method, such as an electrochemical method, as described herein, which removes protons by generating a base, eg, a hydroxide. In some embodiments, the method of removing protons is a combination of: a method, such as an electrochemical method, as described herein, which removes protons without generating a base, e.g., hydroxide, and a method, Such as electrochemical methods, as described herein, which remove protons by generating a base, eg, hydroxide. In some embodiments, the method of proton removal includes electrochemical methods, direct (eg, direct removal of protons) or indirect (eg, generation of hydroxides) proton removal. In some embodiments, a combination of methods, e.g., electrochemical methods, is used, wherein a first method, e.g., electrochemical method, removes protons directly, and a second method, e.g., electrochemical method, removes protons indirectly (e.g., by producing hydroxide).

In some cases, precipitation of the desired product occurred after _CO2 addition (eg, as described above) without the addition of a source of divalent metal ions. Thus, after the water is fed in the feed reactor with _CO , the water is then not in contact with a source of divalent metal ions, such as one or more divalent metal ion salts, eg, calcium chloride, magnesium chloride, sea salt, and the like.

In one embodiment of the present invention, a carbonate precipitation process may be used to selectively precipitate calcium carbonate material from solution to provide the desired ratio of magnesium to calcium, followed by additional _CO dosing, and in some implementations scheme, additional MgMg ion dosing, and a final carbonate precipitation step. This embodiment can be used to utilize concentrated water such as desalinated brine, where the cation content is high enough that adding more Mg ions is difficult. This embodiment can also be used for solutions of any concentration where it is desired to produce two distinct products, a predominantly calcium carbonate material, and then a magnesium carbonate predominant material.

The yield of product from a given precipitation reaction can vary depending on many factors, including the particular type of water used, whether the water is supplemented with divalent metal ions, the particular precipitation protocol used, and the like. In some cases, the precipitation process used to precipitate the product is a high yield precipitation process. In these cases, for each liter of water, produced by a single precipitation reaction (this refers to a single time the water is subjected to precipitation conditions, such as increasing the pH to a value of 9.5 or higher, such as 10 or higher, as described in more detail above The amount of product reviewed) may be 5 g or more, such as 10 g or more, 15 g or more, 20 g or more, 25 g or more, 30 g or more, 35 g or more, 40 g or more, 45 g or more, 50g or more, 60g or more, 70g or more, 80g or more, 90g or more, 100g or more, 120g or more, 140g or more, 160g or more, 180g or more, 200 g or more of storage-stable carbon dioxide sequestration products. In some cases, the amount of product produced is 5 to 200 g, such as 10 to 100 g, including 20 to 100 g, per liter of water. In cases where the divalent metal ion content of the water is not supplemented prior to subjecting the water to precipitation conditions (e.g. where the water is seawater and the seawater is not supplemented with one or more sources of divalent metal ions), the yield of product can be It is 5 to 20 g product/1 liter of water, such as 5 to 10, eg, 6 to 8, g product/1 liter of water. In other cases, where the water is supplemented with a source of divalent metal ions, such as magnesium and/or calcium ions, the yield of product may be higher, 2-fold, 3-fold, 5-fold, 10-fold, 20-fold or higher, such that The yield of such a process may in some embodiments be from 10 to 200, such as from 50 to 200 including 100 to 200 g of product per liter of water subjected to the precipitation conditions.

The yield of product from a given precipitation reaction can vary depending on many factors, including the particular type of water used, whether the water is supplemented with divalent metal ions, the particular precipitation protocol used, and the like. In some cases, the precipitation process used to precipitate the product is a high yield precipitation process. In this case, under an average of 72 hours of continuous operation (i.e. applying precipitation conditions to the water or the absorption solution), the amount of product produced from 1 liter of water (i.e. the absorption solution) may be, for each liter of water, 5g or more, such as 10g or more, 15g or more, 20g or more, 25g or more, 30g or more, 35g or more, 40g or more, 45g or more, 50g or more , 60g or more, 70g or more, 80g or more, 90g or more, 100g or more, 120g or more, 140g or more, 160g or more, 180g or more, 200g or more Storage-stable carbon dioxide sequestration products. In some cases, the amount of product produced per liter of water is 5 to 200 g, such as 10 to 100 g, including 20 to 100 g, under an average of 72 hours of continuous operation. In cases where the divalent metal ion content of the water is not supplemented prior to subjecting the water to precipitation conditions (e.g. where the water is seawater and the seawater is not supplemented with one or more sources of divalent metal ions), the yield of product can be From 5 to 20 g product/1 liter of water, such as 5 to 10, eg, 6 to 8, g product/1 liter of water, at an average of 72 hours of continuous operation. In other cases, where the water is supplemented with a source of divalent metal ions, such as magnesium and/or calcium ions, the yield of product may be higher, 2-fold, 3-fold, 5-fold, 10-fold, 20-fold or higher, such that The yield of such a process may in some embodiments range from 10 to 200, such as 50 to 200 including 100 to 200 g of product per liter of water subjected to the precipitation conditions, under an average of 72 hours of continuous operation.

In certain embodiments, a multi-step approach is used. In these embodiments, a carbonate precipitation process may be used to selectively precipitate calcium carbonate material from solution, followed by additional steps of _CO dosing and subsequent carbonate precipitation. The steps of additional _CO2 dosing and carbonate precipitation can sometimes be repeated 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more times, each cycle precipitating an additional amount of carbonate Material. Sometimes the final pH is from pH 8 to pH 10, such as pH 9 to pH 10, including pH 9.5 to pH 10, eg, pH 9.6 to pH 9.8.

In certain embodiments, two or more reactors may be used in order to carry out the methods described herein. In these embodiments, the process can include a first reactor and a second reactor. In these cases, the first reactor was used to contact the initial water with the source of magnesium ions and to feed the initial water with _CO2 , as described above. The water may be stirred to facilitate dissolution of the source of magnesium ions and to facilitate initial water contact with _CO2 . Occasionally, agitation of the CO2 _- fed water was stopped before the _CO2- fed water was transferred to the second reactor so that undissolved solids could settle by gravity. The _CO fed water is then transferred from the first reactor to the second reactor. After transferring the CO2 _- fed water to the second reactor, a carbonate precipitation step can be performed, as described herein.

In certain embodiments, multi-step processes, as described above, using two or more reactors, as described above, can be used to carry out the methods described herein. In these embodiments, the first reactor is used to contact the initial water with the source of magnesium ions and to feed the initial water with _CO , as described above. Subsequently, CO _fed water was transferred from the first reactor to the second reactor for carbonate precipitation reaction. In certain embodiments, one or more additional steps of _CO dosing and subsequent carbonate precipitation may be performed in a second reactor, as described above.

In certain embodiments, precipitation conditions may be used that favor the formation of a particular morphology of the carbonate compound precipitate. For example, precipitation conditions may be used that favor the formation of an amorphous carbonate compound precipitate over the formation of a crystalline carbonate compound precipitate. In these cases, in addition to contacting the initial water with a source of magnesium ions and dosing the initial water with CO ₂ , a precipitation facilitator may be added as described above. In these cases, the precipitation facilitator promotes the formation of carbonate compound precipitates at lower pH sufficient for nucleation but insufficient for crystal formation and growth. Examples of precipitation facilitators include, but are not limited to, aluminum sulfate ( _Al2SO4 )3. In certain embodiments, the amount of precipitation facilitator added is 1 ppm-1000 ppm, such as 1 ppm-500 ppm, including 10 ppm-200 ppm, such as 25 ppm-75 ppm. In addition, during the formation of carbonate compound precipitates, by alternating _CO2 feeding and subsequent carbonate precipitation, as described above, the pH of the water can be maintained at 6-8, such as 7-8.

Alternatively, in other embodiments, precipitation conditions may be used that favor the formation of a crystalline carbonate compound precipitate over the formation of an amorphous carbonate compound precipitate.

The description below with respect to the figures of the present application provides more details regarding the specific precipitation schemes used in certain embodiments of the present invention.

After producing the precipitated product from water, a composition is produced that includes the precipitated product and mother liquor (ie, the remaining liquid from which the precipitated product was produced). This composition may be a slurry of precipitate and mother liquor.

As noted above, in sequestering carbon dioxide, the precipitated product is handled in some way after its production. The phrase "processing" means that a product is placed in a storage location or for further use in another product (i.e., a manufactured or manufactured item) where at least it is stored in that other product for the expected life of that other product Expect. In some cases, this processing step includes transporting the aforementioned slurry composition to a long-term storage location. The storage location may be an aboveground location, an underground location or an underwater location. In these embodiments, the supernatant component of the slurry may be naturally separated from the precipitate, such as by evaporation, dispersion, etc., after the slurry is placed in the storage location.

Where desired, the resulting precipitated product can be separated from the supernatant component of the slurry. Isolation of the precipitated product can be achieved using any of a number of suitable methods. As further detailed herein, a liquid-solid separator such as Epuramat's Extrem-Separator ("ExSep") liquid-solid separator, Xerox PARC's spiral concentrator, or Epuramat's ExSep or Xerox PARC's Variations of any of the spiral concentrators may be used in some embodiments. Isolation may also be achieved by drying the precipitated product to produce a dry precipitated product. The drying procedure considered involves filtering the precipitate from the mother liquor to produce a filtrate followed by air drying of the filtrate. In case the filtrate is air-dried, the air-drying can be at a temperature of -70 to 120 °C, as desired. In some cases, drying may involve placing the slurry in a dry location, such as a tailings pond, allowing the liquid components of the sediment to evaporate and leaving the desired dry product. Also contemplated is a freeze-drying (ie, lyophilization) procedure in which the precipitate is frozen, the ambient pressure is reduced and enough heat is added that the frozen water in the material sublimates directly from the frozen precipitate phase to gas. Yet another drying process considered is spray drying, in which the liquid containing the precipitate is dried by passing its feed through hot gas, for example, where the liquid feed is pumped through an atomizer into the main drying chamber and the hot gas Pass in either co-current or counter-current relative to the direction of the nebulizer.

Where the precipitated product is separated from the mother liquor, the resulting precipitate can be treated in various ways, as explained in further detail below. For example, sediment can be used as a component of building materials, as discussed in more detail below. Alternatively, the sediment can be placed in a long-term storage location (sometimes referred to in the art as a carbon bank), where the location can be an aboveground location, an underground location, or an underwater location. More details on the considered processing flow are provided below.

The resulting mother liquor can also be processed, as desired. For example, the mother liquor can be returned to the source of the water, eg, the ocean, or to another location. In certain embodiments, the mother liquor can be contacted with a source of _CO2 , eg, as described above, to sequester additional _CO2 . For example, where the mother liquor is to be returned to the ocean, the mother liquor may be contacted with a gas source of _CO2 in a manner sufficient to increase the concentration of carbonate ions present in the mother liquor. Contacting can be performed using any suitable procedure, such as those described above. In certain embodiments, the mother liquor has an alkaline pH, and the contacting with the source of _CO2 is performed in a manner sufficient to lower the pH to 5-9, such as 6-8.5, including 7.5-8.2.

The method of the present invention may be carried out on land or sea, for example, at a land location where suitable water is present or transported to the location, or in the ocean or other alkaline earth metal-containing water bodies (which are naturally occurring or man-made) of). In certain embodiments, the above methods are performed using a system, wherein such systems include those described in more detail below.

The above section of the application provides an overview of various aspects of the methods of the invention. Certain embodiments of the invention will now be further reviewed in more detail, based on certain figures of the invention.

Figure 6A provides a schematic flow diagram of a carbon dioxide sequestration method that can be implemented in a system, where the system can be represented as a stand-alone unit or as an integrated part of another type of unit such as a power generation unit, cement production unit, and the like. In Fig. 6A, water 10 is conveyed to a precipitation reactor 20, eg, by pipeline or other suitable means, and subjected to carbonate mineral precipitation conditions. The water used in the process illustrated in Figure 6A is water that includes, for example, one or more alkaline earth metal ions such as Ca2+ and Mg2+. In certain embodiments of the invention, the water contemplated is water comprising calcium in amounts ranging from 50 ppm to 20,000 ppm, such as from 200 ppm to 5000 ppm and including from 400 ppm to 1000 ppm. Also contemplated is water that includes magnesium in amounts ranging from 50 ppm to 40,000 ppm, such as from 100 ppm to 10,000 ppm and including from 500 ppm to 2500 ppm. In an embodiment of the invention, the water (eg, alkaline earth metal ion-containing water) is brine. As noted above, contemplated brines include many different types of aqueous fluids other than freshwater, such as brackish water, seawater, and brine (including artificial brines such as geothermal plant wastewater, desalination wastewater, etc., as well as natural brines that exist), and other saline-alkaline brines that are more salinity than freshwater. Brine is water saturated or nearly saturated with salt and has a salinity of 50 ppt (parts per thousand) or more. Brackish water is water that is more mellow than freshwater, but not as mellow as seawater, having a salinity of 0.5-35ppt. Seawater may be water from the sea or ocean and has a salinity of about 35 to about 50 ppt. Fresh water is water with a salinity of less than 5 ppt dissolved salts. The brine under consideration may be obtained from naturally occurring sources such as seas, oceans, lakes, swamps, estuaries, lagoons, etc. or from man-made sources, as desired.

As mentioned above, water under consideration also includes fresh water. In certain embodiments, the water used in the present invention may be a mineral-rich, eg, calcium and/or magnesium-rich freshwater source. In some embodiments, fresh water, such as calcium-enriched water, can incorporate magnesium silicate minerals, such as olivine or serpentine, in a solution that becomes acidic due to the addition of carbon dioxide from carbonic acid, the The carbonic acid dissolves the magnesium silicate, resulting in the formation of calcium magnesium silicate carbonate compounds. In certain embodiments, the water source may be fresh water to which metal ions, eg, sodium, potassium, calcium, magnesium, etc., have been added. Metal ions may be added to the freshwater source using any suitable procedure, for example, in the form of a solid, aqueous solution, suspension, and the like.

In certain embodiments, water may be obtained from an industrial facility that also provides a gaseous waste stream. For example, in water cooled industrial plants, such as seawater cooled industrial plants, the water that has been used by the industrial plant can then be sent to the precipitation system and used as water in the precipitation reaction. Where desired, the water can be cooled before entering the precipitation reactor. Such an approach may be used, for example, with a flow-through cooling system. For example, a municipal or agricultural water supply can be used as a flow-through cooling system for industrial equipment. The water from the industrial facility can then be used in the sedimentation process, where the output water has reduced hardness and greater purity. Where desired, such systems may be modified to include safety measures, for example, to detect tampering (such as adding poisons) and to cooperate with government agencies such as Homeland Security or other agencies. Additional interference or attack protection measures may be used in such embodiments.

As shown in Figure 6A, industrial facility gaseous waste stream 30 contacts water in precipitation step 20 to produce CO ₂ fed water (which may occur in a feed reactor, in certain embodiments). Water may be an absorption solution, wherein the absorption solution allows introduction of carbon dioxide and/or other components from the gas into the absorption solution. The absorption solution may be brine, (eg sea water and/or brine), or an alkaline solution. The absorption solution may include solid particulate matter and may be described as a slurry. CO2 _- fed water refers to water that has been in contact with _CO2 gas, where the _CO2 molecules have combined with water molecules to produce, for example, carbonic acid, bicarbonate and carbonate ions. Adding water in this step results in an increase in the " _CO2 content" of the water, for example in the form of carbonic acid, bicarbonate and carbonate ions, and a concomitant reduction in the amount of _CO2 of the waste stream in contact with the water. In some embodiments, the _CO fed water is acidic, having a pH of 6.0 or less, such as 4.0 or less, and including 3.0 and less. In certain embodiments, the amount of CO of the _gas used to feed the water is reduced by 85% or more, such as 99% or more, as a result of the contacting step, such that the process removes 50% or more, such as 75% % or more, eg, 85% or more, including 99% or more of the _CO2 originally present in the gaseous waste stream in contact with the water. Contacting processes considered include, but are not limited to: direct contacting processes, e.g., bubbling gas through a volume of water, co-current contacting, i.e. contact between gas-liquid phase streams flowing in the same direction, countercurrent contacting, i.e. flowing in opposite directions The contact between the gas-liquid phase streams, and so on. The gas stream may contact the water source vertically, horizontally, or at some other angle.

The _CO2 may be contacted with a water source from one or more of the following locations: below, above, or at the surface level of the water (eg, alkaline earth metal ion-containing water). Contact can be achieved by using dippers, bubblers, fluid venturi reactors, spargers, gas filters, sprayers, trays, catalytic bubble column reactors, suction tube reactors or packed column reactors, etc. , which may be appropriate. Where desired, two or more different _CO2- feeding reactors (such as columns or other types of reactor configurations) can be used, for example, in series or in parallel, such as three or more, four or more, etc. In certain embodiments, various means, e.g., mechanical stirring, electromagnetic stirring, rotators, shakers, vibrators, blowers, sonication, for stirring or agitating the reaction solution, are used to increase _CO and water sources contact between.

In the embodiment depicted in FIG. 6A , water from water source 10 ( _e.g. , water comprising alkaline earth metal ions) is first spiked with _CO to produce CO _- fed water, which is then subjected to carbonate mineral precipitation conditions . As depicted in Figure 6A, in the precipitation step 20, the _CO2 gas stream 30 is contacted with water. In the precipitation step 20, the provided gas stream 30 is contacted with suitable water to produce CO ₂ fed water. CO2 _- fed water is water that has been in contact with _CO2 gas, where the _CO2 molecules have combined with water molecules to produce, for example, carbonic acid, bicarbonate and carbonate ions. Adding water in this step results in an increase in the " _CO2 content" of the water, for example in the form of carbonic acid, bicarbonate and carbonate ions, and a concomitant decrease in the _pCO2 of the waste stream in contact with the water. The _CO fed water may be acidic, having a pH of 6 or less, such as 5 or less, and including 4 and less. In some embodiments, the _CO fed water is not acidic, such as having a pH of 7 or greater, such as 7-10, or 7-9, or 7.5-9.5, or 8-10, or 8-9.5, Or a pH of 8-9. In certain embodiments, the _CO2 concentration of the gas used to feed the water is 10% or higher, 25% or higher, including 50% or higher, such as 75% or higher.

_CO2 feeding and carbonate mineral precipitation can be performed in the same or different reactors of the system. Thus, according to certain embodiments of the invention, as illustrated at step 20 in Figure 6A, for example, the addition and precipitation may be performed in the same reactor of the system. In other embodiments of the invention, these two steps can be performed in separate reactors such that the water is first fed with _CO in the feed reactor and then in a separate reactor, the resulting _CO fed water is then Subject to precipitation conditions. Other reactors may be used, for example, feeding water with the desired mineral.

The contacting of the water with the _CO2 source can occur before and/or during the water is subjected to the _CO2 precipitation conditions. Accordingly, embodiments of the invention include methods wherein a volume of water (eg, alkaline earth metal ion-containing water) is contacted with a _CO source prior to subjecting the volume of water to mineral precipitation conditions. Embodiments of the invention also include methods wherein a volume of water is contacted with a source of _CO2 while the volume of water is being subjected to carbonate compound precipitation conditions. Embodiments of the present invention include wherein a volume of water (e.g., water containing alkaline earth metal ions) is subjected to carbonate compound precipitation conditions prior to and while the volume of water is being subjected to carbonate compound precipitation conditions. The method by which water contacts the _CO2 source. In some embodiments, the same water can be cycled more than once, where the first cycle of precipitation primarily removes calcium and magnesium carbonate minerals and leaves water, to which metal ions, e.g., alkaline earth metal ions, can be added, and which can have The more _CO2 that circulates through it, this precipitates more carbonate compounds.

Regardless of when the _CO2 contacts the water, in some cases when the _CO2 contacts the water, the water is not very alkaline such that the water contacted by the _CO2 can have a value of 10 or lower, such as 9.5 or lower, including 9 or lower and Even a pH of 8 or lower. In some embodiments, the water exposed to _CO2 is not water that was first made alkaline by an electrochemical process. In some embodiments, the water exposed to _CO2 is not water that has been made alkaline by the addition of hydroxides, such as sodium hydroxide. In some embodiments, the water is water that has only been made slightly alkaline, such as by adding an amount of an oxide such as calcium oxide or magnesium oxide.

As mentioned above, one of the parameters affecting the efficiency of introducing a gas into a liquid is the solution chemistry of the liquid. Gases will have different solution-specific solubilities, based on the ion content and pH of the solution. For example, carbon dioxide gas binds more readily to a solution with a basic pH, such as an aqueous solution of NaOH, than to a solution with a neutral or acidic pH. In some embodiments, the gas is the flue gas of a process. In some embodiments, the process includes the combustion of fossil fuels. In some embodiments, the gas includes _CO2 . In these embodiments, the methods and apparatus can be tuned to optimize the introduction of _CO2 gas from a gas to a liquid. In such embodiments, various conditions (e.g., solution chemistry, surface area to volume ratio, liquid flow rate to gas flow rate ratio (L/G), residence time) are provided that allow at least 10 grams of _CO to be absorbed , calculated per 100ml of liquid. In some embodiments, conditions are provided which allow at least 20 grams of _CO to be absorbed per 100 ml of liquid, such as at least 30 grams, at least 40 grams, at least 50 grams, at least 60 grams, at least 70 grams, at least 80 grams, at least 90 grams, at least 100 grams, or more than 100 grams of _CO2 is absorbed. In some embodiments, the methods and devices provide conditions (eg, solution chemistry, surface volume ratio, residence time) where at least 50% of the _CO in the gas is removed from the gas into a liquid or slurry. In some embodiments, conditions are provided that allow at least 60% of the _CO in the gas to be removed, such as at least 70%, at least 80%, or at least 90% of the _CO in the gas to be removed from the gas into liquids or slurries. In some embodiments, conditions are provided that allow at least 95% of the _CO2 in the gas to be removed from the gas into a liquid or slurry. In some embodiments, the methods and devices provide conditions (e.g., solution chemistry, surface-to-volume ratio, ratio of liquid flow rate to gas flow rate (L/G), residence time) in which at least 50% of the gas group Particles (such as NOx, SOx, mercury) are removed from the gas into the liquid or slurry. In some embodiments, conditions are provided that allow at least 60% of the gaseous components to be removed, such as at least 70%, at least 80%, or at least 90% of the gaseous components to be removed from the gas into the liquid or in the slurry. In some embodiments, conditions are provided that allow at least 95% of the gas components to be removed from the gas into the liquid or slurry.

Optimization of precipitation reactions is a goal of efficient gas-liquid contacting methods and devices. In some embodiments, a precipitate is formed that includes carbonate and/or bicarbonate material. In some embodiments, a precipitate of secondary cationic carbonate and/or bicarbonate material is formed. In some embodiments, calcium carbonate and/or calcium bicarbonate material is formed. In some embodiments, magnesium carbonate and/or magnesium bicarbonate material is formed. In some embodiments, calcium carbonate and magnesium carbonate and/or calcium bicarbonate and magnesium bicarbonate materials are formed. In some embodiments, carbonates and/or bicarbonates of calcium and magnesium, such as dolomite, are formed.

In some of the embodiments described herein, streams and/or droplets are formed from slurries and subsequently contacted with gases in methods and apparatus. The slurry used to generate the droplets and/or streams may depend on the availability of the location in which the gas-liquid contactor is located and the gas that will contact the droplets and the desired outcome from the interaction between the gas and the droplets . Liquids that may make up the liquid component of the slurry include, but are not limited to: aqueous solutions containing divalent cations at a pH of 10 or greater; seawater; brackish water; man-made liquid wastes from desalination processes; naturally occurring brines; industrial waste A brine; a synthetic brine; a cation-added solution; a silica-added solution; or any combination thereof. The composition of the slurry used includes, but is not limited to, liquid and industrial waste particles, liquid and mineral particles, liquid and sediment, or combinations thereof. As noted above, the solution chemistry can be adjusted to increase the introduction of gas into the liquid or slurry. In some embodiments, droplets and/or streams comprising aqueous solutions are provided. In some embodiments, droplets and/or streams comprising an aqueous solution having a pH of 4-11 are provided. Some embodiments provide droplets and/or streams comprising ion-containing aqueous solutions. Some embodiments provide droplets and/or streams comprising divalent cation-containing aqueous solutions. Some embodiments provide droplets and/or streams comprising aqueous solutions including seawater, dissolved mineral solutions, brine, or any combination thereof. In some embodiments, droplets comprising a basic solution are provided. In some embodiments, droplets and/or streams comprising alkali metal hydroxides are provided. In some embodiments, droplets and/or streams comprising NaOH or KOH or combinations thereof are provided. Some embodiments provide droplets and/or streams comprising solid material. In some embodiments, the droplets and/or the stream include precipitation material resulting from contacting the droplets with the gas. In some embodiments, the droplets and/or streams include particulate matter of industrial waste such as, but not limited to, fly ash, slag, cement kiln dust, mining waste, or any combination thereof. In some embodiments, the droplets and/or streams include precipitation material and industrial waste particulates. In some embodiments, droplets and/or streams comprising mineral particulates are provided. In some embodiments, droplets and/or streams comprising mineral particulates and industrial waste particulates are provided. In some embodiments, droplets and/or streams comprising mineral particulates, industrial waste particulates, and precipitation materials are provided.

There are many methods of making droplets. Using evaporation, such as evaporating water to moisten an area, can produce a very fine smoke of liquid droplets. Non-evaporative techniques for producing droplets include, but are not limited to: pressure atomizers (orifices), rotary atomizers, air-assisted atomizers, air-jet atomizers, ultrasonic atomizers, inkjet atomization nebulizers, MEMS nebulizers, injectors-injection nozzles and electrostatic nebulizers. In embodiments describing liquid and/or slurry droplets, any method of droplet formation may be used. In some embodiments, droplets are produced using a system that includes an ultrasonic transducer. In some embodiments, droplets are produced using a system comprising a pressure atomizer (orifice), a rotary atomizer, an air-assisted atomizer, an air-jet atomizer, or any combination thereof. In some embodiments, a system or apparatus for generating liquid droplets (ie, a liquid introduction unit) comprising an ultrasonic transducer is provided. In some embodiments, a system or apparatus for generating droplets is provided that includes an orifice. In some embodiments, a system or apparatus for generating droplets is provided that includes a dual-fluid jet, an ejector-jet jet, or both. In some embodiments, a system and/or device for generating droplets has an orifice with an opening of 5 microns or less. In some embodiments, a system and/or device for generating droplets has an orifice with an opening of 10 microns or less. In some embodiments, a system and/or device for generating droplets has an orifice with an opening of 10 microns or greater. In some embodiments, the system and/or device for generating droplets has an orifice with a diameter of 25 microns or greater, such as 50 microns or greater, 100 microns or greater, 250 microns or greater, 500 microns or greater opening. In some embodiments, a system and/or device for generating droplets has an orifice with an opening of 1 mm or greater. In some embodiments, a system and/or apparatus for generating droplets comprising a pressure atomizer (orifice), a rotary atomizer, an air-assisted atomizer, an air-jet atomizer, or any combination thereof is provided. Some embodiments provide systems and/or devices capable of receiving a slurry to produce droplets. In some embodiments, systems and/or devices for generating liquid droplets are provided, wherein the liquid droplets are 50 to 1000 micrometers (μm) in diameter. In some embodiments, systems and/or devices for generating droplets are provided, wherein the droplets have an average diameter greater than 1000 micrometers (μm). In some embodiments, systems and/or devices for generating droplets are provided, wherein the droplets have an average diameter greater than 500 microns. In some embodiments, systems and/or devices for generating droplets are provided, wherein the droplets have an average diameter of less than 1 micron. In some embodiments, systems and/or devices for generating droplets are provided, wherein the droplets have an average diameter greater than 5 microns, such as greater than 10 microns, greater than 20 microns, greater than 50 microns, greater than 100 microns, greater than 200 microns, greater than 300 microns, or greater than 400 microns. In some embodiments, systems and/or devices for generating liquid droplets are provided, wherein the liquid droplets have an average diameter of 1 to 400 microns. In some embodiments, systems and/or devices for generating liquid droplets are provided, wherein the liquid droplets have an average diameter of 1 to 500 microns. In some embodiments, systems and/or devices for generating equi-buoyant droplets are provided. Isobuoyant droplets are droplets that neither rise nor sink in an environment in which they are buoyant, such as a gas surrounding the droplet.

It may be possible to optimize the area of the cross-section of the device's contact chamber or column covered by the droplets by varying the type of droplet generation technique used. In particular, it may be possible to optimize the area of the cross-section of the device covered by the droplets by using sprayers of different angles. In some embodiments, a 60° nebulizer is used near the wall of the contacting chamber, while a 90° nebulizer is used in the inner cross-section of the contacting chamber.

The surface area to volume ratio of the liquid in contact with the gas is a factor governing the efficiency with which the gas is introduced into the liquid. In some embodiments, liquid droplets and/or liquid streams are provided having a surface area to volume ratio (SA:V) of 12 m2/liter or greater. In some embodiments, liquid droplets and/or liquid streams are provided having a surface area to volume ratio (SA:V) of 24 m2/liter or greater, such as 60 m2/liter or greater, 80 m2/liter or greater, 120 m2/liter liter or greater, 600m2/liter or greater, or 6000m2/liter or greater. In some embodiments, droplets are provided having an average diameter greater than 500 microns. In some embodiments, droplets are provided having an average diameter of less than 1 micron. In some embodiments, droplets are provided having an average diameter greater than 5 microns, such as greater than 10 microns, greater than 20 microns, greater than 50 microns, greater than 100 microns, greater than 200 microns, greater than 300 microns, or greater than 400 microns. In some embodiments, droplets are provided having an average diameter of 1 to 400 microns. In some embodiments, droplets are provided having an average diameter of 1 to 500 microns. In some embodiments, droplets are provided that are 50 to 1000 micrometers (μm) in diameter. In some embodiments, droplets are provided having an average diameter of 100 micrometers (μm). In some embodiments, methods of generating and/or utilizing equibuantial droplets are provided. Isobuoyant droplets are droplets that neither rise nor sink in an environment in which they are buoyant, such as a gas surrounding the droplet.

In some embodiments of the invention, a specific L/G ratio is indicated. The L/G ratio is a numerical value of the ratio of the flow rate of liquid to the flow rate of gas in the device. Without being bound by theory, the absorption of a gas or a component of a gas into a liquid is directly proportional to the L/G ratio. In some uses of this ratio, the L/G ratio is a dimensionless number and will thus represent volume flow per unit of time relative to another volume flow per unit of time, or per unit of mass flow per unit of time relative to another Time mass flow. In some embodiments, an L/G ratio of 3-50 is used. In some embodiments, an L/G ratio of 3-20 is used. In some embodiments, a L/G ratio of 15 is used. In some embodiments, an L/G ratio of 50-4000 is used. In some embodiments, an L/G ratio of 100-1000 is used. In some embodiments, an L/G ratio of 200-400 is used. In some embodiments, a L/G ratio of 300 is used. In some embodiments, the device and/or system is configured to use an L/G ratio of 3-50. In some embodiments, the device and/or system is configured to use an L/G of 3-20. In some embodiments, the device and/or system is configured to use an L/G ratio of 15. In some embodiments, the device and/or system is configured to use an L/G ratio of 50-4000. In some embodiments, the device and/or system is configured to use an L/G ratio of 100-1000. In some embodiments, the device and/or system is configured to use an L/G ratio of 200-400. In some embodiments, the device and/or system is configured to use an L/G ratio of 300. In certain uses of the L/G ratio, units are quoted to indicate that volume or mass is being compared in the ratio. In some embodiments, a L/G ratio of 0-10,000 gallons per minute per 1000 actual cubic feet is used. In some embodiments, a L/G ratio of 50-5,000 gallons per minute per 1000 actual cubic feet is used. In some embodiments, a L/G ratio of 100-500 gallons per minute per 1000 actual cubic feet is used. In some embodiments, the device and/or system is configured to operate at a liquid flow to gas flow ratio (L/G ratio) of 0-10,000 gallons per minute per 1000 actual cubic feet. In some embodiments, the device and/or system is configured to operate at a liquid flow to gas flow ratio (L/G ratio) of 50-5,000 gallons per minute per 1000 actual cubic feet. In some embodiments, the device and/or system is configured to operate at a liquid flow to gas flow ratio (L/G ratio) of 100-500 gallons per minute per 1000 actual cubic feet.

There are structural features that can be added to the chamber where the liquid or slurry and gas are in contact that enhance the introduction of the gas into the liquid or slurry. Such structural features imply increased interaction between gases as they flow through liquids or slurries by: 1) providing one or more regions for the liquid/gas system to reach equilibrium, or 2) Provides an opportunity for the liquid or slurry to be entrained by the gas and to follow more rotational paths as the liquid or slurry passes through the space of the chamber (eg, as the liquid or slurry falls). In some embodiments, either type of structural feature is used to contact an absorption solution, a contact mixture, or a slurry and a gas. In some embodiments, the device or system includes any type of structural feature for contacting an absorption solution, contacting a mixture, or a slurry with a gas. In some embodiments, or a combination of both types of structural features are used for contacting absorption solutions, contacting mixtures, or slurries and gases. In some embodiments, a device or system includes two types of structural features for contacting an absorption solution, contacting a mixture, or a slurry and a gas.

Structural features that increase the probability of liquid and gas reaching equilibrium in a confined space include packing materials and trays. Packing materials can be structured or unstructured, and can be ceramic, plastic, or metallic, in spherical, honeycomb, ribbon, saddle, ring, or random shape form. Trays are generally sheets of metal with perforations or openings that allow gases and liquids to flow through the trays. The materials from which the packing materials and trays are made are selected based on the chemical properties of the gases, liquids and products expected in the column or reactor, as well as considerations such as physical losses. A column or reactor utilizing packing material or trays can be considered as a collection of stages (ie the length of the column or reactor) where the gas leaving the stage is in equilibrium with the liquid leaving the stage. The theoretical level describes the physical section of the column in which the bulk vapor phase and bulk liquid phase can be approximated to be in equilibrium with respect to the concentrations of species exchanged as gas and liquid pass through the column. Volumetric efficiency can be adjusted by adjusting the packing material or the configuration of the trays. Columns or reactors utilizing packing materials or trays are characterized by a high pressure drop over the entire length of the column or reactor due to liquid head associated with the trays or bed pressure drop associated with the packing material. Columns utilizing packing materials are generally not suitable for contacting slurries and gases, but packing materials have been made commercially viable for accommodating slurries. In some embodiments, trays, packing material, or both are used to contact the absorbing solution, the contacting mixture, or the slurry with the gas. In some embodiments, the device or system includes packing material, trays, or a combination thereof to contact the absorbing solution, contact the mixture, or the slurry and the gas.

Membranes are another type of structural feature that may be included in a column or reactor to facilitate the interaction between gas and liquid. Membranes used in columns or reactors are used to increase the interfacial area between liquid and gas in order to maximize mass transfer rates. Membranes can be composed of many hollow fibers. In such membranes, a gas-liquid interface occurs at the entrance of each hollow fiber pore. Therefore, this type of membrane may be referred to as a microporous membrane. In some embodiments, one or more membranes are used for contacting the absorbing solution, the contacting mixture, or the slurry and the gas. In some embodiments, a device or system includes one or more membranes for contacting an absorbing solution, a contacting mixture, or a slurry and a gas. In some embodiments, one or more membranes are used in combination with packing material and/or trays for contacting the absorbing solution, the contacting mixture, or the slurry and the gas. In some embodiments, the device or system includes one or more membranes combined with packing material and/or trays for contacting the absorbing solution, contacting the mixture, or the slurry and the gas. In some embodiments, one or more microporous membranes are used for contacting the absorbing solution, the contacting mixture, or the slurry and the gas. In some embodiments, a device or system includes one or more microporous membranes for contacting an absorbing solution, a contacting mixture, or a slurry and a gas. In some embodiments, one or more microporous membranes are used in combination with packing material and/or trays for contacting the absorbing solution, the contacting mixture, or the slurry and the gas. In some embodiments, the device or system includes one or more microporous membranes combined with packing material and/or trays for contacting the absorbing solution, contacting the mixture, or the slurry and the gas.

Structural features that allow liquids or slurries to become entrained in the gas as the gas passes through the tower or chamber while forcing the gas and liquid to follow more rotational paths, including shed rows. A row is an array of sheets of material with greater length than width, typically metal, bent in the middle to form an inverted "v" configuration, carried by a ring. Generally, the rows of sheds are arranged such that the position of the sheds alternates with each level in the column or reactor. Thus, a mixture (such as a slurry) or liquid falling from the shed will reach near the roof of the shed below it, causing the mixture or liquid to follow a longer, more swirling path down the length of the column or reactor than It is in the case of no shed row. Rows also affect the flow of gas through the column or reactor. In the space between the roof and the bottom of the shed, above which is where entrainment of falling mixtures or liquids into the gas may occur. This entrainment increases the amount of time the mixture or liquid and gas must interact in the column or reactor. Rows are compatible with liquids and slurries. The angle of repose, which governs the width of the shed, allows the use of shed rows with various solutions and is used to accommodate solid particles. The impregnation of the shed can be adjusted to allow the liquid or slurry to roll off the roof at a velocity that allows the desired interaction with the gas in the column or reactor. Rows also allow for a lower drop in gas pressure over the height of the column or reactor compared to those packed with trays or packing material. In some embodiments, a row is present in a device or system of the invention. In some embodiments, the chamber in which the absorption solution contacts the gas comprises a row. In some embodiments, the chamber in which the contacting mixture and the gas are contacted comprises a row. In some embodiments, the apparatus includes a contacting chamber that includes rows. In some embodiments, a system includes an apparatus that includes a row. In some embodiments, the row of sheds comprises concentric circles of sheds. In some embodiments, the chamber includes a protrusion along the chamber wall into the center of the chamber. In such an embodiment, the protrusion resembles one half of a downwardly sloping shed.

There are embodiments where it is desirable to condense or condense liquid droplets or fine particulate material after contact with the gas. In such embodiments, various methods can be used to induce coalescence of the droplets, including but not limited to: temperature changes, use of elements with additional surface area, use of electrostatic precipitators, or use of streams, plates, or larger liquids. Droplets of liquid to entrain droplets after contact with gas. In some embodiments, a precipitate forms in the droplets while the droplets are still in contact with the gas. In some embodiments, an electrostatic precipitator is used to collect and condense the droplets, having the charge of the precipitates in the droplets, with the precipitate forming in the droplets while still in contact with the gas. In some embodiments, fine particulate matter is formed, and electrostatic precipitators are used to collect these particles.

In some embodiments, it is necessary to redirect the falling liquid or slurry that descends the height of the device in the form of droplets, streams, or plates so that the liquid or slurry does not impart undue energy to the liquid or slurry reservoir and generate foam. In particular, it is desirable in some embodiments to avoid the formation of a stable foam layer that could impair the ability of the pump to work optimally. Structural elements may be used to redirect falling liquid or slurry. In some embodiments, inverted cones are present in the device to reduce foaming. The traditional method of removing the foam layer is to mechanically break up the air bubbles that make up the foam layer. In some embodiments, a nebulizer is used to mechanically break up air bubbles and reduce foaming. In some embodiments, an inverted cone and sprayer is used to reduce foaming.

In some embodiments, a device of the invention for transferring (i.e. combining) a gas component into a liquid comprises a gas inlet, a chamber configured to contact the liquid and the gas; a first liquid at a first position in the chamber An introduction unit and a second liquid introduction unit at a second location in the chamber for contacting the gas; a reservoir configured to contain the liquid after it has contacted the gas; an outlet for the liquid after it has contacted the gas , and at least one of the following flow characteristics: i) at least one array of rows in the chamber; ii) defoaming equipment; iii) at least one pump per liquid introduction unit for pumping liquid through the introduction unit iv) configuring the liquid introduction unit so that the direction of flow of liquid leaving the first unit is different from the direction of flow of liquid leaving the second unit; v) one or more orifice mechanism drain valves) configured to direct the flow of liquid into at least one of the liquid introduction unit, into the gas inlet, or a combination thereof; and vi) changing the area covered by the liquid introduction unit. In such embodiments, the liquid introduction unit may be a sprayer, a liquid column, a liquid flat sparger, or a combination thereof. In such embodiments, the rows may be configured to redistribute the flow of the gas as it enters the chamber such that before interacting with the rows, the gas flows axially along the chamber, thereby Covers a larger area of the chamber cross-section. In some embodiments, the defoaming device can include a cone (eg, an inverted cone) positioned above the reservoir. In such embodiments, cone-facing nebulizers may also be used. In some embodiments, where the area covered by the liquid introduction unit is varied, varying angle sprayers may be used. In some embodiments, the pump used to pump the liquid through the liquid introduction unit is an inverter pump.

Exemplary methods and systems for contacting a gas stream and water use a flat jet stream of contacting gas stream to water. Accordingly, in some embodiments, the present invention provides apparatus for separating carbon dioxide and an industrial waste stream comprising a gas-liquid contactor configured to contact all or a portion of the industrial waste stream with a flat jet stream of liquid, e.g., water thereby dissolving _CO and, in some embodiments, other components of the industrial waste stream, and further comprising operably connected to a gas-liquid contactor for producing, for example, by evaporation, precipitation, etc. A unit of solid composition of all or part of _CO2 . In some embodiments, the solid composition is a composition comprising bicarbonate. In some embodiments, the solid composition is a composition comprising carbonate. In some embodiments, the solid composition includes carbonates and bicarbonates. In some embodiments, the solid composition includes carbonates and/or bicarbonates and one or more other components of industrial waste gases, such as SOx or SOx derivatives, NOx or NOx derivatives, heavy metals or derivatives thereof , particulate matter, VOC or VOC derivatives, or combinations thereof.

An exemplary flat jet flow/gas contacting system is described in US Patent 7,379,487, the disclosure of which is incorporated herein by reference. In some embodiments, contacting a gas stream comprising CO ₂ includes using a two-phase reactor, as described in US Pat. No. 7,379,487. A brief description of the flat jet flow method and system is given below.

In many gas-liquid contact systems, the rate of gas transport to the liquid phase is controlled by the liquid phase mass transfer coefficient k, the interfacial surface area A, and the concentration gradient ΔC between the bulk fluid and the gas-liquid interface. The actual form of the rate of gas absorption into a liquid is then:

Where Ф is the gas absorption rate per unit volume of the reactor (mol/cm3·s), and a is the average absorption rate per unit interface area (mol/cm2·s). a is the gas-liquid interface area (cm2/cm3, or cm-1) per unit volume, p and pi are respectively the partial pressure (bar) of the reagent gas in the bulk gas and at the interface, and CL* is to be compared with Existing gas phase concentration, pi phase equilibrium liquid side concentration (mol/cm3), and CL (mol/cm3) are the average concentrations of dissolved gases in the bulk liquid. kG and kL are the gas side and liquid side mass transfer coefficients (cm/s), respectively.

In many gas-liquid reaction systems, the solubility of CL* is very low and thus limits the control of concentration gradients. Therefore, the main parameters considered in designing an efficient gas-liquid flow reactor are mass transfer and the ratio of interfacial surface area to reactor volume, also known as specific surface area.

In certain embodiments, the horizontal jet gas-liquid contacting system of the present invention is a gas-liquid contacting system that utilizes the increased specific surface area of the flat jet to improve the interaction of the _CO2 -containing gas stream with water (e.g., alkaline earth metal ion-containing water). )interaction between. In certain embodiments, a rigid orifice plate with multiple orifices is used, which produces a very thin flat jet. The flat jet orifice has a V-shaped chamber in one configuration that is connected to a water source, such as water containing alkaline earth metal ions. The flat jet orifice may have a pair of opposing planar walls connected to the top of the V-shaped chamber. The flat jet nozzle may have a tapered nozzle connected to opposite ends of the opposite planar walls of the V-shaped chamber. In another arrangement, the spray orifice may have a circular orifice connected to the liquid source chamber. The flat jet nozzle may have a V-shaped groove that intersects a circular orifice to create an oval orifice. The flat jet orifice may be oriented perpendicular, opposite or parallel to the inlet source of the _CO2 -containing gas stream. The smallest channel of a flat jet nozzle can be greater than 600 microns. The spout may produce a flat jet of liquid having a width that is at least 10 times, or at least 8 times, at least 6 times, or at least 4 times its thickness. Flat jets can be made as thin as 10 microns, for example, 10-15 microns, 10-20 microns, or 10-40 microns, and separated by less than 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3 , or 0.2mm, such as less than 1 mm, in order to produce high filler injection density (β = 0.010.01)) and large specific surface area, a = 10-20cm-1. The thin jet allows more water, e.g., alkaline earth metal ion-containing water, to be subjected to the _CO2 -containing gas stream, resulting in a higher yield of reaction product (per unit liquid mass flow rate) than conventional contactors, e.g. More transfer of _CO2 and/or other components of gas streams, such as SOx, NOx, heavy metals, particulate matter, VOC, and their derivatives and combination to liquids, eg, water.

One embodiment of the present invention will provide a gas-liquid-solid contactor comprising a _CO2 fed reactor with multiple thin flat jet streams that are closely and evenly spaced, have a high specific surface area, have uniform jet velocity, aerodynamic Shaped to minimize gas flow disturbances for liquid jets, free from salt plugging and clogged orifices, and operate in co-flow, counter-flow and parallel-flow gas process streams. In one embodiment, the jet operates in a cross-flow configuration with the gas, eg, the jet is vertically downward from the jet while the gas flows horizontally or approximately horizontally across the jet.

The flat-spray gas-liquid contacting system of the present invention is used to contact a _CO2 -containing gas stream with a liquid, such as water, such as water containing alkaline earth metal ions. The feed reactor comprises a chamber with an inlet source for a _CO2 -containing gas stream and a flat jet orifice for a source of a liquid, eg water such as water containing alkaline earth metal ions. The jets may have a plurality of orifices with a minimum dimension of greater than 200, 300, 400, 500 or 600 microns in length, for example greater than 600 microns in length, and produce a thin flat jet of high specific surface area. The spout may have a pair of parallel opposing plates having a second end connected to the tapered spout. The spout may have a pair of V-shaped plates connected to first ends of a pair of parallel opposing plates. a liquid, such as water such as alkaline earth metal containing water, the orifice may produce a flat jet of water having a width at least 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 times its thickness, For example at least 10 times. The source of liquid, for example water, such as alkaline earth metal-containing water, may be any suitable source (as described above). In certain embodiments, the water source comprises a reservoir having an input for water, eg, alkaline earth metal ion-containing water, such as a pipe or pipeline from the ocean. Where the source of liquid (eg, water such as alkaline earth metal ion-containing water) is seawater, the input is in fluid communication with the source of seawater, such as where the input is a line or feed from ocean water to a land-based system.

A gas-liquid contacting system may include a small number of orifice arrays. The orifices may be staggered such that the jet orifices are separated by 1.5-2.5 cm, for example, 1.7-2.3 cm, such as 1.9-2.1 cm, or 2 cm in one direction, and 1.5-2.5 mm in the other direction, for example , 1.7-2.3mm, such as 1.9-2.1mm, or 2mm, and diagonally 0.5-1.5mm, such as 0.7-1.3mm, such as 0.9-1.1mm, or 1mm. The orifice has a V-shaped inlet and a conical outlet channel to form a jet. The intersection of the inlet and outlet channels creates the orifice. The ratio of spray length to spray width can be 5:1 to 20:1, or 7:1 to 15:1, or 8:1 to 12:1, or 9:1 to 11:1, or 10:1, with a thickness of 10-100 microns, eg, 10-20 microns.

The feed reactor of the present invention may include a flat sparged air-liquid contacting system to produce large specific area water (eg, alkaline earth metal ion-containing water). The feed reactor has a source of CO ₂ -containing gas stream (gas reactant), which is connected to the manifold of the reactor. In certain embodiments, the manifold has a number of holes (openings) that allow injection of the _CO2 -gas stream into the feed reactor. The feed reactor may also have an inlet for water (e.g., water such as alkaline earth metal ion-containing water) (the "liquid reactant") connected by piping to a plurality of flat jet nozzles that produce Flat logistics of water. A flat stream of water (eg, alkaline earth metal ion-containing water) interacts with a _CO2 -containing gas stream to produce a CO2 _- fed water composition that will be subjected to precipitation conditions.

In some embodiments, the jet of the flat jet gas-liquid contacting system of the addition reactor may have a V-shaped chamber connected at the top to the first ends of a pair of opposing plates. The second end of the opposite plate is connected to the conical spout. Water (eg, water containing alkaline earth metal ions) flows into the V-shaped chamber and is forced through the channel between the opposing plates and exits the spout and creates a flat spray. Depending on the orifice area, jet flow rate and velocity, the jet thickness is about 5 to 100 microns and the width is about 1 to 5 centimeters. As a result, the (ratio) of width to thickness can be significantly greater than an order of magnitude. For a jet velocity of about 10 m/s, the length of the flat jet stream can be 15 cm or more. The narrowest channel where the conical orifice meets the opposing planar plate is greater than 600 microns. Such vents allow a large surface area of water (e.g., water containing alkaline earth metal ions), which significantly increases _CO2 and other components (e.g., SOx, NOx, particulate matter, heavy metals, and/or VOCs) in the... Transfer efficiency between a _CO2 -containing gas stream and a liquid film. Further, due to the large jet surface area and small jet thickness, this jet orifice produces a very large specific surface area, 10-20 cm-1, which enables higher volume contact between water and gas streams. In addition to increasing the surface area of water (eg, alkaline earth metal ion-containing water), flat injectors have throat sizes of 600 microns or greater. The large throat size of flat injectors makes it less likely that they will clog. In some embodiments, where clogging is not too much of an issue, the throat size can be smaller, such as 50 microns or greater, 100 microns or greater, 200 microns or greater, 300 microns or greater, 400 microns or greater , or 500 µm or larger. The system may also include components for collecting water (eg, alkaline earth metal ion-containing water) and _CO2 -lean gas streams for reuse.

The CO ₂ -containing gas stream contacts water (eg, alkaline earth metal ion-containing water) by directing the gas to contact a flat jet stream of water. The _CO2 -containing gas stream can flow in almost any direction relative to the flat jet stream, including at right angles to the flat jet stream, parallel to the flat jet stream, anti-parallel to the flat jet stream, or at an angle to the flat jet stream.

Gas from industrial facility 30 may be processed and then used to feed water, as described above. For example, the gas may be subjected to oxidizing conditions to improve the solubility of components of the gas stream (eg, to convert CO to _CO2 , NO to _NO2 , and _SO2 to _SO3 , etc.).

Figure 11 shows an embodiment of the device of the present invention. A slurry comprising liquid and solid components enters the contacting chamber through an inlet duct [100] to a reservoir [105] which also contains the slurry which has been contacted with gas. In some embodiments, a screw conveyor provides comminution and mixing of the slurry and gas as it enters the chamber [110]. In some embodiments, gas enters the chamber through inlet [110]. In some embodiments, in an array of droplet or stream generation systems, there are at least two levels or segments of droplet or stream generation [150 and 155] and conduits for gas movement up the chamber [160] . Slurry transport systems [115, 120, 135, 125, 140, 130] move slurry from storage to droplet or stream generation systems and recycle slurry at different levels of droplet or stream generation. Comminution systems [120, 125, 130] provide particle size reduction of the solid components of the slurry, thereby improving the participation of solids in the gas-introduced liquid. In some embodiments, the comminution system is a screw conveyor in the pipeline [115, 145] of the slurry transport system. In some embodiments, a high efficiency gas-liquid contactor is used to remove more of the desired component from the gas stream. The clear liquid free of solids is provided to a high efficiency gas-liquid contactor [165] and very fine droplets or thin liquid films or other high surface area/volume ratio means are used to contact liquid and gas. In some embodiments, a condenser [170] is required to allow the liquid droplets and/or particulates produced by the high efficiency gas-liquid contactor to fall to the reservoir. The gas after contact with the liquid leaves the chamber [175] and passes through another system or is released into the air. The contacted liquid, including the precipitation material from the contact between the gas and the liquid and the solid components of a very small amount of the slurry, leaves the storage [180] and is passed to other systems [185] such as settling tanks, dewatering systems, and Building manufacturing system.

Figure 12 shows a flow diagram of an embodiment of the method of the present invention. In most embodiments a slurry comprising liquid and solid components is provided [200]. The slurry undergoes crushing to reduce the particle size of the solid components, and the slurry is also mixed [205]. From the slurry, droplets or streams are formed [210] and the liquid in the form of droplets or streams is introduced [215] into a chamber for contacting [220]. The gas is introduced into the contact chamber [225]. The source of the gas may be industrial flue gas, such as that from burning fossil fuels such as coal. After contacting, a contacted slurry is formed and collected in a reservoir in the contacting chamber [230] and a part of this contacted slurry is recycled [235] after crushing and a part is pumped away for solid and liquid Separation [240]. The solids are removed and can be used in many applications including, but not limited to, construction materials, as soil stabilization, paint manufacturing, and lubricant manufacturing. The effluent liquid [245] may have a solution chemistry favorable for use in a high efficiency gas-liquid contactor [255] located in the plant to maximize contact with the gas [250], as it passes through larger droplets and streams to the final stage of contact. Effluent liquids may also be processed using nanofiltration and reverse osmosis [260] to provide mineral and chemical regeneration as well as water, which may be suitable as feed water for desalination or for release into the environment [265].

Figure 13 shows an embodiment of a horizontal configuration of the device of the present invention. Gas enters the chamber through the inlet [300]. A slurry comprising liquid and solid components is conveyed from a reservoir where the slurry is subjected to comminution [330] and passed through an array of droplet generating devices [350] into a contact chamber [310] to produce a spray of droplets [320] that fills the chamber. In some embodiments, there are at least two segments of droplet generation that are operatively connected such that the gas travels along the length of the segments and becomes depleted of gas components over the length of the contacting chamber. The slurry transport system [340, 350, 360, 370] moves the slurry from the contact chamber to the droplet generation system and recirculates the slurry in different stages of droplet or stream generation. The pulverization system in the slurry reservoir [330] provides particle size reduction of the solid components of the slurry, thereby improving the participation of solids in the gas-introduced liquid. The gas after contact with the liquid leaves the chamber and passes through another system or is released into the air. The contacted liquid, including the precipitation material from the contact between the gas and the liquid and the solid components of a very small amount of the slurry, exits the contact chamber [370] and is passed to other systems [380] such as settling tanks, dewatering systems, and Building manufacturing system.

Figure 14 shows an embodiment of the device of the invention in a horizontal configuration (from an end view). A slurry comprising liquid and solid components is conveyed from a reservoir where the slurry is subjected to comminution [400] and passed through an array of droplet generating devices [430] into a contact chamber [410] to generate a spray of droplets [440] that fills the chamber. Gas enters the chamber through the inlet and passes through the chamber [450]. In some embodiments, there are at least two segments of droplet generation that are operatively connected such that the gas travels along the length of the segments and becomes depleted of gas components over the length of the contacting chamber. The slurry transport system [420, 460, 470] moves the slurry from the contact chamber to the droplet generation system and recirculates the slurry in the different stages of droplet or stream generation. The pulverization system in the slurry delivery system [460] provides particle size reduction of the solid components of the slurry, thereby improving the participation of solids in the gas-introduced liquid. The gas after contact with the liquid leaves the chamber and passes through another system or is released into the air. The contacted liquid, including the precipitated material from the contact between the gas and the liquid and the solid components of a very small amount of the slurry, exits the contact chamber and is passed to other systems [480] such as settling tanks, dewatering systems, and building fabrication systems .

Figure 15 shows an embodiment of the invention comprising a gas distribution section, a variable number of contacting sections, and a defuming or final gas absorption section, always located at the top of the apparatus. The gas is in the lowest section, the gas distribution section, above the collected solution, into the unit. Gas flows up through the device and exits the top of the device. The number of contact segments may be 1 to more than one, such as 2 or 3 or more. The number of contacting stages will be determined based on the type of end product desired, the absorption solution or contacting mixture used, the spray (or other form of liquid stream), and optionally, the row used. The section just before the gas leaves the device is the demister section. This section may comprise a high efficiency gas absorption system, eg using a flat membrane of clear liquid or very fine droplets, about less than 100 μm, such as less than 50 μm diameter droplets. In the final stage, a particulate-free solution will be used to maximize absorption and/or droplet collection. The chemical nature of the solutions used in the demisting and final gas absorption stages may be different from the solutions used in any of the contacting stages. Recirculation of the solution collected at the bottom of the device may include comminution of any solids that may be in solution. Recycling may also include separating any solids that may be present from the solution and returning the effluent to the plant, with or without treatment to replenish any chemical deficits in the solution. The device may be portable in nature such that the entire device is contained in a transport container which may be transported by rail (train), water (barge) and/or road (truck). The device may also be modular such that different segments may each be contained within a shipping container and stacked or otherwise operably connected to each other.

Figures 16 and 17 are schematic illustrations of embodiments of the apparatus of the invention in which rows are used. Figure 16 shows the entire device, with a gas inlet above the lower part of the device, where the collected solution will be stored and then withdrawn for further processing. The central section includes rows of sheds, the configuration of which is shown in Figure 17. The upper section of the device shown in Figure 16 includes nebulizers to introduce the absorption solution or contact mixture into the device and a gas outlet.

Figure 18 is a schematic illustration of an embodiment of the invention wherein the device comprises an array of nebulizers. 4 nebulizers are shown; the nebulizers are all directed downwards in the vertically oriented device. Nebulization can be accomplished in any suitable manner, including using an injector or injector-jet nozzle, a two-fluid nozzle, a pressure atomizer, a rotary atomizer, an air-assisted atomizer, an air-jet atomizer or an ultrasonic atomizer or any combination thereof. The flow of gas in the device is upward so that all nebulizers encounter the gas flow in a countercurrent fashion. Gas enters the device at the bottom and flows up the length of the device. The device may include a mist removal section before the gas outlet (not shown). The absorption solution or contacting mixture may be a clear liquid, or it may be a slurry, containing solid components such as minerals, industrial waste (eg fly ash, cement kiln dust) and/or precipitation material, if recycling is used. If recirculation is used, comminution of any solids in the absorption solution may occur. The absorption solution or contacting mixture may include industrial waste brine, naturally occurring alkaline brine, seawater, artificially composed or synthetic brine, or any combination thereof.

Figure 18 is a schematic illustration of an embodiment of the invention wherein the device comprises an array of nebulizers. 4 sprayers are shown, the two center sprayers are optional. The tip sprayer is oriented such that the liquid (ie, absorbing solution or contact mixture) flows countercurrently to the gas flow. The lowermost nebulizers were oriented such that the liquid flowed co-currently with the gas flow (upward in the center of the vertically oriented device). Gas enters the device at the bottom and flows up the length of the device. The device may include rows of sheds in place of the two optional sprayers in the center of the device. The device may include a mist removal section before the gas outlet (not shown). The absorption solution may be a clear liquid, or it may be a slurry, containing solid components such as minerals, industrial waste (eg fly ash, cement kiln dust) and/or sedimentation material, if recycling is used. If recirculation is used, comminution of any solids in the absorption solution may occur.

Figure 20 shows a schematic diagram of the shed row configuration. A top-down or plan view of the configuration is shown on the left-hand side. On the right-hand side a side section of the row configuration is shown. The topmost configuration is the standard configuration of rows of sheds in cylindrical chambers or towers carried by rings. The sheds are staggered so that liquid falling from the upper shed will reach near the top of the lower shed. On the sides, where no full shed exists, downward-sloping inserts are indicated. The configuration in the middle is the configuration of sheds made into concentric rings. These shed rings are carried by wires under the shed, from one side of the chamber or tower to the other. The sheds are staggered, moreover, so that liquid falling from the upper shed will reach near the top of the lower shed. The arrangement of the lowest level of the rows of sheds is configured such that instead of all sheds being aligned parallel to each other through the entire height of the chamber or tower, all other horizontal sheds are oriented at 90° relative to the rows above and below.

Another aspect of highly efficient gas-liquid contact is the time the liquid and gas are in contact so that the gas can be introduced into the liquid. In the case of gas bubbles in a liquid column or liquid droplets surrounded by gas, this contact time may also be referred to as residence time. The residence time of the droplets in the gas can be increased by creating equi-buoyant droplets, as described above. The residence time of a droplet in a gas can also be increased by increasing the length of the path that the droplet follows when it comes into contact with the gas. In some embodiments, the path length is provided by the configuration of the device. Some embodiments take advantage of the convection or motion of the droplets in the contacting chamber, thereby increasing the path length, and thus the residence time, of the droplets in contact with the gas. In some embodiments, the path length is provided by tubing connecting the chambers in which the droplets are generated from the chambers in which they condense. Some embodiments provide liquid droplets to contact gas along long paths. In some embodiments, the long path is a helical path, such as ]] in Figures 21A-22B. In some embodiments, the gas is introduced into the device as an involute feed [Fig. 21A: 400, Fig. 21B: 500, Fig. 22A: 600, Fig. 22B: 700] such that the gas and the liquid droplets in contact with the gas are The contact chamber of the device follows a helical path [Fig. 21A: 410, Fig. 21B: 510, Fig. 22A: 610, Fig. 22B: 710]. Some embodiments utilize an array of gas-inlets [Fig. 21A: 470, Fig. 21B: 540, Fig. 22A: 670, Fig. 22B: 740] to increase the residence time of the droplets in the gas (eg, in the main contacting chamber).

A solution containing a source of secondary cations and a gas source containing _CO can be operably connected to an absorber (eg, a gas-liquid contactor), _{a CO} absorber, as described herein. The absorber can include many different designs including, for example, the gas-liquid contactor 321 of Figures 23A and 23B. As shown in Figure 23B, the gas-liquid contactor can be configured with an inlet (310) in the bottom through which an aqueous solution of divalent cations can be introduced into the gas-liquid contactor. The gas-liquid contactor may also include headers or manifolds 320 (FIGS. 23A, 23B) into which _CO2 -containing gas (330i) may be introduced. FIG. 23B provides a schematic illustration of vortices (ie, turbulent mixing) that can be generated in a solution containing secondary cations while CO ₂ -containing gas is passed through an orifice 322 (eg, an adjustable orifice). Although not illustrated, the gas-liquid contactor may include a number of additional adjustable jets along the length of the gas-liquid contactor. Additional adjustable jets may be used to maintain a vortex, particularly in a system as exemplified in Figure 23A. The gas-liquid contactor may also be configured to have a conical shape that facilitates maintaining and/or enhancing the vortex created in the header or manifold 320 . In such embodiments, additional adjustable jets may still be desirable, particularly when enhanced mixing is desired.

A gas-liquid contactor may include a chamber that includes a plurality of adjustable jets, wherein the jets are configured to inject an aqueous solution including divalent cations into a _CO2 -containing gas (e.g., flue gas from a coal-fired power plant) atmosphere in the room. As shown in FIG. 24 , an orifice 410 (e.g., a common orifice pressure atomizer, etc.) is configured to direct an aqueous solution containing secondary cations against a serrated surface 420 (i.e., a surface comprising many bumps) such that the secondary cation-containing A solution of secondary cations is dispersed into droplets of aqueous solution, effectively increasing the surface area of the incoming secondary cation-containing solution and optimizing the interaction of the secondary cation-containing solution with the _CO2- containing gas. In such embodiments, the jets are configured to operate at low pressures that minimize the energy requirements of the process. In some embodiments, the nozzle operates at a pressure of less than 15 psi, 50 psi, 100 psi, 200 psi, 400 psi, 800 psi, or 1000 psi. In some embodiments, the orifice is configured to have an orifice size of at least 100 microns, 200 microns, 300 microns, 400 microns, 500 microns, 750 microns, or 1000 microns. At such pressures, the orifice, together with the serrated surface, is capable of producing droplets of a solution containing secondary cations, where the droplets have diameters smaller than 0.5 micron, 1 micron, 10 micron, 15 micron, 30 micron, 60 micron, 125 Micron, 250 micron, 500 micron, 1000 micron, 2000 micron, or 4000 micron average diameter.

Another way that can effectively increase the contact time between gas and liquid is to recirculate one within the other. In some embodiments, droplets that have been exposed to a gas coalesce into a liquid solution from which droplets are generated and again contacted with a gas. In some embodiments, the gas that has contacted the droplets is returned to the contacting chamber or device through an array of gas-inlets [Figure 21A: 470, Figure 21B: 540, Figure 22A: 670, Figure 22B: 740]. In some embodiments, both gas and liquid are recycled. In embodiments where methods and apparatus are provided to increase the contact time between a gas and a liquid by increasing the path length of a droplet in a gas, the size of the droplets may range from 100 microns in average diameter to 1 mm or greater, such as the average 200 microns to 1 mm in diameter, 300 microns to 900 microns in average diameter, 400 microns to 900 microns in average diameter, 400 microns to 800 microns in average diameter, 500 microns to 900 microns in average diameter, 500 microns to 800 microns in average diameter, 500 microns in average diameter microns to 700 microns, or an average diameter of 400 microns to 700 microns. In some embodiments, droplets having an average diameter of 500 microns to greater than 1 mm are provided.

Some embodiments take advantage of extended path length, recirculation and high surface area techniques in one contacting chamber. In some embodiments, the liquid used to make the droplets is a slurry and contains solid material. In such embodiments comminutive mixing and recycling of the phases with size-reduced solid components are used together. In some embodiments, the apparatus includes multiple droplet formation stages, some of which utilize comminution and recycling and some of which utilize high surface area technology where the liquid does not contain solid material prior to exposure to the gas. In some embodiments, the method includes mixing a solid and a liquid using pulverization; contacting the solid and liquid mixture, or slurry, with a gas; and separating the solid from the contacted liquid and gas. In some embodiments, the slurry is recycled and contacted with gas several times. In some embodiments, the liquid separated from the solids after the slurry has been exposed to the gas is recycled.

In some embodiments, the devices and systems of the present invention are configured to incorporate greater than 20 tons/hour of carbon dioxide into the absorption solution, under an average of 72 hours of continuous operation. In some embodiments, devices and systems of the present invention are configured to incorporate greater than 40 tons/hour of carbon dioxide into the absorption solution. In some embodiments, devices and systems of the present invention are configured to incorporate greater than 60 tons/hour of carbon dioxide into the absorption solution. In some embodiments, devices and systems of the present invention are configured to incorporate greater than 70 tons/hour of carbon dioxide into the absorption solution. In some embodiments, devices and systems of the present invention are configured to incorporate greater than 80 tons/hour of carbon dioxide into the absorption solution. In some embodiments, devices and systems of the present invention are configured to incorporate greater than 90 tons/hour of carbon dioxide into the absorption solution. In some embodiments, devices and systems of the present invention are configured to incorporate greater than 100 tons/hour of carbon dioxide into the absorption solution. In some embodiments, devices and systems of the present invention are configured to incorporate greater than 110 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the devices and systems of the present invention are configured to incorporate greater than 120 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the devices and systems of the present invention are configured to incorporate greater than 130 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the devices and systems of the present invention are configured to incorporate greater than 140 tons/hour of carbon dioxide into the absorption solution. In some embodiments, devices and systems of the present invention are configured to incorporate greater than 150 tons/hour of carbon dioxide into the absorption solution. In some embodiments, devices and systems of the present invention are configured to incorporate greater than 160 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the devices and systems of the present invention are configured to incorporate greater than 170 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the devices and systems of the present invention are configured to incorporate greater than 180 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the devices and systems of the present invention are configured to incorporate greater than 190 tons/hour of carbon dioxide into the absorption solution. In some embodiments, the devices and systems of the present invention are configured to incorporate greater than 200 tons/hour of carbon dioxide into the absorption solution.

In some embodiments, _the devices and systems of the present invention include devices and systems for removing CO from a gas source, for example, a gas source of industrial _CO such as flue gas from a power plant, or exhaust gas such as from a cement plant , wherein the device and system are configured such that water (e.g. seawater, brine, absorption solution) into which _CO2 has been dissolved by a gaseous source of _CO2 (e.g. an industrial source of carbon dioxide) is subjected to precipitation conditions, wherein the precipitation conditions provide a precipitate , in amounts ranging from 2.6 g of precipitate/1 liter of absorption solution to 26.11 g of precipitate/1 liter of absorption solution, over an average period of 72 hours of continuous application of precipitation conditions. In some embodiments, the device and system are configured to provide precipitation conditions that provide a precipitate in an amount of: 5.2 grams of precipitate per liter of absorption solution to 26.11 grams of precipitate per liter of absorption solution, over an average period of 72 hours of continuous application of precipitation conditions. In some embodiments, the devices and systems are configured to provide precipitation conditions that provide precipitate in an amount of: 7.83 grams of precipitate per liter of absorption solution to 26.11 grams of precipitate per liter of absorption solution, at Precipitation conditions are applied continuously over an average period of 72 hours, such as 9.14 to 26.11, such as 10.44 to 26.11, such as 11.75 to 26.11, such as 13.05 to 26.11, such as 14.36 to 26.11, such as 15.66 to 26.11, such as 16.97 to 26.11, such as 18.27 to 26.11, such as 19.58 to 26.11, such as 20.88 to 26.11, such as 22.19 to 26.11, such as 23.5 to 26.11, such as 24.8 to 26.11 g of precipitate/1 liter of absorption solution.

The carbonate mineral precipitation station 20 (i.e., the reactor) can include a number of different components, such as temperature control components (e.g., configured to heat the water to a desired temperature), chemical additive components, e.g., for introducing chemical pH raising reagents (such as KOH, NaOH) into water, electrolysis components, eg, cathode/anode, etc., gas feeding components, pressurization components (such as where the process is operated under pressurized conditions, such as 50-800psi, or 100-800psi , or 400 to 800 psi, or any other suitable pressure range, is desired), etc., mechanical agitation and physical agitation components and components for recirculating industrial plant flue gas through the settling device.

The carbonate mineral precipitation station 20 may comprise a number of different components that allow monitoring (e.g., on-line monitoring) of one or more parameters such as internal reactor pressure, pH, precipitate particle size, metal-ion concentration, conductivity of the aqueous solution rate, aqueous alkalinity, and pCO ₂ . Monitoring conditions during the carbonate precipitation method may allow calibration adjustments to be made during the precipitation process. For example, calibration adjustments may be made to increase or decrease the production of carbonate compound precipitation. In some embodiments, the carbonate precipitation process is monitored with an on-line monitoring device operably connected to the carbonate mineral precipitation station, the on-line monitoring device comprising a dilution manifold, an ion selective electrode, a voltmeter, a controller, and a diluent source. Figure 25 illustrates one possible online monitor 1600. Operationally, the controller (1660) controls the variable flow control valve (1621). The controller-operated variable flow control valve allows the settling table effluent to enter the dilution manifold (1630), typically after passing through a filter (not shown). in Figure 25) in order to remove carbonate mineral precipitates. The undiluted sedimentation table effluent was then measured for ion concentration. For ion concentration measurements, a voltmeter (1650), for example, is used, connected to one or more electrodes (1640), selective for particular ions (eg, Ca2+ or Mg2+). If the measured voltage is outside the accepted voltage range (eg, such as outside the linear portion of the voltage versus ion concentration curve), the precipitation table effluent in the dilution manifold is diluted with a diluent (1610). A controller, operatively connected to the voltmeter and diluent, monitors and records the delivery of diluent through the controller-operated variable control valve (1610). Controlled diluent delivery is slowed or stopped when the voltage reading falls within the accepted range. Depending on the controller-determined ion concentration of the ions considered in the initial settling table effluent, diluent may be added to the settling table through variable flow control valve 1612 (eg, if the ion concentration is high), or the settling Stage effluent can be drained from the precipitation stage through valve 1622 (eg, if the ion concentration is low), with concomitant delivery of a more concentrated ionic solution through the precipitation stage inlet.

It may be desirable to incorporate one or more components from a gas stream into an absorption solution, such as removing carbon dioxide and optionally SOx, NOx, and other non- _CO acid gases from industrial flue gases, without forming solid precipitates. In this case, controllers, monitoring devices, and precipitation conditions, described in detail elsewhere herein, may be used in order to optimize the introduction of at least one gas component into the absorption solution and continue to prevent the release of one or more components into the in the Earth's atmosphere. If the introduction of components of the gas stream into the absorption solution does not result in precipitation, the resulting solution can be processed further through the system to recover usable absorption solution or to recover water which is potable or suitable for irrigation purposes. Alternatively, if the introduction of gas stream components into the absorption solution does not cause precipitation, the resulting solution may be sent to a retention facility such as, but not limited to, an underground location, including geological formations such as aquifers. Such a solution resulting from the introduction of components of the gas stream into the absorption solution may be transported to the retention facility using any convenient method including, but not limited to, pipelines such as pipes or ditches, tank trucks, pumps, tanks transported by rail or barge, or a combination thereof.

As illustrated in Figure 6A, the precipitated product resulting from precipitation at step 20 can be separated from the precipitation table effluent at step 40 to produce a separate precipitated product. The isolated precipitated product can also be a "wet dehydrated precipitate" since the freshly isolated precipitated product can be dried in a subsequent step. Separation of the settling table effluent from the precipitated product is accomplished using any number of suitable means, including drainage (e.g., gravity settling of the precipitated product followed by drainage), decantation, filtration (e.g., gravity filtration, vacuum filtration, filtration using pressurized air) , centrifuged, pressed, or any combination thereof. In some embodiments, separation of the precipitation product from the precipitation table effluent is achieved by flowing the precipitation table effluent against a baffle, wherein the supernatant liquid is deflected against the baffle and separated from the precipitation product particles, The latter are collected in the collector. In some embodiments, the precipitation product is separated from the precipitation table effluent by flowing the precipitation table effluent in a helical channel, separating the precipitation product particles and collecting the precipitation product from an array of helical channel outlets. Mechanically, at least one liquid-solid separation device is operably connected to the settling table such that the settling table effluent can flow from the settling table to the liquid-solid separation device (e.g., the liquid-solid separation device includes baffles or spiral channels) . The settling table effluent can be passed directly to the liquid-solid separation unit, or the effluent can be pretreated, as described in detail below.

The energy requirements for any of the above separation pathways can be met by adapting the process to use a number of energy-containing waste streams (e.g., waste heat or waste gas streams) provided by industrial facilities; a person skilled in the art should then It is understood that separation methods requiring less energy are desirable in reducing the carbon footprint of the invention.

Concentration and separation of the precipitated product from the effluent of the settling table can be achieved continuously or intermittently, using the liquid-solid separation method and apparatus described in WO 2007/051640 and CA02628270, the disclosures of which are incorporated herein by reference. In some embodiments, the liquid-solid separation device includes a vessel having a funnel-shaped section, a settling table effluent pipe extending in the longitudinal direction arranged in the vessel and a channel for introducing sediment falling through the settling table effluent pipe. The inlet opening for the flow of the table effluent and the removal opening formed at the lower end of the funnel-shaped section for removing the separated precipitated product from the container The opening to the container is characterized by baffles arranged in the area of the inlet opening, the sedimentation table effluent flow Movement is deflected through it. Liquid-solid separators such as Epuramat's Extrem-Separator ("ExSep") liquid-solid separators or variations thereof may be used in some embodiments to separate the precipitation product and the precipitation table effluent.

To separate the precipitated product from water, the settling table effluent is introduced into the bath in the direction of gravity, where the precipitated product particles descend under the force of gravity and are removed from its bottom. This removal of precipitated product particles can be carried out continuously or intermittently. The settling table effluent, as it is introduced into the bath, flows against the baffles by which the flow in the bath is deflected. Controlled by this method, a hydro-physical reaction zone is created in the region of the inlet opening, in which at least significant flow energy of the settling table effluent flow in the direction of gravity is disrupted. Deflecting the flow of the sedimentation table effluent into the sedimentation table effluent pipe in the vertical direction facilitates the separation of the precipitation product particles due to the difference in electric density compared to the water. When the settling table effluent is deflected, the heavier settling product particles have a greater tendency to continue their trajectory in the direction of the settling table effluent pipe (i.e., in the downward direction), while the water is deflected, and with The heavy precipitated product particles separate and rise. When flowing against the baffles (i.e. in the flow direction of the settling table effluent flowing through the settling table effluent pipe, when leaving the settling table effluent pipe downstream of the baffles and mainly after it), basically by Deflection losses cause disruptions in kinetic energy. The settling table effluent is deflected in particular by the settling product particles (i.e., particles having a greater density than water), which would normally descend in the vessel, in a substantially undisturbed manner, upon introduction into the During the bath, the downward movement of the effluent pipe originating from the settling table continued. The deflection would not have the result of having a high density of precipitation product particles, ie the compound of the precipitation product particles having an upward velocity applied to them during the deflection. Such a velocity component should only be applied to the light water during deflection, so that due to the deflection, at the baffles, the water receives the required velocity component in order to rise in the bath.

Alternatively, the concentration and separation of precipitation products from the effluent of the precipitation table can be achieved continuously or intermittently, using the liquid-solid separation method and apparatus described in US 2008/018331, the disclosure of which is incorporated herein by reference. In some embodiments, the liquid-solid separation device comprises an inlet operative to receive the settling table effluent; a channel operative to allow flow of the settling table effluent, the channel being in a helical configuration; a precipitation stage effluent separation precipitation product; and at least one outlet for a precipitation product-depleted supernatant. Liquid-solid separators such as Xerox PARC's spiral concentrators, or variations thereof, may be used in some embodiments to separate the precipitation product from the precipitation table effluent.

The precipitation product is separated from the settling table effluent based on the size and mass separation of the precipitation product particles, which are forced to flow in the helical channel. On the helical section, the inward lateral pressure field from fluid shear competes with the outward centrifugal force allowing separation of the precipitated product particles. At high speeds, centrifugal force prevails and the precipitated product particles move outward. At low speeds, transverse pressure prevails and the precipitated product particles move inward. The magnitude of the two relative forces depends on the flow rate, particle size, radius of curvature of the helical section, channel dimensions, and viscosity of the sedimentation table effluent. At the end of the helical channel, a parallel array of outlets collects the separated particles of the precipitated product. For any particle size, the required channel size is determined by estimating the transfer time to the sidewall. This time is a function of flow rate, channel width, viscosity, and radius of curvature. Larger particles of precipitation product can reach the channel walls before smaller particles, which take more time to reach the side walls. Thus, a helical channel may have multiple outlets along the channel. This technique is inherently scalable over a large size range (from sub-millimeter down to 1 micron).

It may be desirable to pretreat (e.g., coarse filter) the settling table effluent to remove large-sized particles of the precipitated product from the effluent before providing the effluent to a liquid-solid separation device, since large-sized particles can interfere with liquid-solid separation. Separation device or method. Separation of the precipitation product from the precipitation table effluent can be achieved using a single liquid-solid separation device. In some embodiments, a combination of 2, 3, 4, 5, or more than 5 liquid-solid separation devices may be used to separate the precipitation product from the precipitation table effluent. Combinations of liquid-solid separators can be used in series, parallel or a combination of series and parallel, depending on the desired throughput. In some embodiments, the liquid-solid separation device or combination thereof can operate at 100L/min-2,000,000L/min, 100L/min-1,000,000L/min, 100L/min-500,000L/min, 100L/min-250,000L/min min, 100L/min-100,000L/min, 100L/min-50,000L/min, 100L/min-25,000L/min, and 100L/min-20,000L/min process the sedimentation table effluent. In some embodiments, the liquid-solid separation device or combination thereof can operate at 1000L/min-2,000,000L/min, 5000L/min-2,000,000L/min, 10,0000L/min-2,000,000L/min, 20,000L/min- 2,000,000L/min, 25,000L/min-2,000,000L/min, 50,000L/min-2,000,000L/min, 100,000L/min-2,000,000L/min, 250,000L/min-2,000,000L/min, 500,000L/min- 2,000,000L/min, and 1,000,000L/min-2,000,000L/min to treat sedimentation platform effluent. In some embodiments, the liquid-solid separation device or combination thereof can operate at 1000L/min-20,000L/min, 5000L/min-20,000L/min, 10,000L/min-20,000L/min, 1000L/min-10,000L /min, 2000L/min-10,000L/min, 3000L/min-10,000L/min, 4000L/min-10,000L/min, 5000L/min-10,000L/min, 6000L/min-10,000L/min, 7000L/min min-10,000L/min, 8000L/min-10,000L/min, 9000L/min-10,000L/min, or 9500L/min-10,000L/min to process the sedimentation platform effluent.

Combinations of liquid-solid separators in series, parallel or a combination of series and parallel can also be used to increase separation efficiency. Additionally, the supernatant produced by one or more liquid-solid separation devices may be recycled through the liquid-solid separation device to increase separation efficiency. In some embodiments, 30% to 100%, 40% to 100%, 50% to 100%, 60% to 100%, 70% to 100%, 75% to 100%, 80% are collected from the settling table effluent to 100%, 85% to 100%, 90% to 100%, 95% to 100%, 96% to 100%, 97% to 100%, 98% to 100%, 99% to 100% of the precipitated product. Depending on the amount of precipitation product removed from the settling station effluent, the supernatant may be sent back to the settling station or provided to the electrolytic cell of the present invention. In some embodiments, the supernatant, which has a higher concentration of precipitation product, is conveyed back to the settling station for agglomeration of the precipitation product particles. In some embodiments, the supernatant with a higher concentration of dissolved divalent cations (eg, Ca2+ or Mg2+) is sent back to the settling station as a source of divalent cations. In some embodiments, the supernatant, which has relatively low concentrations of precipitated products and dissolved divalent cations, is filtered to remove significant amounts of remaining divalent cations and provided to the electrolytic cells of the present invention.

This removal of precipitated product particles can be carried out continuously or intermittently.

In some embodiments, the precipitation product is not separated or only partially separated from the precipitation table effluent. In such embodiments, the effluent, including some (eg, after passing through the liquid-solid separation device) or all of the precipitated product, can be treated in a number of different ways. In some embodiments, the effluent from the settling station, including some or all of the settling products, is transported to a land or water location and stored there. Transport to the ocean is particularly useful in embodiments wherein the water source is seawater. It will be appreciated that the carbon footprint, the amount of energy used, and/or the amount of _CO2 produced, for a certain amount of _CO2 sequestered by industrial waste gas, is minimized in a method wherein the sediment No further processing other than treatment was performed.

In the embodiment illustrated in Figure 6A, the resulting dehydrated precipitate is then dried to produce a product, as illustrated at step 60 of Figure 6A. Drying can be achieved by air drying the filtrate. Where the filtrate is air dried, the air drying can be at room temperature or elevated temperature. In certain embodiments, the high temperature is provided by the industrial facility gaseous waste stream, as illustrated at step 70 of FIG. 7 . In these embodiments, a gaseous waste stream (eg, flue gas) from a power plant may first be used in a drying step, wherein the gaseous waste stream may have a temperature of 30 to 700°C, such as 75 to 300°C. The gaseous waste stream can be directly contacted with the wet precipitate in the drying stage, or used to indirectly heat a gas (eg air) in the drying stage. By having the gas conveyor from the industrial plant, e.g. the piping originate at a suitable location, e.g. in the HRSG or at some distance on the flue, the desired temperature can be provided in the gaseous waste stream, e.g. based on the industrial plant The details of the exhaust gas and configuration structure are determined. In yet another embodiment, the precipitate is dried by spray drying, wherein the precipitate-containing liquid is dried by feeding it through a hot gas, such as a gaseous waste stream from an industrial facility, for example, where the liquid feed is pumped through the atomizer into the main drying chamber, while the hot gas passes in either co-current or counter-current relative to the direction of the atomizer. In certain embodiments, drying is achieved by freeze-drying (i.e., lyophilization), wherein the precipitate is frozen, the ambient pressure is reduced and sufficient heat is added so that the frozen water in the material sublimates directly from the frozen precipitate phase to gas. Depending on the particular drying process of the system, the drying station may include filter elements, freeze drying structures, spray drying structures, etc.

If desired, the dewatered precipitate product from the separation reactor 40 may be washed prior to drying, as illustrated in optional step 50 of FIG. 6A. The precipitate can be washed with fresh water, for example, to remove salts (such as NaCl) from the dehydrated precipitate. The wash water used may suitably be treated, for example, by treating it in a tailings pond, etc.

In certain embodiments of the invention, the precipitate can be separated, washed and dried, in the same station for all methods, or in different stations for all methods, or any other possible combination. For example, in one embodiment, precipitation and separation can occur in precipitation reactor 20, but drying and washing occur in different reactors. In yet another embodiment, precipitation, separation, and drying may all occur in the precipitation reactor 20, while washing is performed in a different reactor.

After separating the precipitate and mother liquor, eg, as described above, the separated precipitate can be further processed, as desired. In certain embodiments, the precipitate can then be transported to a location for long-term storage, effectively sequestering the _CO2 . For example, sediment can be transported and placed in a long-term storage location, eg, above ground, underground, in deep sea, etc., as desired.

Dried products can be disposed of in many different ways. In certain embodiments, the sediment product is transported to a location for long- _term storage, effectively sequestering CO2 in the form of a stable precipitated product, such as in the form of a storage-stable aboveground _CO2 -storage material . For example, sediment can be stored in long-term storage locations adjacent to industrial equipment and sedimentation systems. In other embodiments, the sediment can be transported and placed in a long-term storage location, e.g., above ground, underground, etc., as desired, where the long-term storage location is remote from the power plant (this is the case in embodiments where real estate near the power plant is scarce). may be desirable). In those embodiments where the sediment is transported to a long-term storage location, it may be transported in empty transport vehicles (e.g., barges, train cars, trucks, etc.), the latter being used for Conveying fuel or other materials to industrial equipment and/or settling plants. In this way, the precipitation product can be transported using the transport vehicle used to bring the fuel to the industrial facility and the material to the precipitation facility (eg, alkali source), thereby sequestering the _CO2 from the industrial facility.

In certain embodiments, the composition is treated in an underwater location. The underwater location can vary, depending on the particular application. While the underwater location may be an inland underwater location, for example, in a lake (including freshwater lakes), in certain embodiments the interest is a marine or seawater underwater location. The composition may still be in the mother liquor without separation or complete separation, or the composition may have been separated from the mother liquor. Underwater locations can be shallow or deep. A shallow location is a location of 200 feet or less, such as 150 feet or less, including 1000 feet or less. Deep locations are those that are 200 feet or greater, such as 500 feet or greater, 1000 feet or greater, 2000 feet or greater, including 5000 feet or greater.

Where desired, the composition consisting of the precipitate and the mother liquor can be stored for a period of time after precipitation and before disposal. For example, the composition may be stored at 1°C-40°C, such as 20°C-25°C, for 1 to 1000 days or longer, such as 1-10 days or longer.

Any suitable procedure for transporting the composition to the processing location may be used and will necessarily vary depending on the precipitation reactor location and the processing location interrelationship, whether the processing location is an aboveground or underground processing location, and the like. In certain embodiments, pipes or similar slurry delivery structures are used, where these pathways may include active pumps, gravity mediated flow, etc., as desired.

While in certain embodiments the precipitate is processed directly at the processing site without further processing after precipitation, in other embodiments the composition may be further processed prior to processing. For example, in certain embodiments, a solid physical shape may be produced from the composition, wherein the resulting shape is then processed at the contemplated processing site. An example of such an embodiment is where an artificial reef structure is produced from a carbonate compound composition, for example, by placing a flowable composition in a suitable mold structure and allowing the composition to cure over time into the desired shape . The resulting solid reef structure can then be stored in a suitable marine location, such as a shallow underwater location, to create an artificial reef, as desired.

In certain embodiments, the precipitate produced by the methods of the invention is treated by using it in an article of manufacture. In other words, using products to make man-made objects, ie making objects. The product may be used by itself or combined with one or more additional materials such that it is a component of an article of manufacture. Contemplated articles of manufacture may vary, with examples of contemplated articles of manufacture including construction materials and non-construction materials such as non-bonded articles of manufacture. The construction materials considered include concrete components such as cement, aggregates (fine and coarse), auxiliary binding materials, etc. Contemplated building materials also include preformed building materials.

_CO2 from gaseous waste streams from industrial facilities is effectively buried in man-made environments where the product is disposed of by incorporating it in building materials. Examples of the use of the product in building materials include cases where the product is used as a building material for certain types of man-made structures, such as buildings (commercial or residential), roads, bridges, levee, dams, and other man-made structures and the like. Building materials may be used as structural or non-structural components of such structures. In such an embodiment, the settling unit may be co-located with the building products factory.

In certain embodiments, the precipitated product is refined (ie, processed) in some manner prior to subsequent use. Refining as exemplified in step 80 of FIG. 6A can include a variety of different procedures. In certain embodiments, the product is mechanically refined, eg, milled, to obtain a product with desired physical properties, eg, particle size and the like. In certain embodiments, the sediment is combined with hydraulic cement, for example, as a secondary binding material, as sand, gravel, as aggregate, and the like. In certain embodiments, one or more components may be added to the sediment, e.g., where the sediment is to be used as cement, e.g., one or more additives, sand, aggregates, auxiliary cement materials, etc. to produce a final product such as concrete or mortar, 90.

In certain embodiments, carbonate compound precipitates are used to produce aggregate. Such aggregates, their method of manufacture, and their use are described in co-pending United States Patent Application (Publication No.) US 2010-0024686A1, which was published on February 4, 2010, which is incorporated herein by reference in its entirety.

In certain embodiments, carbonate compound precipitates are used as components of hydraulic cement. The term "hydraulic cement" is used in its conventional sense to refer to a composition that cures and hardens after combining with water. The setting and hardening of the products produced by the combination of the cement of the present invention with an aqueous fluid results from the production of hydrates, which are formed by the cement upon reaction with water, wherein the hydrates are substantially insoluble in water. Such carbonate compound component hydraulic cements, their method of manufacture, and their use are described in co-pending U.S. Patent Application (Publication No.) US 2009-0020044A1, which was published on January 22, 2009, It is incorporated herein by reference in its entirety.

Also considered is the formed building material. The formed building materials of the present invention can vary widely. "Formed" means shaped, eg, molded, cast, cut or otherwise produced, into a defined physical shape of a man-made structure, ie, a configuration. Shaped building materials are distinguished from amorphous building materials, such as granular (eg, powder) compositions, which do not have a defined and stable shape, but instead conform to the container in which they are contained, eg, a bag or other container. Exemplary formed building materials include, but are not limited to: bricks; slabs; pipes; beams; pots; columns; drywall; Further examples and details regarding formed building materials include those described in US Patent Application No. 12/571,398, filed September 30, 2009, which is incorporated herein by reference in its entirety.

Also contemplated are non-bonded manufactured articles comprising the products of the invention as components. The non-bonded manufactured articles of the present invention can vary widely. Non-bonding means that the composition is not hydraulic cement. Thus, the composition is not a dry composition, which when combined with a curing fluid, such as water, cures to produce a stable product. Exemplary compositions include, but are not limited to: paper products; polymer products; lubricants; asphalt products; paints; personal care products such as cosmetics, toothpaste, deodorants, soaps, and shampoos; human ingestible products , including liquids and solids; agricultural products, such as soil amendment products and animal feed; and more. Further examples and details regarding non-bonded manufactured articles include those described in U.S. Patent Application No. 12/609,491, filed October 30, 2009, which is incorporated herein by reference in its entirety.

The resulting mother liquor can also be processed, as desired. For example, the mother liquor can be returned to the source of the water, eg, the ocean, or to another location. In certain embodiments, the mother liquor can be contacted with a source of _CO2 , eg, as described above, to sequester additional _CO2 . For example, where the mother liquor is to be returned to the ocean, the mother liquor may be contacted with a gas source of _CO2 in a manner sufficient to increase the concentration of carbonate ions present in the mother liquor. Contacting can be performed using any suitable procedure, such as those described above. In certain embodiments, the mother liquor has an alkaline pH, and the contacting with the source of _CO2 is performed in a manner sufficient to lower the pH to 5-9, such as 6-8.5, including 7.5-8.2. Thus, the resulting reaction mother liquor, eg, mineral carbonate-depleted water, may be treated using any suitable procedure. In some embodiments, it may be sent to tailings ponds for disposal. In certain embodiments, it can be processed in naturally occurring bodies of water, eg, oceans, seas, lakes or rivers. In certain embodiments, it can be used as a coolant for industrial equipment, for example, by a process line running between a sedimentation system and the industrial equipment. In certain embodiments, it can be used as gray water, water input for desalination, and subsequently used as fresh water, eg, in irrigation, for human and animal consumption, and the like. Therefore, contemplated are arrangements in which the precipitation unit is co-located with the desalination unit such that output water from the precipitation unit is used as the injection water for the desalination unit.

As noted above, in certain embodiments, the mother liquor produced by the precipitation process can be used to cool a power plant that provides a source of CO ₂ , for example, in a once-through cooling system. In such an embodiment, the heat obtained in the process can then be recycled back to the precipitation unit for further use, as desired. In such embodiments, the primary water source may be from an industrial facility. Such embodiments may be modified to use the suction capabilities provided by industrial equipment, for example, to increase overall efficiency.

Where desired and after production of the CO ₂ -storage product, eg, as described above, the amount of CO ₂ stored in the product is quantified. "Quantitating" refers to determining the amount of _CO2 that has been stored (ie, fixed) in a _CO2 storage product, eg, in numerical form. The determination may be an absolute quantification of the product, where desired, or it may be an approximate quantification, ie imprecise. In some embodiments, quantification is suitable to give a market-accepted measure of the amount of CO ₂ stored.

The amount of CO ₂ in the CO ₂ -storage product can be quantified using any convenient method. In certain embodiments, quantification can be performed by actual measurement of the composition. In these embodiments, a variety of different methods can be used. For example, measuring the mass or volume of a composition. In certain embodiments, such measurements can be performed while the precipitate is in the mother liquor. In these cases, additional methods such as X-ray diffraction can be used to quantify the product. In other embodiments, the measurement is performed after the precipitate has been washed and/or dried. The measurements are then used to quantify the amount of _CO2 stored in the product, for example, by mathematical calculations. For example, a coulometer can be used to obtain a reading of the amount of carbon in the precipitated sequestered product. This coulometer reading can be used to determine the amount of carbonate in the sediment, which can then be converted to sequestered _CO2 , by stoichiometry, based on factors such as the original metal ion content of the water, the chemical The limiting reagent for the reaction, the theoretical yield of the starting material for the reaction, the water of hydration for the precipitated product, etc. In some embodiments, contaminants may be present in the product and other determinations of product purity, eg, elemental analysis, may be necessary to determine the amount of _CO2 being stored.

In other embodiments, isotopic methods are used to determine the carbon content of the product. The ratios of carbon isotopes in fossil fuels differ substantially from the ratios of such isotopes in geological sources such as limestone. Thus, the source or source ratio of carbon in a sample is readily elucidated by mass spectrometry, which quantitatively measures isotopic masses. Thus even though limestone aggregates are used in concrete (which would add to the total carbon determined by coulometric analysis), the use of mass spectrometry for isotope analysis will allow elucidation of the amount of carbon attributable to captured _CO2 from fossil fuel combustion. In this way, the amount of carbon sequestered in sediments or even downstream products associated with sediments, eg concrete, can be determined, particularly where the _CO2 gas used to make the sediments is obtained from the combustion of fossil fuels such as coal. Benefits of this isotopic approach include the ability to determine the carbon content of pure precipitates as well as precipitates introduced into another product, in the form of aggregates or sand in concrete, and the like.

In other embodiments, quantification may be performed by making a theoretical determination of the amount of _CO2 stored, such as by calculating the amount of _CO2 stored. By using the known yield of the method described above, such as where the yield is known from an earlier experimental procedure, the amount of sequestered _CO can be calculated. Known yields can vary depending on a number of factors, including one or more of the following: gas (e.g., _CO2 ) and water input, concentration of metal ions (e.g., alkaline earth metal ions), pH, salinity, temperature , the rate of the gas stream, the selected method embodiment, etc., as described above. The amount of _CO2 stored in a given _process can be easily determined using, standard information, e.g., predetermined amount of CO2 stored/amount of product produced by a given reference process, which is the same as or Roughly approximating the reference method, for example, by determining the amount produced and then calculating the amount of _CO2 that must be stored therein.

_CO2 storage system

Aspects of the invention further include systems, eg, process plants or plants, for sequestering _CO2 , eg, by implementing the methods described above. The system of the invention may have any configuration capable of implementing the particular production method under consideration.

In some embodiments, the present invention provides a system for processing carbon dioxide, as shown in FIG. ) processing carbon dioxide from a carbon dioxide source (130), and wherein the carbon dioxide source includes one or more additional components other than carbon dioxide. As shown in Figure 1, the system may further include a source of divalent cations (150) operatively connected to the processor. The processor may include a contactor such as a gas-liquid or gas-liquid-solid contactor, wherein the contactor is configured to feed an aqueous solution or slurry with carbon dioxide to produce a carbon dioxide-fed composition, which may be a solution or a slurry. In some embodiments, the contactor is configured to produce a composition from carbon dioxide, such as from solvated or hydrated forms of carbon dioxide (e.g., carbonic acid, bicarbonate, carbonate), wherein the composition includes carbonate, bicarbonate Or carbonates and bicarbonates. In some embodiments, the processor can further include a reactor configured to produce a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate from carbon dioxide. In some embodiments, the processor may further include a clarifier configured to settle the composition comprising precipitation material including carbonates, bicarbonates, or carbonates and bicarbonates. As shown in FIG. 2, the system may further include a treatment system (e.g., treatment system 120 of FIG. 2) configured to concentrate a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate , and a supernatant is produced; however, in some embodiments the composition is used without further processing. For example, in the manufacture of building materials, the system of the invention can be configured to use the composition directly from the processor (optionally with minimal post-processing). In another non-limiting example, the system of the present invention can be configured to directly inject the composition from the processor (optionally with minimal post-treatment) to a subterranean location, as described in U.S. Provisional Patent Application 61/232,401 (2009 filed on August 7, 2011, which application is incorporated herein by reference in its entirety). The carbon dioxide source may be any of various industrial sources of carbon dioxide including, but not limited to, coal-fired power plants and cement plants. The proton-removing agent source can be any of a variety of proton-removing agent sources including, but not limited to, natural sources of proton-removing agents and industrial proton-removing agent sources (including industrial waste sources). The source of divalent cations may be from any of a variety of divalent cation sources including, but not limited to, seawater, brine, and freshwater with added minerals. In such embodiments, the source of divalent cations may be operably linked to the source of proton-removing agent or directly to the processor. In some embodiments, the source of divalent cations includes divalent cations of alkaline earth metals (eg, Ca2 ⁺ , Mg2+).

The system of the present invention such as that shown in FIG. 1 may further include a processing system. Thus, in some embodiments, the present invention provides a system for processing carbon dioxide, as shown in Figure 2, wherein the system includes a processor (110) and a processing system (120) configured for an aqueous-based Carbon dioxide from a carbon dioxide source (130) is processed using a proton-removing agent source (140), and wherein the carbon dioxide source includes one or more additional components other than carbon dioxide. As with Figure 1, the system of Figure 2 may further include a source of divalent cations (150) operatively connected to the processor. The processor may include a contactor such as a gas-liquid or gas-liquid-solid contactor, wherein the contactor is configured to feed an aqueous solution or slurry with carbon dioxide to produce a carbon dioxide-fed composition, which may be a solution or a slurry. In some embodiments, the contactor is configured to produce a composition from carbon dioxide, such as from solvated or hydrated forms of carbon dioxide (e.g., carbonic acid, bicarbonate, carbonate), wherein the composition includes carbonate, bicarbonate Or carbonates and bicarbonates. In some embodiments, the processor can further include a reactor configured to produce a composition comprising carbonate, bicarbonate, or carbonate and bicarbonate from carbon dioxide. In some embodiments, the processor may further include a clarifier configured to settle the composition comprising precipitation material including carbonates, bicarbonates, or carbonates and bicarbonates. The treatment system may include a dehydration system configured to concentrate compositions including carbonates, bicarbonates, or carbonates and bicarbonates. The treatment system may further include a filtration system, wherein the filtration system includes at least one filtration unit configured to filter the supernatant from the dewatering system, filter the composition from the processor, or a combination thereof. For example, in some embodiments, the filtration system includes one or more filtration units selected from the group consisting of microfiltration units, ultrafiltration units, nanofiltration units, and reverse osmosis units. In some embodiments, the carbon dioxide treatment system includes a nanofiltration unit configured to increase the concentration of divalent cations in the retentate and decrease the concentration of divalent cations in the retentate. In such an embodiment, the nanofiltration unit retentate can be recycled to the processor of the system in order to produce the composition of the invention. As shown in Figure 4, the system of the present invention can be further configured to recycle at least a portion of the supernatant from the treatment system.

A system such as that shown in FIG. 3 may further include a processor (110) comprising a contactor (112) (e.g., a gas-liquid contactor, a gas-liquid-solid contactor, etc.) and a reactor ( 114), wherein the processor is operatively connected to a source of CO ₂ -containing gas (130), a source of proton-removing agent (140), and a source of divalent cations (150). Such systems of the present invention are configured for aqueous based treatment of carbon dioxide from a carbon dioxide source using a source of proton-removing agents and a source of divalent cations, wherein the carbon dioxide source comprises one or more additional components other than carbon dioxide point. A contactor (112) can be operably connected to each of the carbon dioxide source (130) and the proton-removing agent source (140), and the contactor can be configured for feeding the aqueous solution or slurry with carbon dioxide to produce a carbon dioxide-fed solution or slurry. In some embodiments, the contactor is configured to feed the aqueous solution with carbon dioxide to produce a substantially clear solution (ie, substantially free of precipitation material, such as at least 95% or more free). As shown in Figure 3, the reactor (114) can be operably connected to the contactor (112) and the source (150) of divalent cations, and the reactor can be configured to produce the composition of the present invention, wherein the composition is Solutions or slurries of carbonates, bicarbonates or carbonates and bicarbonates are included. In some embodiments, the reactor is configured to receive carbonate, bicarbonate, or a substantially clear solution of carbonate and bicarbonate from the processor and produce a composition comprising precipitation material (e.g., divalent cation carbonate, bicarbonate or carbonate and bicarbonate slurry). The system as shown in Figure 3 may optionally be operably connected to a processing system which may include a liquid-solid separator (122) or some other dewatering system configured to treat the combined processor-generated to produce a supernatant and a concentrated composition (eg, concentrated relative to carbonate and/or bicarbonate, and any other by-products derived from processing industrial waste streams). The treatment system may further include a filtration system, wherein the filtration system includes at least one filtration unit configured to filter the supernatant from the dewatering system, filter the composition from the processor, or a combination thereof.

In some embodiments, the present invention provides a system for processing carbon dioxide, as shown in Figure 4, wherein the system includes a processor (110) and a processing system (120) configured for an aqueous-based method using protons - The remover source (140) processes carbon dioxide from the carbon dioxide source (130), wherein the carbon dioxide source includes one or more additional components other than carbon dioxide, and further wherein the processor and treatment system are operatively connected for recycling At least a portion of the system supernatant is disposed of. The treatment systems of such carbon dioxide-treatment systems may include dehydration systems and filtration systems. Thus, the dehydration system, the filtration system, or a combination of the dehydration system and the filtration system may be configured to provide at least a portion of the supernatant to the processor for processing carbon dioxide. Although not shown in FIG. 4, the treatment system can also be configured to provide at least a portion of the supernatant to a washing system configured to wash the composition of the present invention, wherein the composition includes precipitation material (e.g., CaCO ₃ , MgCO ₃ or a combination thereof). The processor of the carbon dioxide-treatment system of the present invention can be configured to receive the treatment system supernatant in the following: contactors (e.g., gas-liquid contactors, gas-liquid-solid contactors), reactors, contactors, and A combination of reactors, or any other unit or combination of units in a processor. In some embodiments, the carbon dioxide-treatment system is configured to provide at least a portion of the supernatant to a system or process external to the carbon dioxide treatment system. For example, the system of the present invention can be operatively connected to a desalination unit such that the system provides at least a portion of the treatment system supernatant to the desalination unit for desalination.

In some embodiments, the present invention provides a system for processing carbon dioxide, as shown in FIG. 5, wherein the system includes a processor (110) and a processing system (120) configured for an aqueous based method using protons - the removal agent source (140) processes carbon dioxide from the carbon dioxide source (130), wherein the carbon dioxide source includes one or more additional components other than carbon dioxide, wherein the system further comprises an electrochemical system (160), and further wherein the processing The device, treatment system, and electrochemical system are operatively connected to recycle at least a portion of the treatment system supernatant. As described above with reference to the treatment system of FIG. 4 , the dewatering system, the filtration system, or a combination of the dehydration system and the filtration system can be configured to provide at least a portion of the treatment system supernatant to the processor for processing carbon dioxide. The treatment system can also be configured to provide at least a portion of the treatment system supernatant to an electrochemical system, where the electrochemical system can be configured to generate a proton-removing agent or perform proton removal. As described with reference to FIG. 4 , the treatment system can also be configured to provide at least a portion of the supernatant to a washing system configured to wash the composition of the present invention, wherein the composition includes precipitation material (e.g., CaCO ₃ , MgCO ₃ or its combination). The processor of the carbon dioxide-processing system of the present invention may be configured to receive a processing system supernatant or an electrochemical system stream from: a contactor (e.g., a gas-liquid contactor, a gas-liquid-solid contactor), a reaction reactor, combination of contactor and reactor, or any other unit or combination of units in a processor. In some embodiments, the carbon dioxide-processing system can be configured to provide at least a portion of the supernatant to a system (eg, desalination plant) or process (eg, desalination) outside the carbon dioxide processing system.

Recirculation of the supernatant of the treatment system is beneficial because the recirculation provides efficient use of available resources; minimal disturbance of the surrounding environment; and reduced energy requirements that provide the benefits of the systems and methods of the present invention. Lower (eg, small, neutral or negative) carbon footprint. When the carbon dioxide-processing system of the present invention is operably connected to an industrial facility (e.g., a fossil fuel-fired power plant such as a coal-fired power plant) and uses electricity generated at the industrial facility, the recirculation of supernatant liquid from the treatment system The reduced energy requirements provided provide for reduced parasitic loads on industrial equipment. A carbon dioxide-processing system not configured for recirculation (i.e., a carbon dioxide processing system configured for a one-pass process) such as that shown in Figure 2 may have an additional load of at least 10% of the industrial plant attributable to A fresh source of alkalinity (eg, seawater, brine) is continuously pumped into the system. In such an example, a 100 MW power plant (eg, a coal-fired power plant) would need to provide 10 MW of power to the carbon dioxide-processing system for continuously pumping a fresh source of alkalinity into the system. In contrast, a system for a recirculation configuration such as that shown in Figure 4 or Figure 5 may have less than 10%, such as less than 8%, including less than 6%, for example, less than 4% or less than 2% The additional load of the industrial equipment can be attributable to pumping make-up water and recirculating supernatant. A carbon dioxide-processing system configured for recirculation may, when compared to a system designed for a single pass process, exhibit an additional load reduction. For example, if a CO2-treatment system configured for recirculation consumes 9 MW of electricity to pump the make-up water and recirculate the supernatant and a CO2-treatment system designed for the single-pass process consumes 10 MW of electricity attributable to pumping , then a CO2-treatment system configured for recirculation shows a 10% drop in parasitic load. For systems such as those shown in Figures 4 and 5 (i.e., carbon dioxide-processing systems configured for recirculation), the drop in parasitic load attributable to pumping and recirculation also provides an estimate of the total parasitic load. decline, especially when compared to carbon dioxide-processing systems configured for single-pass processes. In some embodiments, recirculation provides a reduction in the total additional load of the carbon dioxide-processing system, wherein the reduction is at least 2%, such as at least 4%, including at least 6%, such as at least 8% or at least 10%, when compared to At the total additional load of the carbon dioxide-treatment system configured for the single-pass method. For example, if a CO2-treatment system configured for recirculation has an additional load of 15% and a CO2-treatment system designed for a one-pass process has an additional load of 20%, then a CO2-treatment system configured for recirculation shows an overall load of 5%. drop in additional load. For example, a carbon dioxide-processing system configured for recirculation, wherein recirculation includes filtration through a filtration unit such as a nanofiltration unit (e.g., to concentrate divalent cations in the retentate and reduce divalent cations in the permeate), There may be a reduction in total parasitic load of at least 2%, such as at least 4%, including at least 6%, such as at least 8% or at least 10%, when compared to a carbon dioxide-processing system configured for a single pass process.

Figure 6B provides a schematic diagram of a _CO2 -processing system according to an embodiment of the invention. As described herein, and provided in Figure 6B, the system of the present invention can include a source of CO2 _- containing gas (e.g., an industrial waste gas stream such as flue gas from a coal-fired power plant), a source of alkalinity (e.g., proton - a source of removing agent), and a source of divalent cations. The _CO2 -containing gas source, the alkalinity source, and the divalent cation source can each be operably connected to a _CO2 processor such as the absorber described herein, or as shown in Figure 6B, the _CO2 -containing gas source can be is operatively connected to a heat exchange (HX) dryer configured to dry the precipitation material, which in turn is operatively connected to a _CO2 processor. The _CO processor can be configured for gas-liquid or gas-liquid-solid contacting and includes gas-liquid contactors, gas-liquid-solid contactors, reactors, clarifiers, or any combination thereof, to conduct as described herein the above-mentioned absorption. The _CO processor (e.g., absorber) can be configured to provide a composition (e.g., solution, slurry, etc.) comprising carbonate, bicarbonate, or carbonate and bicarbonate to the treatment system of the present invention , which, as shown in the embodiment provided in Figure 6B, includes systems for dehydration, water treatment, chloride removal, drying, and lithification. The dehydration system may be configured to remove bulk water, resulting in dehydrated precipitation material, which, depending on the source of divalent cations and/or the source of alkalinity, may include chloride. configured to use water provided by a water treatment system (e.g., one or more filtration units selected from the group consisting of microfiltration, ultrafiltration, nanofiltration, reverse osmosis, forward osmosis filtration units), chloride The removal system can remove chlorides, and depending on the final product, other salts from the precipitation material. The system as depicted in FIG. 6B can be further configured to provide chloride-depleted precipitation material for subsequent drying in an SCM drying system to provide supplemental cementitious material (SCM). Alternatively, or in addition, the system may be configured to provide chloride-depleted precipitation material to the lithification system in order to produce fine aggregate coarse aggregate. Figure 6B also shows that the system is configured to provide purified exhaust (e.g., _CO2 -poor exhaust gas stream (comprising mainly N2), fresh water (e.g., drinking water), salt water (e.g., NaCl aqueous solution), and a source of concentrated divalent cations , which includes divalent cations left over from _CO2 treatment.

Figure 6C provides a more detailed description of the _CO2 processor of the present invention. For example, in some embodiments, Figure 6C provides a more detailed description of the _CO2 processor of Figure 6B. A _CO2 processor of the present invention such as that shown in FIG. 6B may include an induction fan (ID fan) configured to provide an industrial source _{of CO2} (eg, flue gas) to the absorber. The absorber may further include a balance tank for a source of divalent cations and/or a source of alkalinity (eg, a source of proton-removing agent). With regard to the source of divalent cations, for example, the source of divalent cations can be operably connected to a balancing tank configured to accommodate potentially discontinuous flow (e.g., flow fluctuations), which can be operatively connected to a feed pump , the latter configured to pump a source of divalent cations to the absorber. As shown in Figure 6C, the _CO2 processor may further include a circulation pump configured to recirculate the solution or slurry from the bottom of the absorber to one or more upper stages of the absorber. The non-recirculated solution or slurry can be provided to a product balance tank, which, along with an operably connected product pump, is configured to provide a regulated flow of product to the dewatering system of the present invention. The system can further be configured to stop the recirculation, transfer the entire slurry absorption solution to the product balance tank, and wash the absorber with wash water. As with the source of divalent cations and alkalinity (eg, proton-removing agent source), wash water can be supplied to the absorber from a tank containing wash water through an intermediate pump.

Figure 7 provides a schematic diagram of a system according to one embodiment of the invention. In FIG. 7 , system 100 includes water source 110 . In certain embodiments, the water source 110 includes a structure having an input for water (eg, alkaline earth metal ion-containing water), such as a pipe or pipeline from the ocean or the like. Where the source of water processed by the system generating the sediment is seawater, the input is in fluid communication with the seawater source, for example, as in where the input is a pipeline or feed from ocean water to a land-based system, or in the hull of a ship Inlet holes in, for example, where the system is part of a ship, for example, in marine-based systems.

Also shown in FIG. 7 is a CO ₂ source 130 . The system also includes tubes, conduits, or conduits that direct the CO ₂ to the system 100 . The gaseous waste stream used in the process of the invention may be provided to the precipitation site in any suitable manner by an industrial plant which conveys the gaseous waste stream from the industrial plant to the settling unit. In certain embodiments, the waste stream has a gas conveyor, eg, a pipe, from a location of the industrial facility, eg, a flue of the industrial facility, to one or more locations at the settling location. The source of the gaseous waste stream may be at a remote location relative to the settling location such that the source of the gaseous waste stream is located 1 mile or more, such as 10 miles or more, including 100 miles or more, from the settling location. For example, a gaseous waste stream can be transported from a remote industrial facility to a settling location via a _CO2 gas transport system, such as a pipeline. The CO ₂ -containing gas produced by the industrial plant may or may not be processed, eg, to remove other components, etc., before it reaches a precipitation location (ie, a carbonate compound precipitation unit). In other cases, the source of the gaseous waste stream is adjacent to the precipitation site, where such cases may include cases where the deposition site is integrated with the source of the gaseous waste stream, such as a power plant with an integrated carbonate compound precipitation reactor.

Where desired, a portion, but less than all, of the gaseous waste stream from the industrial plant may be used in the precipitation reaction. In these embodiments, the portion of the gaseous waste stream used for precipitation may be 75% or less, such as 60% or less and including 50% and less. In other embodiments, a substantially entirely gaseous waste stream produced by an industrial facility, such as substantially all flue gas produced by an industrial facility, is used in the precipitation. In these embodiments, 80% or more, such as 90% or more, including 95% or more, up to 100% of the gaseous waste stream (e.g., flue gas) produced by the source may be used during precipitation .

As noted above, the gaseous waste stream may be a gaseous waste stream obtained from a flue or co-function structure of an industrial facility. In these embodiments, a process line, eg, piping, is connected to the flue so that gas exits the flue through the process line and is transported to a suitable location in the precipitation system (described in more detail below). Depending on the particular configuration of the portion of the precipitation system in which the gaseous waste stream is used, the source location from which the gaseous waste stream is obtained may be changed, for example, to provide a waste stream having a suitable or desired temperature. Thus, in certain embodiments, where a gaseous waste stream having a temperature of 0°C to 1,800°C, such as 60°C to 700°C is desired, the flue gas is at the exit point of the boiler or gas turbine, kiln, Or at any point through a power plant or chimney, may be obtained. Where desired, the flue gas is maintained at a temperature above the dew point, eg, 125°C, to avoid condensation and related complications. Where this is not possible, steps can be taken to reduce the adverse effects of condensation, e.g., use of stainless steel, fluorocarbon (e.g. poly(tetrafluoroethylene)) line piping, dilution with water and pH control, etc., Pipes are not damaged quickly.

To provide efficiencies, industrial equipment producing gaseous waste streams can be co-located with sedimentation systems. "Coexisting" means that the distance between the industrial equipment and the settling system is 10 to 500 yards, such as 25 to 400 yards, including 30 to 350 yards. Where desired, the settling and industrial equipment can be positioned relative to each other to minimize temperature loss and avoid condensation, as well as minimize piping costs, for example, where the settling unit is located within 40 yards of the industrial equipment.

Also contemplated are, in certain embodiments, fully integrated installations that include industrial functions (eg, power generation, cement production, etc.) and the precipitation system of the present invention. In such an integrated plant, conventional industrial equipment and precipitation systems, such as those described below, are modified to provide the desired integrated plant. Changes include, but are not limited to: coordination of chimneys, pumps, controls, instrumentation, monitoring, use of plant energy, e.g., steam turbine energy to run various parts of sedimentation components, e.g., mechanical presses, pumps, compressors, use of energy from cement And/or heat from steam or heat from air-to-air heat exchangers in power plants, etc.

In certain embodiments, _{the CO2} -containing gas stream can be pretreated or preprocessed (e.g., with _H2O2 ) and then contacted with water, such as alkaline earth metal-containing water (e.g., in an addition reaction device). Exemplary pretreatment or preprocessing steps may include: temperature adjustment (e.g., heating or cooling), decompression, extrusion, introduction of additional components (e.g., hydrate promoter gas), oxidation of various components to It transforms into a form that is more easily sequestered in a stable form and so on. In certain embodiments, pretreatment of the gaseous waste stream improves absorption of components of the CO ₂ -containing gas stream into water, such as alkaline earth metal-containing water. Exemplary pretreatments for improved absorption include subjecting the CO ₂ -containing gas stream to oxidative conditions.

The water source 110 and the CO ₂ gas stream source 130 of FIG. 7 are connected to the CO ₂ feeder in the precipitation reactor 120 . The precipitation reactor 120 can include many different design features, such as temperature regulators (e.g., configured to heat the water to a desired temperature), chemical additive components, e.g., for introducing chemical pH raising agents (e.g., hydroxides, metal oxides material, or fly ash) into water, electrochemical components such as cathode/anode, mechanical agitation and physical agitation mechanisms and components for recirculating industrial plant flue gas through precipitation devices. The precipitation reactor 120 may also include design features that allow monitoring of one or more parameters such as internal reactor pressure, pH, precipitate particle size, metal-ion concentration, conductivity of the aqueous solution, alkalinity of the aqueous solution, and _pCO2 . Such reactor 120 can be operated as a batch process or as a continuous process.

In some embodiments, a contactor (eg, a gas-liquid or gas-liquid-solid contactor) is isolated from the system. In such systems, the absorbing solution is sent to the processing station after exposure to the gas. In some embodiments, the absorbing solution after contacting the gas and any products of contacting the absorbing solution with the gas is passed to other systems (ie, process stations), including, but not limited to, settling tanks, dehydration systems, and building fabrication systems. In some embodiments, the contacting mixture after contacting the gas, which includes liquid components, any products of contacting the contacting mixture with the gas, and optionally solid components other than precipitates, is passed to other systems, including but Not limited to, settling tanks, dewatering systems and building fabrication systems. In some embodiments, the gas-exposed slurry, which includes liquid components, solid components, and any products of contacting the slurry with the gas, is passed to other systems, including but not limited to, settling tanks, dewatering systems, and buildings manufacturing system. In some embodiments, the solid components of the absorption solution, if any, and the products of contacting the absorption solution with the gas are separated from the absorption solution that has been contacted with the gas. In some embodiments, the solid components (if any) of the contacting mixture and the products of contacting the contacting mixture with the gas are separated from the contacting mixture that has been contacted with the gas. In some embodiments, the solid components of the slurry, if any, and the products of contacting the slurry with the gas are separated from the slurry that has been contacted with the gas. In some embodiments, separation of the solids from the absorption solution that has been contacted with the gas, contacted mixture, or slurry is accomplished by sieves, presses, centrifuges, spray dryers, air-assisted methods, heat dehydration methods, or any combination thereof. In some embodiments, the effluent liquid remaining after separation of the solids from the gas-exposed absorption solution, contact mixture, or slurry is processed through a system including, but not limited to, nanofiltration, reverse osmosis, chemical regeneration, Desalination, adjustment of solution chemistry for recycle, pH adjustment for release, or any combination thereof. In some embodiments, the solids separated from the absorption solution, contact mixture or slurry that has been contacted with the gas are sent to the construction material production system. In some embodiments, the device is a portable device contained in a transport container such that it can be transported by rail (train), water (barge) and/or road (truck) or any combination thereof to any desired location. In some embodiments, the portable meter is separate from the system. In some embodiments, the entire system is a portable system contained in one or more transport containers, which can be transported by rail (train), waterway (barge) and/or road (truck) or any combination thereof to any desired destination. Location.

Sometimes, to affect the amount of the gas component introduced into the liquid or slurry, the gas needs to contact the liquid or slurry more times than is possible in one pass through the device of the invention. In some embodiments, the gas is recycled in order to affect the amount of gas components introduced into the liquid or slurry. The introduction of the gaseous components into the liquid or slurry may be performed using multiple devices, such that the gas passes from one device to one or more subsequent devices. Subsequent devices may utilize different: liquids or slurries; structural features within the towers, chambers, or reactors of the device; droplet generation systems or devices; or have a different general orientation than the first device. In some embodiments, systems of the invention include arrays of devices of the invention. In such embodiments, the array may include devices through which the gas is passed sequentially, one device after the other, or the array may include devices through which the gas is passed simultaneously such that the devices are used in parallel. In some embodiments, an array includes rows of multiple devices. In some embodiments, the gas enters simultaneously into a first device of several devices lined up and then flows into subsequent devices such that effectively a series of devices operate in parallel.

In some embodiments, the system of the present invention seeks to optimize the horsepower required to absorb and the physical footprint of the device to accomplish this. In such embodiments, the system includes at least two devices of the invention for contacting a mixture (eg, slurry or contact liquid) with a gas to remove one or more component gases (eg, _CO2 , SOx). The first device is oriented such that its long axis is horizontal and such that it is placed close to the ground. The purpose of this orientation is that this part of the absorber will have a low liquid head requirement, thus making it easier to pump the contact mixture (ie absorbing solution) to the top of the contact chamber of the device, ie requiring less energy. The contact mixture in a horizontal section of the device may be different along the length of that section, or it may be the same mixture. The contact mixture in the horizontal part of the plant may be a supernatant or a slurry, which may or may not be recycled. The flow of the inlet gas and the flow of the contacting mixture may be co-current or counter-current, or the flow of gas and solution may vary in stages over the horizontal length of the device. The contact mixture in the horizontally oriented apparatus may be recirculated within the apparatus to effectively induce a counter flow of the contact mixture relative to the inlet gas flow. The second device in the system is vertically oriented such that its length is perpendicular to the ground. Vertically oriented devices can be staged (more common than unstaged) and the contact mixture flow can be cocurrent or countercurrent to the flow of the inlet gas. The vertical section of the absorber will have demisters before the gas outlet. It is also possible for this section to recycle the contact mixture to stages in a vertically oriented plant or to a horizontally oriented plant. It is also possible that the contact mixture is a clear liquid or a slurry in several of the following stages. The slurry comprises solid components which may be minerals, industrial waste (eg fly ash, cement kiln dust) and/or solid sediment from the process (where recycling is used). If the contact mixture includes a slurry, comminution can be separated from the recirculation system. The liquid component of the serum or slurry may be seawater, naturally occurring alkaline brines, industrial waste brines, desalination effluent brines, synthetic brines, fresh water, solutions with added divalent cations, solutions with added alkalinity or its combination.

Figure 26 is a schematic diagram of an embodiment of the invention wherein the system includes two devices, one horizontally oriented, near the ground, and a second device, vertically oriented. The configuration shown in Figure 26 (and likewise, Figures 27 and 28) minimizes horsepower requirements and the physical footprint requirements of the system. A lower, horizontally oriented unit requires less hydraulic head, and thus requires less horsepower to operate. A taller vertically oriented device requires less area for its physical footprint. The solution in the vertically oriented device can be recycled to the horizontally oriented device, recycled only in the vertically oriented device, partially recycled in the vertically oriented device and partially recycled in the horizontally oriented device, or not recirculated cycle. A vertically oriented device may have a mist removal section, just before the gas outlet, which accepts clear liquid (ie, free of solid particulate matter) as its intake. The vertically oriented device can accept either serum or slurry as its intake to the main part of the device, 3 nebulizers are shown in the figure. A system comprising two devices may be a portable system such that the system is contained in a transport container which may be transported by rail, water and/or road.

Figure 27 is a schematic illustration of an embodiment of the invention, similar to that shown in Figure 26, in which the system includes two devices, one horizontally oriented, near the ground, and a second device, vertically oriented. In the embodiment shown in Figure 27, the flow of gas in the first device (which is horizontally oriented, close to the ground) is forced to follow a rotational path. The nature of the path followed by the gas creates regions of countercurrent and cocurrent contact between the gas and the solution in the first (ie, lower) device. As in Figure 26, the solution in the vertically oriented device can be recycled to the horizontally oriented device, recycled only in the vertically oriented device, partially in the vertically oriented device and partially in the horizontally oriented device , or without recycling. A vertically oriented device may have a mist removal section, just before the gas outlet, which accepts clear liquid (ie, free of solid particulate matter) as its intake. The vertically oriented device can accept either serum or slurry as its intake to the main part of the device, 3 nebulizers are shown in the figure. A system comprising two devices may be a portable system such that the system is contained in a transport container which may be transported by rail, water and/or road.

Figure 28 is a schematic illustration of an embodiment of the invention, similar to that shown in Figures 26 and 27, in which the system includes two devices, one horizontally oriented, near the ground, and a second device, vertically oriented. In the embodiment shown in Figure 28, the solution (e.g. absorbing solution, contacting mixture) in the device in a horizontal orientation is recirculated in the device such that the solution initially enters the device at the point furthest from the gas inlet. device. Use a pump closer to the gas inlet area and then recirculate the solution. This recirculation effectively creates a counterflow between the overall fluid flow and the gas flow in the device, however the structure of the device allows the gas flow to be rotated such that the gas is locally alternately co-current and countercurrent flow. As in Figures 26 and 27, the solution in the vertically oriented device can be recycled to the horizontally oriented device, recycled only in the vertically oriented device, partially in the vertically oriented device and partially in the horizontally oriented device Recirculation, or no recirculation. A vertically oriented device may have a mist removal section, just before the gas outlet, which accepts clear liquid (ie, free of solid particulate matter) as its intake. The vertically oriented device can accept either serum or slurry as its intake to the main part of the device, 3 nebulizers are shown in the figure. A system comprising two devices may be a portable system such that the system is contained in a transport container which may be transported by rail, water and/or road.

Figure 29 is a schematic illustration of an embodiment of the invention wherein different types of devices are used in series. The device is a device using an array of sprayers or a combination of sprayers and rows. The device also has a fluid (ie, absorbing solution or contacting mixture) flowing co-currently and counter-currently with respect to the gas flow. The fluid (i.e. absorbing solution or contacting mixture) in the respective units may be the same or different, and it may be recirculated within the respective units or from one unit to the other, resulting in the desired gas introduction (i.e. absorption) and Sometimes precipitation.

Figures 30 and 31 are diagrams showing an embodiment of the invention of the system of the invention wherein the devices are arranged in rows and gases flow into the devices in parallel and in series. Figure 30 shows an arrangement in which the gas flows into more than one device, and in these first devices the gas and liquid (e.g. absorption solution, contact mixture) flow is co-current and the gas then flows into more than one subsequent device in which the flow is countercurrent. Figure 31 shows an arrangement where gas flows into more than one device, where the gas and liquid flow is countercurrent in the first of the multiple devices, then in subsequent multiple devices the flow is cocurrent . In the respective plant, the solution or the contact mixture can be recycled within the plant or from one plant to another in order to obtain the desired removal of components of the gas (eg CO ₂ , SOx) or precipitates.

The precipitation reactor 120, further includes an output transport means for the mother liquor. In some embodiments, the output transport may be configured to transport mother liquor to tailings ponds for disposal or in naturally occurring bodies of water such as oceans, seas, lakes or rivers. In other embodiments, the system can be configured to allow the mother liquor to be used as a coolant for industrial equipment through a process line running between the precipitation system and the industrial equipment. In certain embodiments, a precipitation unit may be co-located with a desalination unit such that output water from the precipitation unit is used as the desalination unit's injection water. The system can include a means of transport (ie, pipelines) where output water (eg, mother liquor) can be pumped directly into the desalination unit.

Figure 32 shows a schematic diagram of the plumbing and instrumentation used in an embodiment of the invention. Simplified diagram showing two possible sources of flue gas from a power plant. Flue gas is shown, which enters the bottom of the contact chamber (ie the item labeled absorber). The contact chamber has an outlet conduit at the bottom and connections to a recirculation system, including pumps and switch tubes. In the center of the contact chamber is the nebulizer, at the top of the chamber is the demister section (ie demister) and then the gas outlet. Shown is the spray water supply for the demister section, which is separate from the water supply for the chamber center section. The solution source in the center of the chamber also has a connection mechanism to at least one source of sodium hydroxide (eg electrochemical, alkaline brine). A slurry mill is also shown in Figure 32. These mills may be the location for comminuting the solid components of the slurry, where the solid components may be precipitation material, minerals or industrial waste (eg fly ash, cement kiln dust). In some embodiments, the contact chamber or absorber shown in Figure 32 can be portable such that it fits in a standard shipping container and can be transported by train, barge and/or truck to any facility, if desired.

The system illustrated in Figure 7 further includes a liquid-solid separation unit 140 for separating the precipitated carbonate mineral composition and the precipitation system effluent. Liquid-solid separation units can achieve separation of precipitation products from precipitation system effluents by: drainage (e.g., gravity settling of precipitation products followed by drainage), decantation, filtration (e.g., gravity filtration, vacuum filtration, use of pressurized air filtration), centrifugation, pressing, or any combination thereof. In some embodiments, the liquid-solid separation device includes a baffle against which the settling table effluent flows to separate the precipitated product from the supernatant. In such embodiments, the liquid-solid separation device may further include a collector for collecting the precipitated product. A source of liquid-solid separator useful in some embodiments is Epuramat's Extrem-Separator ("ExSep") liquid-solid separator or variants thereof. In some embodiments, the liquid-solid separation device includes a spiral channel into which the sedimentation table effluent flows to separate the precipitated product from the supernatant. In such embodiments, the liquid-solid separation device may further comprise an array of helical channel outlets for collecting the precipitated product. A source of liquid-solid separator that may be used in some embodiments is Xerox PARC's spiral concentrator or variants thereof. At least one liquid-solid separation device is operatively connected to the settling table such that settling table effluent can flow from the settling table to the liquid-solid separation device (eg, the liquid-solid separation device includes baffles or spiral channels). As detailed above, a number of different liquid-solid units can be used together, in any arrangement (e.g., in parallel, in series, or combinations thereof), and the settling table effluent can flow directly to the liquid-solid separation unit, or The effluent can be pretreated.

The system also includes a washing station, 150, wherein the bulk dewatered precipitate 140 from the separation station is washed, for example, to remove salts and other solutes from the precipitate, and then dried in a drying station.

The system further includes a drying station 160 for drying the precipitated carbonate mineral composition produced by the carbonate mineral precipitation station. Depending on the particular drying protocol of the system, the drying station may include filter elements, freeze drying structures, spray drying structures, etc., as described more fully above. The system may include a conveyor, eg, piping, from the industrial plant that connects to the dryer so that the gaseous waste stream (ie, industrial plant flue gas) can contact the wet sediment directly in the drying bench.

The dried precipitate may undergo further processing, eg, grinding, milling, in a refining station 180 in order to obtain desired physical properties. One or more components can be added to the sediment, where the sediment is used as a building material.

The system further comprises an outlet conveyor, for example, a conveyor belt, a slurry pump, which allows the sediment to be removed from one or more of: a reactor, a drying station, a washing station or a refining station. The product of the precipitation reaction can be handled in many different ways. Sediment can be transported to long-term storage locations in empty transport vehicles such as barges, train cars, trucks, etc., which can include above- and below-ground storage facilities. In other embodiments, the sediment may be disposed of in an underwater location. Any suitable process for transporting the composition to a processing location may be used. In certain embodiments, pipes or similar slurry delivery structures may be used, where such pathways may include active pumps, gravity mediated flow, and the like.

In certain embodiments, the system will further include a station for preparing construction materials, such as cement, from the sediment. The workbench can be configured to produce various cements, aggregates, or cementitious materials from sediment, for example, as described in co-pending U.S. Patent Application (Publication No.) 2009/0020044 (published November 25, 2008, which is incorporated herein by reference in its entirety).

As noted above, the system may exist on land or at sea. For example, the system may be a land-based system that is located in a coastal location, such as close to a seawater source, or even in an inland location where water is piped into the system from a saltwater source, such as the ocean. Alternatively, the system may be a water-based system, ie a system that exists on or in water. Such a system may exist on a ship, ocean-based platform, etc., as desired. In certain embodiments, the system can be co-located with industrial equipment at any convenient location. The settling unit may be a land-based unit that is co-located with land-based industrial equipment, eg, in coastal areas, such as close to a water source (eg, seawater). Also considered are inland locations where water is piped directly into the system from a source (eg, industrial facility, remote lake, remote ocean). Alternatively, the settling means may be present on water, eg, on a barge, boat, ocean-based platform, etc., as desired, eg, where real estate near industrial equipment is lacking. In certain embodiments, the settling unit may be a mobile unit such that it is easily co-located with industrial equipment.

The system of the present invention co-located with industrial equipment such as a power plant can be configured to allow synchronization of the activities of the industrial equipment and the settling plant. In some cases, the activity of one device may not necessarily match the activity of another. For example, a precipitation unit may need to be reduced or stopped from receiving a gaseous waste stream, but an industrial plant may need to remain in operation. Conversely, situations may arise where the industrial plant is reduced or out of operation while the settling plant is not. To address situations where a settling plant or industrial plant may need to reduce or cease its activity, design features that provide for continuous operation of one of the co-located devices while the other is reduced or ceased operation may be used, as detailed above. For example, in certain embodiments, the system of the present invention may include blowers, fans, and/or compressors at various points along the connection line between the industrial plant and the settling plant, in order to control the The occurrence of back pressure in the pipeline. In certain embodiments, a gas storage facility may exist between the industrial facility and the precipitation unit. Where desired, the settling unit may include emission monitors to assess any gaseous emissions produced by the settling unit, as required by Air Quality Agencies.

Aspects of the invention include the use of a _CO2 -containing industrial facility gaseous waste stream, eg, industrial facility flue gas, at one or more stages of the process in which a stable _CO2 -containing product is stored by precipitation. Thus, industrial plant gaseous waste streams containing _CO2 are used in the precipitation process. In an embodiment of the invention, the gaseous waste stream is used in one or more steps of the precipitation process _, e.g. , where the precipitated carbonate compounds are dried and so on.

Where desired, the flue gas from the industrial plant can be recirculated through the precipitation unit until the total adsorbed remaining _CO2 approaches 100%, or a point of diminishing returns is achieved so that the remaining flue gas can be processed using an alternative process and/or released into the atmosphere.

In some embodiments, the devices and systems of the present invention can be operatively connected to a power plant that produces electricity and industrial waste gases (ie, flue gases). In such embodiments, the devices and systems of the present invention may be considered emission control systems for the removal of certain components from industrial waste gases. In some embodiments, industrial waste gases include carbon dioxide, SOx, NOx, heavy metals, non- _CO2 acid gases, and fly ash. In some embodiments, the devices and systems of the present invention may function as emission control systems configured to remove carbon dioxide from industrial waste gases. In some embodiments, the devices and systems of the present invention may serve as emission control systems configured to remove at least carbon dioxide and additionally remove SOx from industrial exhaust gases. In some embodiments, carbon dioxide and optionally SOx are removed by an emission control system comprising the devices and/or systems of the present invention while utilizing a minimal amount of electricity generated by the power plant, for example less than 30% of the electricity generated by the power plant generated electricity. In some embodiments, the emission control system of the present invention can be implemented to utilize less than 30% of the electricity generated by a power plant, including using or receiving alkaline solution from an electrochemical system configured to produce a caustic solution , in particular of the type of low voltage electrochemical system described further herein. In some embodiments, the emission control system of the present invention is connected to a power plant and is configured to absorb at least 50% of the carbon dioxide from the exhaust and use less than 30% of the energy produced by the power plant. In some embodiments, the emission control system of the present invention is coupled to a power plant and is configured to absorb at least 90% of sulfur oxides (SOx) from the exhaust and use less than 30% of the energy produced by the power plant. In some embodiments, the emission control system of the present invention is connected to a power plant and is configured to absorb at least 50% of the carbon dioxide and at least 80% of the sulfur oxides (SOx) from the exhaust and use less than 30% of that produced by the power plant energy of. In some embodiments, the devices and systems of the present invention may be used with existing emission control systems in place at fossil fuel burning plants. In some embodiments, existing emission control systems may include or utilize: electrostatic precipitators for particulate matter collection, SOx control technology, NOx control technology, physical filtration technology for particulate matter collection, mercury control technology, among other controls measure.

As mentioned above, the precipitation system of the present invention can be co-located with industrial equipment. An example of such a system is illustrated in FIG. 7 . In Figure 7, the flue gas outlet 170 from the power plant 200 is used for the precipitation reactor 120 as the _CO2 source 130 and dryer 160 and heat source. Where desired, back pressure control is used to at least reduce, if not eliminate, the occurrence of back pressure that may result from directing a portion, if not all, of the industrial plant gaseous waste stream to the settling unit 100 . Any suitable means of controlling the occurrence of back pressure may be used. In certain embodiments, blowers, fans and/or compressors are provided at certain points along the connecting process line between the industrial plant and the settling unit. In certain embodiments, a blower is installed to draw the flue gas into the duct, which sends the flue gas to the precipitation unit. The blower used in these embodiments may be an electrically or mechanically driven blower. In these embodiments, back pressure is reduced to levels of 5 inches or less, such as 1 inch or less, if present at all. In certain embodiments, a gas storage facility may exist between the industrial facility and the precipitation unit. When present, the gas storage facility can be used as a surge, shutdown and smoothing system so that there is a uniform flow of flue gas to the settling unit.

Aspects of the invention include synchronizing the activities of industrial equipment and settling plants. In some cases, the activity of one device may not necessarily match the activity of another. For example, a precipitation unit may need to be reduced or stopped from receiving a gaseous waste stream, but an industrial plant may need to remain in operation. Conversely, situations may arise where the industrial plant is reduced or out of operation, whereas the settling plant is not. To address this situation, it may be useful if the devices can be configured to provide one of the co-located devices with continuous operation while the other reduces or ceases operation. For example, to address situations in which a settling plant has to reduce or eliminate the amount of gaseous waste stream it receives from industrial equipment, the system can be configured so that blowers and pipes carrying the waste stream to the settling plant are shut down in a controlled sequence to minimize The pressure varies and the industrial plant flue acts as an auxiliary stack for discharging the gaseous waste stream. Likewise, if an industrial facility reduces or eliminates the production of its gaseous waste stream, for example, if the industrial facility is dispatched in whole or in part, or if there is a curtailment of the industrial facility's output at some pre-agreed level, then the system can be configured to allow The precipitation unit continues to operate, for example, by providing an alternative source of CO ₂ , by providing an alternative heating process in the dryer, etc.

Where desired, the settling plant may include emission monitors to assess any gaseous emissions produced by the settling plant and make necessary reports to regulatory agencies, all electronically (typically every 15 minutes), on a daily, monthly basis Weekly, monthly, quarterly and yearly. In certain embodiments, the gas handling at the settling plant is sufficiently closed such that the discharge air from the settling plant, which contains substantially all unused flue gas from the industrial plant, is directed to the chimney for Statutory and regulatory requirements of a state, state, or other political jurisdiction may install the required continuous emission monitoring system.

In certain embodiments, the gaseous waste stream produced by the industrial facility and delivered to the precipitation unit has been treated in accordance with Air Quality Agencies requirements such that the flue gas delivered to the precipitation unit already complies with air quality requirements. In these embodiments, the precipitation unit may or may not have an alternate treatment system in place in the event of a settling unit shutdown. However, if the flue gas being conveyed has been only partially treated or not treated at all, the precipitation plant may include air pollution control devices in order to meet regulatory requirements, or seek regulatory authority to discharge partially treated flue gas for a short period of time. In other embodiments, the flue gas is sent to a precipitation unit for all processing. In such an embodiment, the system may include containment for situations where the settling unit cannot accept the waste stream, for example, by ensuring that pollution controls installed in the industrial facility are on and control emissions, as provided by the Air Quality Agency (Air Quality Agencies).

The settling unit co-located with the industrial plant may be located in any suitable location, on land or on water. For example, the settling unit may be a land-based unit that is co-located with land-based industrial equipment, for example, in coastal areas, such as close to seawater sources. Also considered are inland locations where water is piped directly into the system from a source (eg, industrial facility, remote lake, remote ocean). Alternatively, the settling device may be present on water, eg, on a barge, ship, ocean-based platform, etc., as desired, eg, where real estate near industrial equipment is lacking. In certain embodiments, the settling unit may be a mobile unit such that it is easily co-located with industrial equipment.

As noted above, it is contemplated that in certain embodiments the waste stream will be generated by an integrated gasification combined cycle (IGCC) unit. In these types of installations, raw fuels such as coal, biomass, etc. are first subjected to a gasification process to produce syngas, which is then transformed, producing quantities of _CO2 , CO and _H2 . The product of the gasification process can be sent to a precipitation unit to remove CO ₂ first, and the resulting CO ₂ scrubbed product is returned to the power plant for use as fuel. In such an embodiment, a line from the gasification unit of the power plant may exist between the power plant and the settling unit, and a second return line may exist between the settling unit and the power plant to convert the aspirated syngas transported back to the power plant.

In certain embodiments, the co-located industrial plant and precipitation plant (or integrated plant) are operated with additional _CO2 abatement methods. For example, material handling, vehicles and earth-moving equipment, locomotives could be configured to use biofuels instead of fossil fuels. In such an embodiment, the location may include a fuel tank for storing biofuel.

In addition to sequestering _CO2 , embodiments of the present invention also sequester other components of gaseous waste streams generated by industrial facilities. For example, embodiments of the present invention result in the sequestration of at least a portion of one or more of NOx, SOx, VOC, mercury, and particulate matter that may be present in a waste stream such that one or more of these products are immobilized in solid deposits in the product.

In FIG. 7 , a precipitation system 100 is co-located with an industrial plant 200 . However, the precipitation system 100 is not integrated with the industrial plant 200 . In certain embodiments, therefore, of further interest is an integrated plant which, in addition to an industrial plant, includes power generation, water treatment (seawater desalination or mineral-rich freshwater treatment) and sedimentation components, as described in the U.S. patent application (Publication No.) 2009/0001020, whose publication date is January 1, 2009, which is incorporated herein by reference in its entirety. The water source for the settling unit may be derived from the waste stream of the water treatment unit. The resulting mother liquor from the carbonate precipitation unit can be used as feedstock for a water treatment unit. The resulting integrated device essentially uses fuel, minerals, and untreated water as inputs, and outputs energy, processed industrial products, eg, cement, clean water, clean air, and carbon sequestration building materials.

Figure 33 provides an example where the precipitation system 100 is integrated with an industrial plant (in this case a coal fired power plant 300). In power plant 300, coal 310 is used as fuel for steam boiler 315 to generate steam, which in turn runs a turbine (not shown) to generate electricity. The steam boiler 315 also produces bottom ash or boiler slag 325 and flue gas 320 . Flue gas 320 contains fly ash, _CO2 and sulfates. Flue gas 320 and bottom ash 325 are combined with water from water source 330 in reactor 340 and undergo a precipitation reaction, as described above. Pump 350 facilitates transport of the precipitated product from reactor 340 to spray dryer 360, which uses flue gas 320 to spray dry the precipitated product for subsequent disposal, such as placement in a landfill or use in construction products. Treated flue gas 370 exits spray dryer 360 and is then exhausted to atmosphere in stack 380 . Treated flue gas 370 is a gas in which fly ash, sulfur, and CO ₂ content has been substantially reduced, if not completely removed, compared to flue gas 320 . As an example of the system shown in Figure 33, the _CO2 source could be flue gas from coal or other fuel combustion contacting a volume of brine with little or no pretreatment of the flue gas. In these embodiments, the use of fuels such as high-sulfur coal, sub-bituminous coal, lignite, etc., which are often inexpensive and considered low-quality, is practical due to the removal of SOx and other pollutants as well as the removal of _CO2 capacity. These fuels can also provide higher levels of secondary reactants such as alumina and silica, in the fly ash carried by the flue gas, producing modified carbonate mineral deposits with beneficial properties.

When co-located with a power plant, the method of the invention provides for the sequestration of substantial amounts of _CO2 from the gaseous waste stream produced by the power plant, with limited energy requirements. In some cases, the method provides removal of 5% or more, 10% or more, 25% or more, 50% or more, 75% or more of the _CO2 from the gaseous waste stream, and The energy requirement is 50% or less, such as 30% or less, including 25% or less. The energy requirement is the amount of energy produced by the power plant required to operate the carbon dioxide storage process. In some cases, the above levels of _CO2 removal are achieved with energy requirements of 20% or less, 15% or less, 10% or less.

Another type of industrial plant that can be co-located with the settling plant of the present invention is a cement plant, such as the Portland cement plant. Figure 34 provides a schematic diagram of an exemplary Portland cement production facility. In Figure 34, limestone 400 along with shale and other additives 410 are ground to suitable size and passed through precalciner 500 which uses waste heat from flue gas 430 to preheat the mixture, waste heat from kiln 510 to Improve operational efficiency. The preheated mixture enters the kiln 510 where it is further heated by burning coal 420 . The resulting clinker 480 is collected and stored in a silo 570 where it is mixed with additives 571 such as gypsum, limestone etc. and ground in a ball mill 580 to the desired size. The product leaving the ball mill is Portland cement 490, which is stored in cement silos 590 and then shipped to customers.

Flue gas 430 from kiln 510 contains gaseous and particulate pollutants. Particulate matter pollutants are known as kiln dust 440 and are removed from the flue gas by electrostatic precipitators or baghouses 520 . Kiln dust so removed is usually sent to landfill 600, although occasionally kiln dust is recycled to the kiln, or sold as a secondary binding material. The flue gas is then drawn by fan 540 into wet scrubber 550, where sulfur oxides in the flue gas are removed by reaction with a slurry of quicklime, producing calcium sulfite (eg, gypsum) slurry 480, which is typically recovered in recovery tank 572 Dewatered and disposed of in landfill 600. Flue gas 430 exits wet scrubber 430 and is released to the atmosphere through stack 560 . The flue gas so released has a high concentration of _CO2 , which is released by the combustion of the coal and by the calcination of the oxidized limestone required for Portland cement.

Figure 35 shows a schematic diagram of an exemplary co-located cement plant and settling unit according to one embodiment of the present invention. The process in this example is the same as in Figure 34, but the flue gas treatment system of Figure 34 is replaced by a carbonate precipitation unit. Once the flue gas leaves the precalciner 500, it is sucked by the fan 540 into the reactor 630, where a precipitation reaction is induced using seawater 620 and alkali 625. The resulting slurry 631 is pumped by pump 640 to a drying station 650 where the water 651 is drained and the dried bonding material 660 is stored for shipment to the customer. Flue gas 430 is exhausted from stack 670 along with some, if not all, of the removed pollutants (including mercury, SOx, particulate matter, and CO ₂ ).

Figure 35 shows a schematic diagram of an exemplary cement plant that does not require a limestone quarry, according to one embodiment of the present invention. In such an embodiment, the product of reactor 630 may be in the form of relatively pure calcium carbonate, during part of its operation, and other forms of building materials, during other parts of the time. In this example, instead of mined limestone, precalciner 500 and kiln 510 are filled with a mixture of shale and other components 410 mixed with relatively pure precipitated calcium carbonate 670 . The aforementioned, and incorporated by reference, US Patent Application (Publication No.) 2009/0020044, published Nov. 25, 2008, describes in detail a process for the precipitation of aragonite calcium carbonate from seawater using flue gas. By using the product of the flue gas treatment reactor as feedstock, the cement plant extracts its calcium ions from the seawater through the precipitated product and only needs the mined limestone in the first short period of operation until enough precipitated calcium carbonate is produced to use it. In the feeding kiln.

In some embodiments of the invention, the absorption solution is contacted with a gas source of carbon dioxide to combine carbon dioxide and perhaps one or more other components from the source of carbon dioxide gas in one device or system such that a separate emission control system or device. In some embodiments, the absorption solution is contacted with a gas source of carbon dioxide to bind carbon dioxide and perhaps one or more other components from the carbon dioxide gas source, and the resulting contacted absorption solution is treated without subjecting the solution to precipitation conditions.

In an embodiment of the invention, carbonate precipitation is carried out in two stages. The first stage selectively precipitates calcium carbonate, which can then be used as a raw material for a cement plant, as illustrated in FIG. 36 . The second precipitation stage can produce many different materials, including cement, aggregates, above-ground carbon storage materials, etc.

Portland cement is 60-70% by mass of CaO, which is produced by heating _CaCO3 , requiring heating, for every molecule of CaO released, one molecule of _CO2 is released. Due to the additional _CO2 released from fuel combustion, the output of precipitated _CaCO3 from the precipitation plant will exceed the amount required to provide raw material to the cement plant. In this case, a portion of the settling unit's operating time may be devoted to producing other bonding materials 660, such as those described in U.S. Patent Application (Publication No.) 2009/0020044, published Nov. 25, 2008 , which is incorporated herein by reference in its entirety.

Portland cement 490 produced as shown in FIG. 36 is carbon neutral in that CO ₂ from its manufacturing process is sequestered into precipitated carbonate minerals 670 and cementitious material 660 . Portland cement 490 can be sold as is, or blended or interground with cementitious material 660 to produce a blended cement.

An example of a contemplated continuous feed system is depicted in FIG. 37 . In FIG. 37 , the system 1100 includes a water source (eg, a pipe from the ocean to provide seawater) 1101 that is in fluid communication with a reactor 1110 . Also present in reactor 1110 is a source of Ca/Mg/OH ions and catalyst 1111 which has been added in sufficient quantities to increase the Mg/Ca ion ratio in the water present in reactor 1110 to 3 or more. Reactor 1110 can be configured as a packed bed column and configured to be fed with bicarbonate, if desired. The CO ₂ -containing gas, eg, flue gas 1112 , is combined with the water in the reactor 1110 via the sparger/bubbler 1113 . A source of Mg ions and _CO2 are combined with water in reactor 1110 to produce CO2 _- fed acidic water, which exits reactor 1110 at a pH of 4.8-7.5. Next, the _CO2- fed sour water flows through conduit 1120, where it is circulated by means of: mixing through different levels of alkalinity, e.g., 8.5 and 9.8, by using various _CO2 gas injectors 1121, OH-regulators 1123 (such as introducing pH-enhancing agents, electrodes, etc.) and static mixer 1122, which are located at various locations along conduit 1120. The flow rate through conduit 1120 can be controlled as desired, for example, to 1 GPM to 1,000,000 GPM, such as 30 GPM to 100,000 GPM and including 4,000 GPM to 60,000 GPM. The length of conduit 1120 can vary, from 100 ft to 20,000 ft, such as 1000 ft to 7000 ft. At the end of conduit 1120, a product 1130 is obtained in the form of a slurry comprising precipitated _CO2 -storage product and mother liquor. The resulting slurry is then transferred to a liquid-solid separation unit and clarifier, as illustrated at 1140 .

In certain embodiments, two or more reactors may be used in order to carry out the methods described herein. Schematics of embodiments using two reactors are shown in FIGS. 38 , 39 and 40 . In such an embodiment, the process may include a first reactor 1210 and a second reactor 1220 . In these cases, a first reactor 1210 is used to contact initial water, such as fresh seawater 1230, with a source of magnesium ions 1240, and to feed the initial water to a _CO2 -containing gas, such as flue gas 1250 (where This step is also known as bicarbonate addition). Flue gas 1250 may be contacted with water in first reactor 1210 via sparger/bubbler 1280 . The water is stirred with stirrer 1260 to facilitate dissolution of the source of magnesium ions and to facilitate initial contact of the water with the _CO2- containing gas. Occasionally, agitation of the CO2 _- fed sour water is stopped before the _CO2- fed sour water is transferred to the second reactor 1220 so that undissolved solids can settle by gravity. The _CO fed sour water is then transferred from the first reactor 1210 to the second reactor 1220 via conduit 1270.

After transferring the CO ₂ -fed sour water to the second reactor 1220, a carbonate precipitation step may be performed. Occasionally, the formation of a carbonate-containing precipitate is promoted by contacting the pH-enhancing agent 1290 with water in the second reactor 1220. The contents of the second reactor 1220 may be stirred with a stirrer 1295 . In certain embodiments, one or more additional steps of _CO dosing and subsequent carbonate precipitation may be performed in a second reactor, as described above. In these cases, additional CO ₂ -containing gas, such as flue gas 1255 , is passed through sparger/bubbler 1285 and contacted with water in second reactor 520 . The resulting slurry product includes precipitated _CO2 -storage product and mother liquor, which is then transferred to a water/solids separator or clarifier, as described above.

combination

The compositions of the present invention may be solutions, solids or heterogeneous materials (e.g. slurries) comprising carbonates, bicarbonates or carbonates and bicarbonates, optionally of divalent cations such as Ca2+, Mg2+, or a combination thereof. The amount of carbon in such compositions (eg, storage-stable carbon dioxide sequestration products such as precipitation materials) produced by the methods of the invention can vary. In some embodiments, the composition includes an amount of carbon (as determined by using the procedure described in more detail below, such as isotopic analysis, e.g., 13c isotopic analysis): 1% to 15% (w/w), such as 5 to 15% (w/w), including 5 to 14% (w/w), 5 to 13% (w/w), 6 to 14% (w/w), 6 to 12% (w/w) and 7 to 12% (w/w), where a significant amount of carbon may be carbon originating from a _CO2 source (as determined by the scheme described in more detail below). In such embodiments, 10 to 100%, such as 50 to 100%, including 90 to 100%, of the carbon present in the composition (e.g., a storage-stable carbon dioxide sequestration product such as a precipitation material) is derived from the CO _source (eg, industrial waste streams including carbon dioxide). In some cases, the amount of carbon traceable to the source of carbon dioxide present in the composition is 50% or more, 60% or more, 70% or more, 80% or more, 90% or more , 95% or more, 99% or more, including 100%.

Compositions of the invention (e.g., precipitation materials comprising carbonates, bicarbonates, or carbonates and bicarbonates) can store 50 tons or more of CO ₂ , such as 100 tons or more of CO ₂ , including 150 tons or more of CO ₂ , such as 200 tons or more of CO ₂ , such as 250 tons or more of CO ₂ , including 300 tons or more of CO ₂ , such as 350 tons or more of CO ₂ , including 400 tons or more of CO ₂ , such as 450 tons or more of CO ₂ , such as 500 tons or more of CO ₂ , including 550 tons or more of CO ₂ , such as 600 tons or more of CO ₂ , including 650 tons or more of CO ₂ , such as 700 tons or more of CO ₂ , for every 1000 tons of the composition. Thus, in some embodiments, compositions of the invention (e.g., precipitation materials comprising carbonates, bicarbonates, or carbonates and bicarbonates) comprise 5% or more CO ₂ , such as 10% or More _CO2 , including 25% or more _CO2 , such as 50% or more _CO2 , such as 75% or more _CO2 , including 90% or more _CO2 . Such compositions, in particular the precipitation materials of the present invention, are useful in the built environment. In some embodiments, the compositions can be used as components of articles of manufacture, such as building materials (eg, cement components, aggregates, concrete, or combinations thereof). The composition maintains a storage-stable _CO2 -storage product, since use of the composition in manufactured items, such as building materials, does not result in re-release of sequestered _CO2 . In some embodiments, the compositions of the present invention (e.g., precipitation materials comprising carbonates, bicarbonates, or both carbonates and bicarbonates), when combined with Portland cement, can dissolve and interact with Portland cement. The compounds of the blue cement bind without releasing CO ₂ .

The conditions used to convert _CO to carbonate, bicarbonate, or carbonate and bicarbonate may result in one or more additional components and/or co-products thereof (i.e., produced by one or more products produced by additional components), where such additional components include sulfur oxides (SOx); nitrogen oxides (NOx); carbon monoxide (CO); metals such as antimony (Sb), arsenic (As), barium ( Ba), beryllium (Be), boron (B), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), lead (Pb), manganese (Mn), mercury (Hg), molybdenum ( Mo), nickel (Ni), radium (Ra), selenium (Se), silver (Ag), strontium (Sr), thallium (Tl), vanadium (V), and zinc (Zn); particulate matter; halides; organic matter ; Toxic substances; Radioactive isotopes, etc. In some embodiments, such one or more additional components and/or co-products may be part of a solution comprising carbonate, bicarbonate, or carbonate and bicarbonate. In some embodiments, such one or more additional components and/or by-products may be part of the precipitation material of the present invention by precipitating one or more additional components and/or by-products and carbon salt, bicarbonate or carbonate and bicarbonate by trapping one or more additional components and/or in the precipitation material comprising carbonate, bicarbonate or carbonate and bicarbonate Ancillary products, or by some combination thereof. In some embodiments, such one or more additional components and/or co-products may be part of a slurry comprising any combination of the solutions described above and precipitation material.

In addition to carbonates and/or bicarbonates, the compositions of the present invention may include sulfates, sulfites, and the like. In some embodiments, the composition includes 70-99.9% carbonate and/or bicarbonate and 0.05-30% sulfate and/or sulfite. For example, the composition can include at least 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99.9% carbonate and/or bicarbonate. Such compositions may further comprise at least 0.05%, 0.1%, 0.5%, 1.0%, 5.0%, 10%, 15%, 20%, 25% or 30% sulfate and/or sulfite. In some embodiments, the compositions of the present invention include sulfur-based compounds of calcium, magnesium, or combinations thereof, optionally precipitated or captured in exhaust gas streams that include SOx (e.g., _SO2 , _SO3 , etc.) in the sedimentation material. For example, magnesium and calcium can react to form _MgSO4 and _CaSO4 , respectively, and other magnesium- and calcium-containing compounds (e.g., sulfites), which effectively remove sulfur from waste gas streams (e.g., flue gas streams) , without a desulfurization step such as flue gas desulfurization ("FGD"). In addition, compositions including CaSO ₄ , MgSO ₄ and related compounds can be formed without additional release of CO ₂ . In cases where high levels of sulfur-based compounds (e.g., sulfates) are present, the aqueous solution can be enriched in calcium and/or magnesium so that the calcium and/or magnesium can be used in the formation of CaSO ₄ , MgSO ₄ and/or related compounds Before, during or after formation of carbonate compounds. In some embodiments, multiple reaction products (e.g., MgCO ₃ , CaCO ₃ , CaSO ₄ , mixtures of the above, etc.) are collected at different stages, while in other embodiments a single reaction product (e.g., including carbonates, Precipitated material such as sulfates) is collected.

The compositions of the present invention may include nitrates, nitrites and/or the like. In some embodiments, the compositions of the present invention include such nitrogen-based compounds of calcium, magnesium, or combinations thereof, optionally precipitated or captured in exhaust gas streams that include NOx (e.g., NO ₂ , NO ₃ , etc.) in the resulting precipitated material. For example, magnesium and calcium can react to form Mg(NO ₃ ) 2 and Ca(NO ₃ ) 2 , respectively, and other magnesium- and calcium-containing compounds (eg, nitrates), which effectively Nitrogen is removed from the gas stream) without a selective catalytic reduction ("SCR") step or a non-selective catalytic reduction ("NSCR") step. Additionally, compositions including Ca( _NO3 )2, Mg( _NO3 )2, and related compounds can be formed without additional release _{of CO2} . The compositions of the present invention may further include other components, such as trace metals (eg, mercury). Using mercury as a non-limiting example of a trace metal, compositions of the present invention may include elemental mercury (HgO), Hg2+-containing mercury salts (e.g., HgCl2, _HgCO3 , etc.), Hg+-containing mercury salts (e.g., Hg2Cl2, Hg2CO ₃ , etc.), mercury compounds containing Hg2+ (for example, HgO, organic mercury compounds, etc.), mercury compounds containing Hg+ (for example, Hg2O, organic mercury compounds, etc.), particulate mercury (Hg( p)) etc. In some embodiments, the compositions of the present invention include mercury-based compounds that are optionally precipitated or trapped in precipitation material produced from exhaust gas streams that include trace amounts of metals such as mercury. In some embodiments, the composition includes mercury (or another metal) at a concentration of at least 0.1, 0.5, 1, 5, 10, 50, 100, 500, 1,000, 5,000, 10,000 ppb. Mercury can react to form _HgCO3 or _Hg2CO3 and other mercury-containing compounds (e.g., chlorides, oxides), which effectively removes mercury from waste gas streams (e.g., flue gas streams) without specific or nonspecific Mercury removal technology. Additionally, compositions including mercury and/or other trace metals can be formed without additional release of _CO2 .

The precipitation material of the present invention may include several carbonates and/or several carbonate mineral phases, which result from co-precipitation, wherein the precipitation material may include, for example, calcium carbonate (e.g., calcite) and magnesium carbonate (e.g., Trihydrate magnesite). Precipitation material may also include individual carbonates in a single mineral phase, including, but not limited to, calcium carbonate (e.g., calcite), magnesium carbonate (e.g., magnesite), calcium magnesium carbonate (e.g., dolomite) Or iron carbon aluminum silicate (ferro-carbo-aluminosilicate). Since different carbonates can precipitate sequentially, the precipitation material can be, depending on the conditions under which it was obtained, relatively enriched (e.g., 90% to 95%) or significantly enriched in a carbonate and/or a mineral phase. Enriched (e.g., 95%-99.9%), or the precipitated material may include an amount of other carbonate and/or other mineral phase(s), wherein the desired mineral phase is 50-90% precipitated Material. It will be appreciated that, in some embodiments, the precipitation material may include one or more hydroxides (eg, Ca(OH)2, Mg(OH)2) in addition to carbonate. It will also be understood that any carbonate or hydroxide present in the precipitation material may be fully or partially amorphous. In some embodiments, the carbonates and/or hydroxides are completely amorphous. It will also be understood that any carbonate or hydroxide present in the precipitation material may be fully or partially crystalline. In some embodiments, the carbonates and/or hydroxides are fully crystalline.

While many different carbonate-containing salts and compounds are possible due to the variability of the feedstock, precipitation materials comprising magnesium carbonate, calcium carbonate, or combinations thereof are particularly useful. The precipitation material may comprise two or more different carbonate compounds, three or more different carbonate compounds, four or more different carbonate compounds, five or more different Carbonate compounds, etc., including non-distinct, amorphous carbonate compounds. The precipitation material of the present invention may comprise a compound having the molecular formula Xm(CO ₃ )n, wherein X is any element or combination of elements which can be chemically bonded with a carbonate group or a multiple thereof and m and n are chemical A positive integer for the measurement. In some embodiments, X can be an alkaline earth metal (an element in Group IIA of the Periodic Table of the Elements) or an alkali metal (an element in Group IA of the Periodic Table of Elements), or some combination thereof. In some embodiments, the precipitation material includes dolomite (CaMg(CO ₃ ) 2 ), orthodolomite, wortite, (CaMg3(CO ₃ ) 4 ), and/or hydrocarbite (Ca2Mg11(CO ₃ ) 13·H ₂ O), which is a carbonate mineral including calcium and magnesium. In some embodiments, the precipitation material includes calcium carbonate in one or more phases selected from calcite, aragonite, vaterite, or combinations thereof. In some embodiments, the precipitation material comprises a hydrated form of calcium carbonate (e.g., Ca(CO ₃ )·nH ₂ O) in which one or more structural waters are present in the molecular formula selected from molarite (CaCO ₃ ·6H ₂ O), amorphous calcium carbonate (CaCO ₃ ·nH ₂ O), calcite monohydrate (CaCO ₃ ·H ₂ O), or combinations thereof. In some embodiments, the precipitation material includes magnesium carbonate, wherein the magnesium carbonate does not have any water of hydration. In some embodiments, the precipitation material includes magnesium carbonate, where the magnesium carbonate can have a number of different waters of hydration (e.g., Mg(CO ₃ )·nH ₂ O), selected from 1, 2, 3, 4, or more than 4 hydrated water. In some embodiments, the precipitation material includes 1, 2, 3, 4, or more than 4 different magnesium carbonate phases, wherein the magnesium carbonate phases differ in the number of waters of hydration. _For example, _the precipitation material may _include magnesite (MgCO ₃ ) _, brucite (MgCO ₃ . 5H ₂ O) and amorphous magnesium carbonate. In some embodiments, the precipitation material includes magnesium carbonate, which includes hydroxide and water of hydration, such as hydromagnesite (MgCO ₃ Mg(OH)2 3H ₂ O), hydromagnesite (Mg5(CO ₃ )4(OH)2· _3H2O ) or a combination thereof. Thus, the precipitation material may comprise carbonates of calcium, magnesium, or combinations thereof, in all or some of the hydrated forms listed herein. The precipitation rate can also affect the properties of the precipitated material, with the fastest precipitation rates being obtained with the desired contact crystallization solution. Without seeding, rapid precipitation can be obtained, for example, by rapidly increasing the pH of the precipitation reaction mixture, which results in a more amorphous component. Furthermore, the higher the pH, the faster the precipitation, which results in more amorphous precipitation material.

In some cases, the amount by weight of the calcium carbonate compound in the precipitation material may exceed the amount by weight of the magnesium carbonate compound in the precipitation material. For example, the amount by weight of the calcium carbonate compound in the precipitation material may exceed the amount by weight of the magnesium carbonate compound in the precipitation material by 5% or more, such as 10% or more, 15% or more, 20% or more, 25% or more, 30% or more. In some cases, the weight ratio of calcium carbonate compound to magnesium carbonate compound in the precipitation material is 1.5-5 to 1, such as 2-4 to 1, including 2-3 to 1. In some cases, the amount by weight of the magnesium carbonate compound in the precipitation material may exceed the amount by weight of the calcium carbonate compound in the precipitation material. For example, the amount by weight of the magnesium carbonate compound in the precipitation material may exceed the amount by weight of the calcium carbonate compound in the precipitation material by 5% or more, such as 10% or more, 15% or more, 20% or more, 25% or more, 30% or more. In some cases, the weight ratio of magnesium carbonate compound to calcium carbonate compound in the precipitation material is 1.5-5 to 1, such as 2-4 to 1, including 2-3 to 1.

The precipitation material produced by the method of the present invention may include carbonate compounds which, when combined with fresh water, dissolve the initial precipitation material to produce freshwater precipitation material comprising carbonate compounds, compared to the carbonic acid content of the original precipitation material. Salt compounds, which are more stable in fresh water. (Although when combined with fresh water, the carbonate compounds of the original precipitation material can be dissolved, resulting in a new composition. Therefore, in any such reaction, _CO2 gas is not released in a significant amount, or sometimes, Not at all.) The carbonate compounds of the initial precipitation material may be more stable compounds in brine than they are in fresh water, so that the carbonate compounds may be considered metastable in brine. The amount of carbonate in the precipitation material, as determined by coulometric titration, may be 40% or higher, such as 70% or higher, including 80% or higher.

Adjusting the major ion ratio during precipitation can affect the properties of the precipitation material. The major ion ratio has a strong influence on polymorph formation. For example, as the magnesium:calcium ratio in water increases, aragonite becomes the predominant polymorph of calcium carbonate in precipitation material, compared to low-magnesium calcite. At low magnesium: calcium ratios, low-magnesium calcite becomes the predominant polymorph. In some embodiments, wherein both Ca2+ and Mg2+ are present in the water, the ratio of Ca2+ to Mg2+ (i.e., Ca2+:Mg2+) in the water is from 500:1 to 1:500, such as 100:1 to 1:100, such as 50:1 - 1:50, such as 20:1-1:20, such as 10:1-1:10. In some embodiments, wherein both Ca2+ and Mg2+ are present in the water, the ratio of Ca2+ to Mg2+ (ie, Ca2+:Mg2+) in the water is from 5:1 to 1:1. In some embodiments, wherein both Ca2+ and Mg2+ are present in the water, the ratio of Ca2+ to Mg2+ (ie, Ca2+:Mg2+) in the water is 4:1. In some embodiments, wherein both Ca2+ and Mg2+ are present in the water, the ratio of Ca2+ to Mg2+ (ie, Ca2+:Mg2+) in the water is from 1:1 to 1:10. In some embodiments, where both Ca2+ and Mg2+ are present in water, the ratio of Mg2+ to Ca2+ (i.e., Mg2+:Ca2+, which is the reciprocal of Ca2+:Mg2+) in the water is 10:1-1:1, such as 5:1- 2:1. In some embodiments, where both Ca2+ and Mg2+ are present in the water, the ratio of Mg2+ to Ca2+ (ie, Mg2+:Ca2+, which is the reciprocal of Ca2+:Mg2+) in the water is 4:1. In some embodiments, where both Ca2+ and Mg2+ are present, the ratio of Ca2+ to Mg2+ (i.e., Ca2+:Mg2+) in the precipitation material is from 10:1 to 1:1; from 1:1 to 1:2.5; from 1:2.5 to 1:5; 1:5 to 1:10; 1:10 to 1:25; 1:25 to 1:50; 1:50 to 1:100; 1:100 to 1:150; 1:150 to 1: 200; 1:200 to 1:250; 1:250 to 1:500; 1:500 to 1:1000 or the range thereof. For example, in some embodiments, the ratio of Ca2+ to Mg2+ in the precipitation material is between 1:1 and 1:10; 1:5 and 1:25; 1:10 and 1:50; 1:25 and 1:100; 1:50 and 1:500; or between 1:100 and 1:1000. In some embodiments, the ratio of Mg2+ to Ca2+ (i.e., Mg2+:Ca2+) in the precipitation material is between 1:1 and 1:2.5; 1:2.5 and 1:5; 1:5 and 1:10; 1:10 and 1:25; 1:25 and 1:50; 1:50 and 1:100; 1:100 and 1:150; 1:150 and 1:200; 1:200 and 1:250; 1:250 and 1 :500; between 1:500 and 1:1000 or the range thereof. For example, in some embodiments, the ratio of Mg2+ to Ca2+ in the precipitation material is between 1:1 and 1:10; 1:5 and 1:25; 1:10 and 1:50; 1:25 and 1:100; 1:50 and 1:500; or between 1:100 and 1:1000.

Due to the variability of the starting materials, carbonate-containing salts and compounds including counterions other than calcium or magnesium are possible. For example, in some embodiments, compositions (eg, precipitation materials) of the invention include calcium carbonate in the form of aragonite. In such embodiments, calcium may be replaced by a number of different metals, including but not limited to strontium, lead and zinc, each of which, in one form or another, may be present in one or more of the present invention In starting materials (eg, waste gas streams, sources of proton-removing agents, sources of divalent cations, etc.). The composition may include, for example, strontium aragonite, which is a strontium-rich aragonite, or the composition may include a mixture of aragonite and strontite (eg, (Ca,Sr)CO ₃ ). The composition may include, for example, aragonite, which is a lead-rich aragonite, or the composition may include a mixture of aragonite and schenite (eg, (Ca,Pb)CO ₃ ). The composition may include, for example, sauconite, which is a Zn-rich aragonite, or the composition may include a mixture of aragonite and smithsonite (eg, (Ca,Zn)CO ₃ ). In view of the above exemplary embodiments, the composition (e.g., precipitation material) may include As, Ag, Ba, Be, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Se, Sb, Tl, V, or Zn carbonates, bicarbonates, or carbonates and bicarbonates. For example, compositions of the present invention may include carbonates of Ag, Ba, Be, Cd, Co, Cu, Ni, Pb, Tl, Zn, or combinations thereof. Carbonates, bicarbonates, or carbonates and bicarbonates of the above metals may be formed independently (eg, strontite) or present in a matrix of magnesium and/or calcium (eg, strontium aragonite). Metals such as As, Ag, Ba, Be, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Se, Sb, Tl, V and Zn can be produced from waste gas streams, proton-removing agent sources, divalent cation sources or a combination thereof. Metals and other components present in such sources (e.g., waste gas streams, sources of proton-removing agents, sources of divalent cations) that do not form carbonates, bicarbonates, or carbonates and bicarbonates can be trapped in the precipitate in the material or adsorbed on the precipitating material.

Precipitation material, which includes one or more synthetic carbonates derived from industrial CO ₂ , reflecting the fossil fuel (for example, coal, oil, natural gas, or flue gas) from which industrial CO ₂ (from burning fossil fuels) originated ) relative carbon isotopic composition (δ13C). The relative carbon isotopic composition (δ13C) value, in units of ‰ (parts per thousand), is a measure of the ratio of the concentrations of two stable isotopes of carbon, namely 12C and 13C, relative to the concentration of a fossilized arrowstone standard (PDB standard) .

δ ¹³ C‰＝[( ¹³ C/ ¹² C sample - ¹³ C/ ¹² C PDB standard)/( ¹³ C/ ¹² C PDB standard)]x1000

Thus, the δ13C value of the synthesized carbonate-containing precipitation material was used as a fingerprint of the _CO2 gas source. δ13C values may vary due to different sources (ie, fossil fuel sources), but compositions of the invention typically, but not necessarily, have δ13C values in the range of -9‰ to -35‰. In some embodiments, the synthetic carbonate-containing precipitation material has a δ13C of -1‰ to -50‰, -5‰ to -40‰, -5‰ to -35‰, -7‰ to -40‰ , -7‰ to -35‰, -9‰ to -40‰, or -9‰ to -35‰. In some embodiments, the synthetic carbonate-containing precipitation material has a δ13C value less than (i.e., more negative than) -3‰, -5‰, -6‰, -7‰, -8‰, -9‰, -10‰, -11‰, -12‰, -13‰, -14‰, -15‰, -16‰, -17‰, -18‰, -19‰, -20‰, -21‰, -22 ‰, -23‰, -24‰, -25‰, -26‰, -27‰, -28‰, -29‰, -30‰, -31‰, -32‰, -33‰, -34‰, -35‰, -36‰, -37‰, -38‰, -39‰, -40‰, -41‰, -42‰, -43‰, -44‰, or -45‰, where the δ13C value is more negative , the synthesized carbonate-containing composition is more enriched in 12C. Any suitable method can be used to measure the δ13C value, including, but not limited to, mass spectrometry or off-axis integrating cavity output spectroscopy (off-axis ICOS).

In addition to the magnesium and calcium containing products of the precipitation reaction, compounds and materials including silicon, aluminum, iron and other elements can also be prepared and incorporated in the precipitation material using the methods and systems of the present invention. The precipitation of such compounds in the precipitation material or the addition of such compounds to the precipitation material may be desirable in order to alter the reactivity of the cement comprising the precipitation material resulting from the process, or to alter the properties of the cured cement and concrete produced therefrom. performance. Materials comprising metal silicates may be added to the precipitation reaction mixture as a source of these components to produce carbonate-containing precipitation material comprising one or more components such as amorphous silica, Amorphous aluminosilicate, crystalline silica, calcium silicate, calcium aluminum silicate, etc. In some embodiments, the precipitation material includes carbonates (e.g., calcium carbonate, magnesium carbonate) and silica, wherein the carbonate:silica ratio is 1:1-1:1.5; 1:1.5-1: 2; 1:2-1:2.5; 1:2.5-1:3; 1:3-1:3.5; 1:3.5-1:4; 1:4-1:4.5; 1:4.5-1:5; 1:5-1:7.5; 1:7.5-1:10; 1:10-1:15; 1:15-1:20 or the range thereof. For example, in some embodiments, the precipitation material includes carbonate and silica, wherein the carbonate:silica ratio is 1:1-1:5, 1:5-1:10, or 1:5-1 : 20. In some embodiments, the precipitation material comprises silica and carbonate (e.g., calcium carbonate, magnesium carbonate), wherein the silica:carbonate ratio is 1:1-1:1.5; 1:1.5-1: 2; 1:2-1:2.5; 1:2.5-1:3; 1:3-1:3.5; 1:3.5-1:4; 1:4-1:4.5; 1:4.5-1:5; 1:5-1:7.5; 1:7.5-1:10; 1:10-1:15; 1:15-1:20 or the range thereof. For example, in some embodiments, the precipitation material includes silica and carbonate, wherein the silica:carbonate ratio is 1:1-1:5, 1:5-1:10 or 1:5-1 : 20. In general terms, the precipitation material produced by the method of the present invention comprises a mixture of silicon-based material and at least one carbonate phase. In summary, the faster the reaction rate, the more silica is incorporated into the carbonate-containing precipitation material, provided that silica is present in the precipitation reaction mixture (i.e., provided that no remove silica).

The precipitation material may be in a storage stable form (which may simply be air-dried precipitation material) and may be stored above ground under exposed conditions (i.e., open to the atmosphere) without significant, if any, decomposition ( or CO ₂ loss) for extended periods of time. In some embodiments, the precipitation material can be stable under exposure conditions for 1 year or longer, 5 years or longer, 10 years or longer, 25 years or longer, 50 years or longer, 100 years or Longer, 250 years or more, 1,000 years or more, 10,000 years or more, 1,000,000 years or more, or even 100,000,000 years or more. Precipitation material in storage stable form may be stable under various environmental conditions, eg temperature -100°C to 600°C and humidity 0-100%, where conditions may be calm, windy or stormy. Because when stored above ground at normal rainwater pH, the stored stable form of the precipitated material undergoes little, if any, decomposition, and the amount of decomposition, if any, in terms of _CO2 gas release from the product Measured, not to exceed 5% per annum, in certain embodiments not to exceed 1% per annum or 0.001% per annum. Indeed, the precipitation material provided by the present invention does not release more than 1%, 5% or 10% of its total _CO2 when exposed to standard conditions of temperature and humidity, including rainfall at normal pH, up to at least 1, 2, 5, 10 or 20 years, or up to more than 20 years, for example, more than 100 years. In some embodiments, the precipitation material does not release greater than 1% of its total _CO2 when exposed to standard conditions of temperature and humidity, including rainfall at normal pH, for at least 1 year. In some embodiments, the precipitation material does not release greater than 5% of its total _CO2 when exposed to standard conditions of temperature and humidity, including rainfall at normal pH, for at least 1 year. In some embodiments, the precipitation material does not release greater than 10% of its total _CO2 when exposed to standard conditions of temperature and humidity, including rainfall at normal pH, for at least 1 year. In some embodiments, the precipitation material has not released greater than 1% of its total _CO2 when exposed to standard conditions of temperature and humidity, including rainfall at normal pH, for at least 10 years. In some embodiments, the precipitation material has not released greater than 1% of its total _CO2 when exposed to standard conditions of temperature and humidity, including rainfall at normal pH, for at least 100 years. In some embodiments, the precipitation material has not released greater than 1% of its total _CO2 when exposed to standard conditions of temperature and humidity, including rainfall at normal pH, for at least 1000 years.

Any suitable surrogate marker or test that is reasonably predictable of such stability may be used. For example, accelerated testing, including elevated temperature conditions and/or moderate to more extreme pH conditions, can reasonably indicate stability over extended periods of time. For example, depending on the intended use and environment of the precipitation material, a sample of the precipitation material may be exposed to 1, 2, 5, 25, 50, 100, 200 or 500 days, and its loss of carbon is less than 1%, 2%, 3%, 4%, 5%, 10%, 20%, 30% or 50% can be considered stable for the precipitation material of the present invention Sufficient evidence of persistence over a period of time (eg, 1, 10, 100, 1000, or greater than 1000 years).

A number of suitable methods can be used to test the stability of the precipitation material, including physical testing methods and chemical testing methods, where the methods are suitable for determining that the compounds in the precipitation material are similar or equivalent to naturally occurring compounds known to have the above-mentioned stability. compounds (eg, limestone). The _CO2 content of the precipitation material can be monitored by any suitable method, one such non-limiting example is coulometric analysis. Other conditions may be adjusted as appropriate, including pH, pressure, UV radiation, etc., also depending on the expected or likely environment. It should be understood that any suitable conditions may be used, which a person skilled in the art would reasonably infer, given the necessary stability over the indicated times. Additionally, if accepted chemical knowledge indicates that the precipitation material will have the requisite stability for the time indicated, this may also be used in addition to or instead of actual measurements. For example, certain carbonate compounds, which may be part of the precipitation material of the present invention (e.g., in a given polymorphic form), may be geologically well known and known to have survived normal climates for tens of years, hundreds, or even thousands of years without appreciable decomposition, and thus have the requisite stability.

The carbonate-containing precipitation material used to sequester _CO2 in a form that is stable over long periods of time (eg, geological timescales) can be stored for extended periods of time, as described above. The precipitation material, if desired to obtain a certain ratio of carbonate to silica, can also be mixed with a silicon-based material (e.g., from a silicon-based material after digestion of a material including metallosilicates; commercially available SiO ₂ ; etc.) to form pozzolanic materials. The pozzolanic materials of the present invention are siliceous or aluminosilicate materials which, when combined with a base such as calcium hydroxide (Ca(OH)2), exhibit bonding properties by forming calcium silicates and other bonding materials. _SiO2 -containing materials such as pozzolans, fly ash, silica fume, highly reactive metakaolin and ground granulated blast furnace slag, among others, can be used to enhance compositions of the present invention that produce pozzolanic materials. In some embodiments, the pozzolanic materials of the present invention are enhanced with 0.5% to 1.0%, 1.0% to 2.0%; 2.0% to 4.0%, 4.0% to 6.0%, 6.0% to 8.0%, 8.0% to 10.0%, 10.0% to 15.0%, 15.0% to 20.0%, 20.0% to 30.0%, 30.0% to 40.0%, 40.0% to 50.0%, or their overlapping ranges, _SiO2 -containing materials. Such _SiO2 -containing materials can be obtained, for example, from electrostatic precipitators or fabric filters of the present invention.

As noted above, in some embodiments, the precipitation material includes metastable carbonate compounds that are more stable in salt water than in fresh water such that when contacted with fresh water at any pH, it dissolves and reprecipitates as other fresh water Stabilizing minerals. In certain embodiments, the carbonate compound is present in the form of small particles, e.g., a particle size of 0.1 μm to 100 μm, 1 to 100 μm, 10-100 μm, 50 to 100 μm, as detected by scanning electron microscopy. determined by SEM. In some embodiments, the carbonate compound has a particle size of 0.5 to 10 μm, as determined by SEM. In some embodiments, the particle sizes exhibit a monomodal distribution. In some embodiments, the particle size exhibits a bimodal or multimodal distribution. In certain embodiments, the particles have a high surface area, e.g., 0.5 to 100 m/gm, 0.5 to 50 m/gm, or 0.5 to 2.m/gm, as determined by BET (Brauner, Emmit, & Teller) surface area analysis. In some embodiments, the precipitation material can include rod-shaped crystals and/or amorphous solids. Rod crystals can vary in structure, and in certain embodiments have a length to diameter ratio of 500 to 1, 250 to 1, or 10 to 1. In certain embodiments, the crystals have a length of 0.5 μm to 500 μm, 1 μm to 250 μm, or 5 μm to 100 μm. In other embodiments, substantially completely amorphous solids are produced.

The spray-dried material (eg, precipitation material, silica-based material, pozzolanic material, etc.), can have a consistent particle size (ie, the spray-dried material can have a relatively narrow particle size distribution) by virtue of spray drying. Thus, in some embodiments, at least 50%, 60%, 70%, 80%, 90%, 95%, 97%, or 99% of the spray-dried material falls within ±10 microns, ±20 microns, ±30 microns, ±40 microns, ±50 microns, ±75 microns, ±100 microns or ±250 microns. In some embodiments, the given average particle size is 5-500 microns. In some embodiments, the given average particle size is 5-250 microns. In some embodiments, the given average particle size is 5-100 microns. In some embodiments, the given average particle size is 5-50 microns. In some embodiments, the given average particle size is 5-25 microns. For example, in some embodiments, at least 70% of the spray-dried material falls within ±50 microns of a given mean particle size, where the given mean particle size is 5-500 microns, such as 50-250 microns or 100- 200 microns. Such spray-dried materials can be used to make the cement, fine aggregate, mortar, coarse aggregate, concrete and/or pozzolan cement of the present invention; however, those skilled in the art will recognize that cement, fine aggregate, mortar, coarse The manufacture of aggregates, concrete and/or pozzolan cement does not require spray-dried settling material. Air-dried precipitation materials, for example, can also be used to make cements, fine aggregates, mortars, coarse aggregates, concrete and/or pozzolan cements of the present invention.

Example

In conjunction with the above description, the following examples are provided to those skilled in the art to fully disclose and illustrate how to make and use the invention. This example is presented to provide what is believed to be the most useful and readily understood procedural and conceptual illustration of certain embodiments of the invention. Likewise, this example is not intended to limit the scope of what the inventors believe their invention to be, nor does this example set forth all of the tests or only those that were performed. Efforts have been made to ensure accuracy with respect to numbers used (eg, amounts, temperature, etc.), but some experimental errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, molecular weight is weight average molecular weight, temperature is in degrees Centigrade, and pressure is at or near atmospheric.

Example I. Precipitation of P00099

A.P00099 precipitation method

The following protocol was used to generate the P00099 precipitate. 380L of filtered seawater is pumped into cylindrical polyethylene 60° tapered bottom tanks. The reaction tank is an open system with the left exposed to ambient atmosphere. The reaction tank was continuously stirred using an overhead mixer. The pH, room temperature and water temperature were continuously monitored throughout the reaction.

25 g of particulate (Ca,Mg)O (also known as calcined dolomite or calcined dolomite) were mixed into the seawater. Calcined dolomite that has settled to the bottom of the tank is manually recirculated from the bottom of the tank through the top to promote thorough mixing and dissolution of the reactants. A second 25 g of calcined dolomite was added in the same manner, including manual recirculation of the settled reactants. When the pH of the water reached 9.2, a gas mixture of 10% _CO2 (and 90% compressed air) was slowly diffused into the solution through a ceramic airstone. When the pH of the solution dropped to 9.0, an additional 25 g addition of calcined dolomite was added to the reaction tank, which caused the pH to rise again. When the pH of the solution continued to drop to 9.0 (or below), the calcined dolomite was added repeatedly until the total amount added was 225 g. Recirculation of the settled reactants was performed manually between each calcined dolomite addition.

After the final addition of calcined dolomite, the continuous diffusion of gas through the solution was stopped. The reaction was stirred for an additional 2 hours. During this period, the pH continued to rise. To maintain the pH at 9.0-9.2, when the pH rises above 9.2, additional gas is diffused through the reaction until it reaches 9.0. During this 2 hour period, 4 manual recirculations of the settled reactants were also performed.

Two hours after the last addition of calcined dolomite, stirring, gas diffusion and recirculation of settled reactants were stopped. The reaction tank was left to stand for 15 hours (opened to the atmosphere).

After a period of 15 hours, the supernatant was removed from the top of the reaction tank using a submersible pump. The rest of the mixture was removed from the bottom of the tank. The collected mixture was allowed to settle for 2 hours. After settling, the supernatant was decanted. The rest of the slurry was vacuum filtered in a Büchner funnel through 11 μm pore size filter paper. The collected filter cake was put into a heat-resistant glass dish and baked at 110° C. for 24 hours.

The dried product was ground in a ball mill and size fractionated through a series of screens to produce a P00099 precipitate.

B. Material Analysis

Of the different sieves collected, only those containing particles retained on the 38 μm opening sieve and passed through the 75 μm opening sieve were used.

1. Chemical properties

XRF was used to analyze the elemental composition of the P00099 precipitates used for blending. The results for the QUIKRETE™ Type I/II Portland cement used in the blend and for the major elements of the P00099 precipitate are reported in Table 4 below.

Table 4. XRF analysis of Type I/II Portland cement and P00099-002 used in this blend.

samples Na ₂ O (%) MgO(%) Al ₂ O ₃ (%) SiO ₂ (%) P ₂ O ₅ (ppm) SO ₃ (%) Cl(%) K ₂ O (%) CaO(%) Fe ₂ O ₃ (%) Sr(ppm) CO ₃ (% diff OPC1 2.15 1.95 4.32 20.31 2336 2.54 0.072 0.36 62.88 3.88 1099 0.002 P00099 1.36 3.44 0.14 0.083 462 0.65 1.123 0.04 45.75 0.12 3589 46.82

XRD analysis of the precipitate showed the presence of aragonite and magnesium calcite (composition close to Mg _0.1 Ca _0.9 CO ₃ ) and small amounts of bruxite and halite (Table 5). FT-IR analysis of the P00099 precipitate confirmed the presence of aragonite, calcite and borschite.

Table 5. XRD analysis of the precipitate.

samples Aragonite Magnesium calcite Magnesite rock plate P00099 79.9 17.1 2.8 0.2

The total inorganic carbon content measured by coulometric analysis is in good agreement with the values derived from the XRD Rietveld estimated composition combined with the XRF elemental composition. Table 6 provides the coulometric analysis of P00099 compared to %C from XRD/XRF data.

Table 6. Coulomb analysis of P00099 compared to %C from XRD/XRF data.

Total C from coulometric analysis Total C from other analyzed data 10.93±0.16% 11.5%

2. Physical properties

SEM observations on the precipitate confirmed the predominance of aragonite (acicular) and the size of particle aggregates. The measured BET specific surface areas ("SSA") of Portland cement and P00099 precipitates are given in Table 7.

Table 7. BET specific surface area ("SSA") of Portland cement and P00099 precipitates.

Type I/II Quikrete Portland Cement P00099 1.18±0.04m ² /g 8.31±0.04m ² /g

The particle size distribution was determined after 2 min of pre-ultrasonic dispersion for separating aggregated particles.

Example II. Use of Fly Ash as Alkali Source

A. method

500 mol of seawater (initial pH = 8.01) was continuously stirred in a glass beaker using a magnetic stirring bar. The pH and temperature of the reaction were continuously monitored. Class F fly ash (-10% CaO) was added as a powder increment such that the pH was balanced between additions.

B. Results and Observations:

After adding 5.00 g of fly ash, the pH reached 9.00.

34.14g-->pH9.50

168.89g-->pH9.76

219.47g-->pH10.94

254.13g-->pH11.20

300.87g-->pH11.28

(The amount of fly ash listed is the cumulative total, ie, the total amount added during the test time points.)

Much more fly ash than distilled water is required to raise the pH of seawater. The initial pH increase (8-9) required much less fly ash than further increases. The pH remained fairly constant at around 9.7 for most of the reaction time. The rate of increase in pH accelerated after ~10. Also of note is the initial drop in pH when fly ash is added. This pH drop is quickly overcome by the action of calcium hydroxide. SEM images of the vacuum-dried slurry from this reaction indicated that some fly ash spheres had partially dissolved. The rest of the spheres appear to be embedded in what may be a cement-like material.

c. conclusion

In dilute (distilled) water, small amounts of Class F fly ash (<1 g/L) have been found to immediately raise the pH from 7 (neutral) to ~11. This small amount necessary to raise the pH is likely due to the unbuffered properties of distilled water. Seawater is highly buffered by carbonates, and thus it consumes large amounts of fly ash to raise the pH to a similar degree.

Example III. High Yield Production

A. Method 1

A gas mixture of 20% _CO2 /80% air was sparged into 1 L of seawater until a pH<5 was reached. Once reached, 1.0 g of Mg(OH) ₂ was added to the 1 L of carbonic acid/seawater solution. The 20/80 gas mixture was sprayed for 20 minutes to ensure maximum dissolution of Mg(OH) ₂ and gas. After dissolution, spraying was stopped and 2M NaOH was added until a pH of 9.8 was reached. The 20/80 gas spray was restarted until pH 8.5 was reached. Continue 2M NaOH and reverse 20/80 gas addition to maintain the pH at 8.5-9.8 until a total of 200ml of 2M NaOH has been added. A yield of 6.91 g was observed with a coulometer reading of 10.6% carbon (-80% carbonate).

B. Method 2

A gas mixture of 20% _CO2 /80% air was sparged into 1 L of seawater until a pH<5 was reached. Once reached, 2.69 g of Mg(OH) ₂ was added to the 1 L of carbonic acid/seawater solution. The 20/80 gas mixture was sprayed for 20 minutes to ensure maximum dissolution of Mg(OH) ₂ and gas. After dissolution, spraying was stopped and 2M NaOH was added until a pH of 9.8 was reached. The 20/80 gas spray was restarted until pH 8.5 was reached. Continue 2M NaOH and reverse 20/80 gas addition to maintain the pH at 8.5-9.8 until a total of 200ml of 2M NaOH has been added. A yield of 10.24 g was observed with a coulometer reading of 9.7% carbon (-75% carbonate).

SEM, EDS and X-ray diffraction of the precipitated carbonates indicated the presence of amorphous and crystalline Ca and Mg carbonates, as well as the presence of Ca/Mg carbonates. Pictures of the precipitate are provided in Figures 41 and 42.

C. Method 3

Spray _CO2 into 1L of seawater until pH7 or lower is reached. Add 0-5.0 g of Mg ion supplement (called "Moss Mag" and obtained from Calera Corporation's Moss Landing site, former site of Kaiser Aluminum & Chemical Corporation and National Refractorie in Moss Landing California, where the supplement is at Mg-rich waste products present in the tailings pond at the site) while mixing and continuously sparging _CO2 . 0.175 ppm of Al ₂ (SO ₄ ) ₃ was added. Continuous sparging of _CO2 and addition of base while maintaining the pH at 7 to 8, terminated at pH 7. The _CO2 sparge was stopped and base was added until a pH of 9.0 to 10.4 was reached. As shown in Figure 43, the above reaction conditions favored the formation of amorphous carbonate compound precipitates. The resulting amorphous precipitated product is readily spray dried to yield a dry product.

D. Method 4

As shown in Figures 38, 39 and 40, in certain embodiments, a multi-step, multi-reactor approach is used to carry out the methods disclosed herein. In the first reactor, a source of magnesium ions obtained from the Moss Landing, California site (hereinafter referred to as Moss Mag) was placed in the solution using carbonic acid and stirred. The pH of the seawater in the first reactor was maintained at pH 7.0 or lower during the Moss Mag dissolution process. In certain embodiments, 1.0 g of 50-150 μm Moss Mag is dissolved per 1 L of seawater to form a solution. A pH of 6.2-6.6 or a hardness reading of >0.08 g/l indicates that the appropriate amount of Moss Mag is dissolved in the solution. A source of _CO2 such as flue gas is sparged into the water in the first reactor. About 40-50% of the total flue gas consumed in the whole reaction is dissolved into the seawater in this step. The flue gas was sprayed until the pH no longer responded to the dissolution of the flue gas, which took approximately 30-60 minutes. Stirring is stopped to allow unreacted MossMag, sand or other large particles to settle by gravity, then the acidic water with _CO2 is transferred from the first reactor to the second reactor.

The acidic water with _CO2 is then transferred from the first reactor to the second reactor. This second reactor is used both to create nucleation sites and for crystal growth. After the solution was transferred from the first reactor to the second reactor, the following steps were carried out:

1. Add 50% NaOH until a pH of 9.5 is reached. For example for a 1000 gallon reaction, 20-25 kg of 50% NaOH is added using a metering pump capable of pumping 5-25 ml/s of 50% NaOH. After reaching a pH of 9.5, the addition of 50% NaOH was stopped.

2. A _CO2 source comprising a mixture of 20% _CO2 /80% compressed air was sparged into the second reactor until pH 8.5 was reached. After reaching a pH of 8.5, the CO _sparging was stopped.

3. Alternate steps of adding 50% NaOH to the reactor to raise the pH and sparging _CO2 to lower the pH. The pH was maintained at 8.5–9.8 during the alternating addition of 50% NaOH and sparging of _CO2 . The alternating metering of 50% NaOH and sparging of _CO2 was continued until a total of 90 kg (ie 65-70 kg in this step + 20-25 kg in the first step) of 50% NaOH had been added to the reactor.

4. After the final addition of 50% NaOH, the final pH is 9.6-9.8.

5. Stirring was stopped, and the precipitate was gravity settled overnight, followed by water/solid separation. Optionally, after cessation of agitation, the precipitate was allowed to settle by gravity for 15 minutes, followed by accelerated water/solid separation. The precipitate was kept at a temperature below 50°C.

The resulting yield is 30-50 lbs of precipitate/1000 gallon reactor and depends on Mg ion dissolution and total hardness prior to precipitation.

Example IV. _CO2 Absorption

A. Method 1

In this example, laboratory scale carbon dioxide absorption is described. 4.00 L of seawater was magnetically stirred while 100% _CO2 was resprayed through the solution for 19 minutes, where the pH reached a minimum of 4.89. To this solution was added 32.00 g of jet milled Mg(OH) ₂ over 2 minutes. At the same time, while the Mg(OH) ₂ was dissolved, CO ₂ was continuously added for a total of 18 minutes to maintain the pH at 7.90 to 8.00. Next, 100.00 mL of 2M NaOH was added over 5 minutes while maintaining the pH at 8.00 to 8.10 by adding CO ₂ . To facilitate precipitation, 275 mL of 2M NaOH was added over 5 minutes and the resulting solution was stirred for an additional 52 minutes. The slurry was vacuum filtered and dried in an oven at 50° C. for 22 hours to recover 19.5 g of calcium and magnesium carbonates (primary aragonite and bischite, respectively) per 1 L of initial seawater solution.

B. Method 2

In this example, laboratory scale carbon dioxide absorption is described. A 100 gallon conical bottom plastic reaction vessel was filled with 100 gallons (380 L) of seawater which was used throughout the process with an overhead agitator (portable mixer w/shaft, 2-4" SS propeller blades (1-push , 1-pull), and mounting frame) for stirring. The first step is to spray the solution with CO concentrated to 20% CO ₂ and 80% compressed air at a flow rate of 25 scfh. The equilibrium _point is determined by the stabilization of the solution pH The second step is to add 2.70g/L Mg(OH) ₂ (1.02kg) and remix. To further promote the dissolution of Mg(OH) ₂ CO _is sprayed through the solution. The third step is Add 50 wt% NaOH solution until pH 9.8 is reached, followed by sparging additional CO to lower the pH to 8.0. Repeat the latter _two adding 50 wt% NaOH to bring the pH to 9.8 and sparging _CO to lower the pH to 8.0 steps until a total of 16.0 kg of 50 wt% NaOH has been added to the solution, where the last added NaOH was used to achieve pH 10.0. The precipitate was separated and collected from this solution with a yield of 10.24 g/L of calcium carbonate and magnesium carbonate hydrate.

C. Method 3

In this example, laboratory scale carbon dioxide absorption is described. A 100 gallon conical bottom plastic reaction vessel was filled with 100 gallons (380 L) of seawater which was stirred with an overhead stirrer throughout the process. The first step is to spray the solution with _CO2 concentrated to 20% by volume at a flow rate of 100 scfm (standard cubic feet per minute). Determine the equilibrium point when the _CO2 concentration in the vessel headspace is close to that of the inlet gas. The calculated _CO absorption at this step is understandably low. The second step was to slowly add 379 g of Mg(OH) ₂ to avoid a sharp increase in pH, which would favor undesired carbonate precipitation. To further facilitate the dissolution of Mg(OH) ₂ , _CO2 was sparged through the solution, resulting in a final pH of 6.3. The final step is the continuous capture of _CO2 in solution. Over a period of 3.5 hours, 4.9 kg of NaOH was added to balance the pH at 7.9 while spraying and reacting _CO2 to form bicarbonate ions. The calculated _CO2 absorption at this step is 68%-70%. The results are presented in Figure 44, which shows the change in pH and _CO2 uptake (instantaneous and cumulative). Artifacts at point 1 in the pH diagram are from removing the pH probe to add Mg(OH) ₂ .

D. Method 4

In this example, industrial scale carbon dioxide absorption is described. The 1000 gallon reaction vessel was filled with 900 gallons (3400 L) of seawater, which was stirred throughout the process. The first step was to top up the solution with 3.3 kg Mg(OH) ₂ , which increased both the pH and the magnesium content. Next, 10% by volume of _CO2 was sprayed and the pH was maintained at 7.9 by continuous addition of up to 30 kg of NaOH. These steps lasted a total of 5-6 hours. Finally 38 kg NaOH was added to raise the pH to allow carbonate formation and precipitation. This step lasts 10-20 minutes. The solution was stirred for 1 more hour to allow further precipitation. The reaction was allowed to settle overnight. The solution was decanted and the solid product was recovered by press or vacuum filtration. In addition, the solution can be rinsed after the decanting process; water is thus added, and the sample is press filtered. Optionally, water is added after the initial vacuum filtration, agitation and refiltration. Finally the product is spray dried. The overall yield was 5-7 g/L of initial solution.

Example V. High Yield Dissolution of Mafic Minerals in HCl

In this example, the dissolution of olivine followed by the precipitation of _CO2 is described. Olivine (10.01 g, particle size ~5.8 μm) was dissolved using a 10% HCl (475.66 g) solution at 50°C. After the solution was stirred for 10 hours and left for 9 hours to provide a Mg2 ⁺ (aq) concentration of 0.2491 mol/L, it was vacuum filtered hot to recover 404.52 g of filtrate. The solution was neutralized with 15.01 g of NaOH (solid) and 5.23 g of NaOH (aq) (50 wt% solution) over a period of 1 hour. Simultaneously, 100% _CO2 was re-sprayed through the mixture to provide a final pH of 8.9, where a precipitate formed. The slurry was vacuum filtered and dried at 50°C for 17 hours to yield 19.26 g containing MgCO ₃ ·H ₂ O, NaCl, Fe-based compounds and Si-based compounds.

Example VI. Electrochemistry

Exemplary results achieved with a two-electrode system according to the invention are summarized in Table 8 below.

Table 8. Low energy electrochemical two-electrode methods and systems.

The voltage V across the electrodes time (min) Initial pH of the anode Final pH of the anode The initial pH of the cathode The final pH of the cathode 0.45V 0.30V in the first chamber, 0.15V in the second chamber 30 4.994 5.204 7.801 7.431

In this example, an electrochemical system for the deprotonation of seawater, which has been filled with CO ₂ , is described. The cell used consisted of two 1 L compartments separated by a palladium foil. The first chamber was filled with _CO2 until pH 4.994 was reached. A sacrificial tin anode was placed in the first chamber, and the tin electrode and palladium diaphragm were kept under constant current control of 100 nA/cm ² , which represented a voltage of 0.30V. The second chamber consists of tin electrodes and _SnCl2 dissolved in seawater. The palladium diaphragm and tin electrodes in the second chamber were kept at 0.15V here. The system was run for 30 minutes, and as shown in Table 8, the system exhibited an increase in pH in the first electrolyte, and a decrease in pH in the second electrolyte.

Exemplary results achieved with this ionic membrane system are summarized in Table 9 below.

Table 9. Low energy electrochemical ion exchange systems and methods.

The voltage V across the electrodes time (min) Initial pH of the anode Final pH of the anode The initial pH of the cathode The final pH of the cathode 0.6 2000 6.7 3.8 6.8 10.8 1.0 2000 6.6 3.5 6.8 11.1

In this example, an electrochemical cell is described for the production of NaOH and HCl at low operating voltages using an ion exchange membrane located between the anode and cathode. The cell used consisted of two 250 mL compartments separated by an anion exchange membrane (PC-SA-250-250 (PCT GmbH of Germany)). 0.5 M NaCl in 18 MΩ in water was used in both chambers. Both the anode and cathode were made of 10cmx5cm, 45 mesh Pt screen. The anode chamber had _H gas sparged under the Pt electrodes, and these two electrodes were kept at a bias of 0.6 V and 1.0 V for 2000 s. As shown in Table 9, both tests achieved a significant increase in pH in the cathodic compartment, and a decrease in pH in the anodic compartment.

Example VII. Liquid-Solid Separation

A. Method 1

In this prophetic example, a laboratory-scale separation of precipitation products from precipitation site effluents is described. A precipitation product slurry was prepared as described above in Example IV.

A slurry containing the precipitation product was produced in a reaction vessel (see Example IV), which is referred to as the precipitation site in this example. After the precipitation product slurry is formed, the slurry is provided to a liquid-solid separation device as a precipitation site discharge. The settling site effluent pipe is used to provide the slurry to the liquid-solid separation device and direct the slurry to flow against a baffle through which to deflect the flow of the settling site effluent. The heavier precipitation product particles continue their downward travel path along the settling site discharge pipe (i.e., in the direction of gravity) to the collector while the supernatant is deflected, separated from the settling product particles, and passed through the liquid-solid The upper part of the separation device leaves. The precipitated product formed is removed from the collector and dried to produce calcium carbonate and magnesium carbonate hydrate.

B. Method 2

In this prophetic example, a laboratory-scale separation of precipitation products from precipitation site effluents is described. A precipitation product slurry was prepared as described above in Example IV.

A slurry containing the precipitation product was produced in a reaction vessel (see Example IV), which is referred to as the precipitation site in this example. After the precipitation product slurry is formed, the slurry is provided as a precipitation site discharge to a liquid-solid separation device, wherein the slurry is allowed to flow in a helical channel. At the end of the helical channel, parallel-arranged outlets collect the separated precipitation product particles. The precipitated product formed is removed from the collector and dried to produce calcium carbonate and magnesium carbonate hydrate.

Example 1. This example shows the use of an ultrasonic nebulizer in one chamber to generate droplets with a high surface area to volume ratio, which are then contacted with carbon dioxide in another chamber. The system of this embodiment is similar to FIG. 45 .

This first system used a commercially available ultrasonic nebulizer [Figure 45: 200] consisting of 10 transducers capable of nebulizing approximately 4 L of water per hour. A 4 inch (10.16 cm) inline fan [at 220] was used to move the mist of droplets [215] into the mixing chamber [245]. This gas is then recirculated from the mixing chamber [240] and back into the converter chamber [220] while pure _CO2 flows continuously through the system [225]. A saturated solution of sodium bicarbonate, reconstituted with 108 g of dry NaOH pellets, was used as the source of caustic for nebulization. This solution is poured into the chamber surrounding the converter [205]. The pH of the mist collected in the mixing chamber [245] was measured at several time intervals (5min, 10min, 20min). It was found that the pH of the mist was always below 8, where the initial pH of the solution was above 13.5. After 20 minutes of operation with the transducer, fan and _CO gas, a precipitate of sodium bicarbonate and sodium carbonate filled the transducer chamber.

Example 2. This example uses a chamber to generate a droplet, contact the droplet with a gas, and precipitate solid material. The apparatus of this embodiment is similar to FIG. 46 .

The device is made as a box with the following dimensions: 6 feet (182.88 cm) high, 4 (121.92 cm) wide and 6 inches (15.24 cm) deep. There are shelves 2 feet (60.96 cm) from the top (which surround a commercially available 10-transducer ultrasound unit [Fig. 46: 300]) and fans (which circulate the gas in a circular pattern). The bottom of the tank is conical, which allows the settled slurry [350] to flow to the storage tank [360]. The rack [310] is filled with 2.7N sodium hydroxide solution and is continuously filled from the storage tank [340] by a recirculation pump. Pure _CO2 [370] was pumped through the chamber, and after several hours, sodium bicarbonate and sodium carbonate precipitates formed on the walls of the chamber.

Example 3. This example demonstrates the use of recirculation and alkaline chemical solutions to absorb carbon dioxide gas.

The device uses pure _CO2 as the gas and consists of horizontal tubes 6 inches (15.24 cm) in diameter and 1.5 (45.72 cm) feet long. A low pressure pump recirculates the solution to the jet orifice, which produces droplets with a much larger droplet size than those produced by an ultrasonic nebulizer. The tube was filled with 2.75N sodium hydroxide (NaOH), and the pump was turned on to atomize the NaOH into the _CO2- rich chamber. After 1 hour and 40 minutes, the resulting solution contained a large amount of precipitate at pH 8.2, indicating that sodium bicarbonate and sodium carbonate had precipitated due to supersaturation of the solution with CO ₂ .

Example 4. This example demonstrates the use of a high surface to volume tap water droplet to incorporate carbon dioxide gas into the droplet such that the droplet is nearly fully saturated with _CO2 within the first 5 minutes of contact with the gas.

The device consists of an 8 inch (20.32 cm) diameter, 48 inch (121.92 cm) long tube with four ultrasonic transducers equally spaced along the bottom. The absorber was tested using normal tap water with an initial pH of 7.8. The mist collected by the converter was collected after 5 minutes and tested. The pH of the bulk tap water was 6.3 and the pH of the collected mist was 5.44. The collected mist was then sprayed with more _CO2 for 30 minutes in a separate spraying system, and it has been found that the minimum pH that can be achieved is 5.39, which is close to full saturation within the first 5 minutes.

Example 5. To treat flue gas from a 200 MW power plant, absorb it into 100 million gallons per day (MGD) of brine, where 75MGD is an alkaline brine with an alkalinity of 500mEq and 25MGD is a calcium concentration of 25,000ppm of hard salt water. When using US coal (ie, the coal is not lignite), the power plant produces 200 tons/hour of carbon dioxide emissions. The carbon dioxide capture rate was 90%, which means that 180 tons/hr of carbon dioxide was mixed into the absorption solution containing the brine listed above. Once the calcium carbonate is separated from the brine and dried, and assuming continuous operation of the treatment plant (ie, emission control system), 408.6 tons of calcium carbonate are formed per hour, which equates to approximately 9800 tons of product per day. This indicates that 0.196 lbs of product/gallon of brine was produced, which equates to 23.5 g of product/L of brine. When the capture rate is reduced, for example from 90% to 45%, 90 tons/hr of carbon dioxide is captured and thus 204.3 tons/hr of calcium carbonate is formed, which equals 0.098 lb/gal (11.75 g/l) . When increasing the size of the power plant, for example from 200 MW to 400 MWh, at 90% capture rate, the amount of carbon dioxide captured is 360 tons/hr and thus forms 817.2 tons of calcium carbonate, which corresponds to approximately 19600 tons of product/day (24 hours), assuming continuous operation at steady state.

Example 6. As described here, processes have been developed for capturing carbon dioxide and sulfur oxides from power plant flue gases. The process is a two-step process that uses alkaline/overbasic materials plus calcium and/or other divalent cations to capture and convert carbon dioxide and sulfur oxides to solid carbonate and sulfate. These solids can then be converted into end products for sale or disposal. This approach eliminates the need to separate and compress captured carbon dioxide for geological storage. A demonstration plant was used to determine the commercial-scale processing and energy required to remove carbon dioxide from power plant flue gases. The demonstration plant removes carbon dioxide from a slip stream of flue gas produced by an adjacent natural gas fired combined cycle power plant. The design flow rate of flue gas capable of being processed in this demonstration plant is approximately 20,000 standard cubic feet per minute ("scfm"), which is equivalent to a natural gas fired combined cycle generating approximately 40 megawatts ("MW") of power. Flow generated in a power plant. This flue gas flow is equivalent to that from a coal-fired facility of approximately 10 MW of power. Absorption on smaller-scale coal-fired flue gases was also studied in a pilot plant with the aim of establishing another demonstration plant adjacent to the coal-fired power plant to evaluate the more Recovery and conversion of high concentrations of carbon dioxide and sulfur oxides. Some highlights include:

●In one test, running continuously for a typical two-hour steady-state period, using caustic and calcium chloride as materials to simulate brine, and a flue gas flow rate of 12,000 scfm, this achieved a minimum CO2 removal of 80% . The carbon dioxide removal rate was about 86%. Power consumption is 521 kilowatts ("kW"), which is equivalent to 8.6% of the power produced while producing the flue gas flow processed (based on the power produced by an equivalent coal-fired flue gas flow) .

- The demonstration plant instrumentation and control mechanism allow to obtain the data required to quantify the removal of carbon dioxide obtained and the internal power consumption required for the configuration of the absorber as well as the operating conditions and power consumption for the purpose of carbon dioxide removal.

80% CO2 removal from coal fired flue gas initially with 15% CO2 compared to 80% CO2 removal from natural gas fired gas turbine flue gas initially with 4% CO2 (down to less than 1%) % CO2 (down to 3% CO2) should be easier.

• The demonstration plant and support plant have been designed to be flexible enough in terms of test plant components and operating conditions to run options and then determine or subsequently improve promising internal configurations and operating conditions which ultimately lead to optimal results.

• The demonstration plant is large enough to observe and relate any large-scale specific issues. The demonstration unit also has sufficient flexibility in the area of scrubber liquid preparation to allow testing of integrated solutions for brine and alkali sources intended for commercial use.

Demonstration plant method description and design

The following is a description of the methodology designed for the demonstration plant currently installed and operating. The site where the demonstration unit is located includes equipment used in the 1940s to recover magnesium from seawater, and the experimental site uses some of the existing large inground tank capacity at the site for the demonstration unit . A large part of the process is the absorber column ("absorber"), which scrubs the flue gas, removing carbon dioxide from the flue gas by absorbing it into a scrubbing slurry. The detergent liquid comprises one or more divalent cationic metals, such as calcium, either dissolved or as finely divided suspended solids. The scrubbing liquid also contains a high pH alkali source such as sodium hydroxide. The flue gas leaving the natural gas fired power plant has a temperature of approximately 175-200 degrees Fahrenheit ("°F"). The flue gas was transported from a natural gas fired power plant to the demonstration unit through 36 inch uninsulated carbon steel pipe. Two natural gas fired power plant stacks are tapped so that the flue gas flow can be taken from either stack or both. This natural gas fired power plant allows the demonstration plant to capture flue gas up to 24,000 scfm in as little as 12 hours or less. This is equivalent to the flue gas produced in a natural gas fired power plant producing approximately 4.6 MW of power. The flue gas enters the absorber at a temperature of about 70-110°F, depending on the ambient temperature, and the flow rate of the flue gas through the tube. The flue gas pipe runs underground from the natural gas fired power plant to the demonstration unit. Provision was made to collect any condensate from the cooled flue gas in the duct on both sides (ie, both the natural gas fired power plant side and the demonstration plant side). Condensate collected on the natural gas fired power plant side is sent back to the natural gas fired power plant. The condensate collected on the demonstration unit side was sent to fresh water storage for the demonstration unit.

The demonstration plant has been designed to achieve (as a target for commercial operation) 80% carbon dioxide removal in flue gas obtained from natural gas fired power plants, while limiting the required power consumption to no greater than The production of air volume represents 8% of the power output. Due to the excess air required, natural gas fired gas turbines such as those used in natural gas fired power plants produce more flue gas per unit of power produced than coal fired steam power. Thus, the amount of flue gas that must be processed on a per MW basis for generation of electricity for flue gas carbon dioxide removal for coal-fired utility power generation can typically be less than for natural gas-fired combined cycle power generation. Because coal contains more carbon than natural gas on a per unit weight basis of fuel and produces less flue gas per unit power output, the flue gas concentration of carbon dioxide at the inlet of an absorber for coal-fired power generation Will be higher than the CO2 concentration used in the flue gas of natural gas fired power plants. A higher absorber inlet carbon dioxide concentration will facilitate the removal of any given percentage of carbon dioxide from the flue gas.

Natural gas fired power plant flue gas typically contains 3.9-4.2 vol% carbon dioxide and is substantially free of sulfur oxides. Assume a "carbon concentration" for a coal-fired power plant of 0.9 metric tons of carbon dioxide produced per megawatt-hour ("MWh") of power generation, and a flue gas composition with 15% carbon dioxide by volume (approximately 6% excess air, and is water saturated at 90°F). The need to remove sulfur dioxide is not considered in the calculations and therefore does not need to be removed from natural gas fired power plant flue gases. The total amount of flue gas produced by a theoretical coal-fired power plant while producing 10 MW was calculated. The flue gas volume is 20000 scfm, therefore the demonstration plant is designed to process 20000 scfm. The power consumption target for this demonstration plant is thus kept below 800 kW (8% of 10 MW) when processing 20000 scfm.

A forced-draft centrifugal fan is used to push flue gas from a natural gas-fired power plant and push it through the demonstration unit. The fan uses a variable frequency drive ("VFD") to control the flow of flue gas. Vents are provided upstream of the fan to gradually provide suction on the ducts from the natural gas fired power plant. This vent is closed when a flow from a natural gas fired power plant develops in the pipeline. The pipe length from the natural gas fired power plant stack to the upstream vent is approximately 2400 feet. Between the fan and the absorber is approximately another 300 feet of pipe for a total pipe length of 2718 feet. Since most commercially available absorbers are connected as close as possible to the flue gas stack, the fan power (which is included in the power consumption of the demonstration unit for moving the flue gas through most of this line) Not calculated as part of the power consumption of other devices. The power required just for the absorber can also be calculated from the pressure drop and flue gas flow along the absorber. The pressure drop along the absorber was measured by a pressure gauge at the flue gas inlet (absorber discharge to atmosphere). Flue gas flow to and from the absorber was measured using a hot wire anemometer inserted into the turbulent flow.

In this demonstration plant, the aim was to use a representative chemistry of naturally occurring hard and alkaline brines, which are used in commercial operations. These include but are not limited to calcium chloride, calcium hydroxide, sodium hydroxide, sodium chloride, sodium carbonate and sodium borate. Power plant fly ash (which is a source of both cations and alkali) can also be used as part of the required scrubbing reagents. Currently, calcium hydroxide and/or calcium chloride are used as the source of this divalent cation, sodium hydroxide and/or calcium hydroxide are used as the source of alkalinity, and either fresh water or sea water are used to form the absorbent used in the absorber of the demonstration plant. liquid. Calcium hydroxide is representative of hydrated calcium oxide ("CaO") in fly ash or cement kiln dust, and has been used for start-up and initial operation of the demonstration plant. Calcium chloride was used to simulate the calcium hardness in brine expected to be used in commercial operations. Its purpose is to expand the chemicals used to include sodium carbonate and other compounds found beneath the surface of the reservoir. These chemicals will be tested to determine their ability to enhance the desired properties in the dewatered solids (from the pure slurry recovered from the absorber) to produce by-products.

For start-up and commissioning of the demonstration plant, calcium hydroxide was used. Solid calcium hydroxide (93.5% purity, make up mainly calcium carbonate) was delivered by truck to the demonstration plant location. The calcium hydroxide is mixed with fresh and/or sea water in a 120,000 gallon capacity caustic mixing tank which is an existing outdoor open tank at the site. The ability to add supernatant (the aqueous phase from the Epuramat solid-water separator ("Epuramat"), which is described below) is set at a later time. Seawater is supplied from an existing harbor pump which supplies seawater to approximately 1,000,000 gallon seawater storage tanks. This stored seawater is pumped through sand filters to remove particulates and organic solids before being used to reduce the risk of fouling. The liquid in the alkali mixing tank is recirculated through a turbine which combines solid calcium hydroxide with the slurry in the tank. Agitators and pumps are used to keep the slurry well mixed. The slurry is then pumped to a caustic mix tank. The caustic mixing tank was an existing outdoor open tank at the facility with a capacity of 140,000 gallons. A stirrer was used to keep the contents of the tank well mixed. In the caustic mixing tank, liquid (currently filtered seawater, but eventually supernatant) can be added to maintain the weight content of the calcium hydroxide slurry at approximately 6% by weight calcium hydroxide solids. The slurry solids content was monitored by taking samples from the tank and measuring the total solids. The slurry was pumped from the caustic mixing tank to a 10,000 gallon capacity caustic shock tank.

When used, the liquid calcium chloride solution is delivered by truck. Base production systems are also used in this cation source processing. Store the calcium chloride solution in an alkali mixing tank. It is then diluted in the alkali mixing tank. Calcium chloride and water are simultaneously pumped into the alkali mixing tank. The diluted calcium chloride is then pumped to the alkali shock tank. This diluted calcium chloride is pumped into the header of the slurry feed line for the appropriate/selected level of absorber.

Dilute sodium hydroxide is fed from one of the two caustic dilution tanks to the caustic shock tank to provide a source of alkali for carbon dioxide absorption. Dilute sodium hydroxide solution was produced by combining 50% by weight sodium hydroxide solution (stored in two 10,000 gallon capacity tanks) with fresh water in one of the caustic dilution tanks. The contents of the alkali shock tank were pumped to the absorber by the absorber feed pump. Diluted sodium hydroxide can also be pumped directly into any of the six headers that feed the slurry to the absorber.

Between running operations, the contents of the caustic mixing tank are sent to the caustic mixing tank and the caustic mixing tank is flushed with fresh water or sea water. The flush is sent to the T1 slurry storage tank, which is currently used to store pure absorber product slurry. The contents of the caustic mix tank were also emptied directly or via an absorber into the T1 slurry storage tank between operations because the contents of the caustic mix tank could absorb carbon dioxide from contact with the air spray.

The flue gas enters the absorber below the scrubbing stage and above the liquid collection tank. The flue gas flows upwards through the absorber through six levels or stages (numbered sequentially from the bottom level up) in the absorber where fresh and recycled scrubbing liquid can be injected and internals installed (using rim support ring attached to the inside diameter of the absorber). The scrubbing liquid flows down the absorber from its injection point under the force of gravity. After passing up the scrubbing stage, the flue gas then passes through a liquid demister (a vapor-liquid separator used to remove entrained liquid by impingement) and exits the top of the absorber to the atmosphere. There is no need to reheat the flue gas. After the absorber, the flue gas at the absorber outlet temperature is allowed to vent to the environment. Gas sampling of the flue gas to measure the carbon dioxide concentration is performed above the demister and immediately before entering the absorber. The conventional method for this carbon dioxide measurement is through a Continuous Emissions Monitoring System ("CEMS"), which uses two different analytical devices. ThermoEnvironmental Model60i is used as the main measurement, and Servomex 1440D gas analyzer is used as backup and for various verification. Gas samples can also be collected manually for laboratory analysis.

The absorber inners comprise rows at a first level. The rows (inverted angle irons) protrude along the diameter of the absorber, perpendicular to the flow of the flue gas, and are connected to the support ring of the absorber shell. Each absorber level has 5 headers, perpendicular to the flue gas flow, which can be used to connect jets. Measure the pressure drop along the orifice. Accumulate liquid from laundry into liquid collection sump. Liquid is recirculated from the bottom of the absorber to one or more stages through three parallel recirculation pumps. To avoid liquid accumulation in the absorber, purge stream (whose flow is controlled at the liquid sump level) is removed from the recirculating scrubber liquid and sent to the absorber product shock tank. The absorber product transfer pump is used to move the product slurry to an Epuramat vessel where the slurry is dewatered from about 5-7 wt% solids to 20-40 wt% solids to form a liquid supernatant and a thickened slurry. The Epuramat is designed to receive a suction flow pumped to the top of the vessel, where the slurry then flows under gravity down a central feed tube and via an adjustable diffuser/separator positioned towards the bottom of the unit. The device leaves and enters the loop area. The diffuser is designed to induce a transition from turbulent to laminar flow whereby solid materials are separated under a shear gradient to form a clear liquor and a thickened slurry flow.

Install the Epuramat, and now for a test run. The contents of the absorber product shock tank are now sent to an outdoor T1 slurry open storage tank which has a capacity of 2,500,000 gallons and is used to separate the slurry solids from the liquid by gravity. Once the Epuramat is running, the dewatered slurry from the Epuramat is sent to the T1 slurry storage tank and the liquid sump is sent to the sump shock tank. The supernatant is pumped from the supernatant impact tank to the outdoor T4 open supernatant storage tank of 2,500,000 gallons. This supernatant is recycled to the caustic mixing tank to reduce process water consumption and utilize unreacted caustic.

Currently, to control the amount in the T1 slurry storage tank, the pH of the supernatant at the top of the tank from the settled absorber purge slurry is checked and allowed to drain. Recirculation of liquid in the process may reduce or may eliminate the need to drain any liquid from the process. If the pH is too high and needs to be adjusted, carbon dioxide is added by bubbling carbon dioxide through the liquid so that the liquid is less alkaline (lower pH) and suitable for discharge. Some of the solids accumulated in the T1 slurry storage tank were used to make and evaluate products from dewatered solids in other units located at this location. Once the Epuramat is running, excess supernatant from the demonstration unit can be discharged from the T4 tank into the bay (and carbon dioxide added as needed for pH adjustment).

In addition to testing absorber slurry dewatering with the Epuramat (which is designed to receive the full absorber flush flow), the additional purpose was to test 4-6 other slurries on a smaller scale with a pilot plant provided by the manufacturer dehydration system. Slurry flow to these pilot plants was provided from the absorber product impingement tank.

After dewatering, the aim was to test the device for additional dewatering and processing of the thickened slurry to assess what end product could be produced from the absorber solids.

All of the main pumps in this demonstration plant used VFDs. Liquid flow is measured by pump speed and by magnetic flow meters. Flows to levels 4, 5 and 6 of the absorber were measured with magnetic flow meters. Currently, there are no magnetic flowmeters installed for levels 1, 2 and 3; when measurements from levels 1, 2 or 3 are required, the other level flowmeters are reinstalled from other levels. Flow meters for flow levels 1-3 will be installed over the next few weeks. The measured pressure drop along the orifice and the theoretical flow for the orifice design are also used to monitor for orifice clogging by comparing the theoretical flow to the actual flow.

To shut down the operation of the absorber (or to "flush it out"), the flow of flue gas from the natural gas fired power plant is stopped, the flow of fresh scrubbing solution is stopped, and the recirculation of the scrubbing solution is stopped. Fresh water from the spray storage tank is then pumped into the top of the absorber through a spout located below the mist eliminator. The water spray can also be directed into the nozzle above the mist eliminator to clean it as desired.

Demonstration plant design and operation

To evaluate and optimize CO2 absorption and power consumption, the following engineering design parameters are provided:

●Location and number of liquid injection points

●Liquid spray pattern and droplet size range and nozzle pressure reduction

●Liquid spray volume relative to gas flow rate

● Internals for mixing and mass transfer

●Gas residence time in liquid spray

The alkali concentration fed to the process can also be adjusted by adding water in the caustic dilution tank and feed liquid storage tank respectively. Subject to the limitations of any existing design in terms of pumping or flue gas fan capabilities, the ability to experiment with and modify these parameters should allow determination of the "best" plant arrangement and Operating conditions. While testing the internals, the size (diameter) of the absorber was sufficient to avoid wall effects and to observe (and then resolve) any problems related to poor flue gas or scrubbing liquid distribution that might occur. Some valves (mainly used as on/off valves to establish and direct flow of scrubber fluid in different configurations) were manually operated while the test continued to improve operability and holdover.

As mentioned above, two continuous flue gas carbon dioxide and oxygen concentration monitoring devices were used in parallel to measure absorber carbon dioxide removal as a function of operating conditions and device configuration. These instruments can be checked online by switching to ambient air supply and calibrated with gas standards at the beginning of each day's operation.

In addition to CEMS data, other recorded data includes, but is not limited to, pH, gas flow, liquid flow, pressure, temperature, and percent solids. For manual sampling of gases, liquids and slurries follow the methodology for chain control and data processing.

To monitor power consumption, the power input to the VFD drives of all pumps and flue gas fans is monitored. Electricity meter readings for official power consumption were also monitored. The difference between the total VFD power usage and the electricity meter reading is due to lamps, agitators, meters, control systems and other demonstrative device loads. A large number of these loads will tend to be reduced across the scale of the plant relative to the major engine loads listed in Table 1. Therefore, electricity meter readings are used as conservative values. In addition, the power required for the flue gas induced draft ("ID") fan is expected to be proportional to the relative reduction in the overall size of the plant, given the close connection of the absorption unit to the flue gas stack of the plant.

Table 1. Main power load of the demonstration device

project Load (kW) Flue Gas ID Fan 25 Recirculation pump A 192 Recirculation pump B 196 Recirculation pump C 78 (calculated value) All transfer pumps 14 Total from VFD 505 (inner circulation pump C) Other load (difference) 16 sum from meter 521 Epuramat (not running) 35 (estimated value) Total 556

NOTE: Load is from 2/23/2010, running at 12000scfm, and flowing entirely on the recirculation pump.

After the flue gas flow and liquid flow for operation were established, the demonstration plant was placed in steady state operation (no fluctuations in liquid flow gallons per minute or flue gas acfm). Steady state is usually established in less than 1 hour. Once steady state is obtained, data collection begins formally. Typically, 1 hour or 2 hours after the data was acquired, the operating conditions were changed so that a different set of operating conditions could be tested. Typical test time covering several runs is 12-20 hours.

Test Data

Full data has been collected for at least two run cycles. The difference between these two run cycles is the fresh brine and sodium hydroxide (caustic) feed content (flow rate). Both run cycles met a minimum carbon dioxide removal rate of 80%. However, the run cycle with higher content of fresh brine and caustic feed was higher than the target 8% power consumption. The run cycle with lower levels of fresh brine and caustic feed was close to the target power consumption of 8% (equivalent to 8.6% at a flue gas flow of 521 kW used). This run used calcium chloride as the cation material, sodium hydroxide as the base material, and a flue gas flow rate of 12000 scfm. The absorber recirculation pump was run at full capacity. The carbon dioxide removal rate was about 86%. The operating parameters were still evaluated.

If the flue gas flow is raised theoretically to the design flow of 20,000 scfm while maintaining other specific operating conditions, the overall power used would be expected to be slightly higher (approximately 44kW) due to the required flue The air fan power will increase (about 175% or more, because the fan power is proportional to the square of the flue gas flow), but the power consumption value will be reduced (from 8.6% to about 5.6%), because the additional flue Gas represents more than 67% of coal-fired electricity generation. The carbon dioxide removal rate is expected to decrease due to the decreased available scrubbing liquid units on a per unit gas basis. Actual carbon dioxide removal rates will need to be determined experimentally.

observe

Foaming in the absorber has been observed. This foaming is controlled by installing impingement plates in the liquid pool.

Sodium chloride (" _CaCl2 ") is compatible with water when calcium chloride ("CaCl2") is used as a source of cations to remove carbon dioxide (" _CO2 "), and sodium hydroxide ("NaOH") is used as a source of high pH alkalinity ("H ₂ O") and calcium carbonate ("CaCO ₃ "), which are formed by:

CaCl ₂ +CO ₂ +2NaOH-->CaCO ₃ +2NaCl+H ₂ O

The calcium carbonate is removed as a solid by mechanical dewatering of the scrubber liquid (ie in an Epuramat or other device). In order to avoid the accumulation of sodium chloride from the supernatant recycle, it must be purged from the system. Because sodium chloride is highly soluble, it can be removed with water during the mechanical dehydration step as residual liquid with dehydrated solids. It has already been considered to add to this method the execution of a washing step and/or separation by particle size during the drying process. It has been determined that sodium chloride forms very small evaporated salt crystals which can be removed from the larger particles in the spray dryer.

Carbon dioxide removal is performed at temperatures below typical power plant stack gas temperatures. Carbon dioxide absorption is enhanced by lower temperatures. This lower temperature also reduces the volumetric gas flow that must be processed. It is intended to operate commercially available absorbers over the approximate temperature range tested by the demonstration unit. Its purpose is to use the enthalpy from the cooling of power plant stack gases for use in the processing of dry dewatered solids. The processed flue gas may in some embodiments be reheated to provide additional buoyancy to vertically disperse the flue gas (eg, to avoid ground fog due to condensation). The reheat capability can utilize SOx scrubber systems in existing power plants.

The rate at which carbon dioxide can be absorbed into the scrubbing liquid is limited by mass transfer. Based on laboratory and pilot plant data, it has been concluded that the primary drag is the acquisition of carbon dioxide (from the flue gas) along the liquid side boundary layer of the droplet. Thus, the rate and amount of carbon dioxide that can be absorbed is proportional to the surface area of the liquid (or slurry) droplet. A larger surface area provides more paths for absorption, especially at a constant absorption rate. The amount of droplet surface area is a function of droplet size (smaller droplets have more surface per unit volume) and the number of droplets or the volume of the liquid in question. In practical terms, the amount of liquid used is expressed as gpm (slurry)/1000 scfm flue gas ("L/G" ratio). A higher L/G will remove more carbon dioxide than a lower L/G if all other operating parameters are held constant. The amount or percentage of carbon dioxide removed can also be increased by increasing the residence time (time exposed to liquid droplets) of the flue gas in the absorber. Each of these options has an associated cost. Increasing L/G increases the power required to pump additional liquid slurries. Reducing the slurry droplet size also increases the power consumption for the process, since more energy is required to produce smaller droplets (and to produce smaller solid particles for the slurry). Increasing the absorber residence time increases the size (and cost) of the absorber. Different configurations of residence time, spray design, liquid flow and internals were tested to establish design parameters for a commercial scale absorber.

The mass transfer of carbon dioxide also depends on the relative concentrations of carbon dioxide in the flue gas and liquid. Since the absorbed carbon dioxide gas reacts in the scrubbing liquid to form calcium carbonate solids, it can be assumed that the concentration of carbon dioxide in this liquid is always very low, close to zero. Therefore, a higher concentration of carbon dioxide in the flue gas will increase the transfer rate of carbon dioxide into the liquid. Thus, removing 80% of the carbon dioxide (down to less than 1%) from a natural gas fired gas turbine flue gas initially having 4% carbon dioxide removes 80% CO2 (down to 3% CO2) is easier. This phenomenon confirms the assumption that it should be possible to generate electricity from a coal-fired power plant equivalent to as high as 10 MW with less than the amount of power actually expended to remove 80% of Flue gas Natural gas fired power plant flue gas volume removes 80% of the carbon dioxide.

Pilot plant tests using the above described coal fires have been continuously carried out. Based on multi-pollutant testing of the absorption method on coal flue gas in this pilot plant, the method:

●Using the US EPA reference method to remove most trace metal emissions, reaching the level of no detection;

- capture mercury with a removal efficiency greater than (">") 80% (depending on the type of coal fired);

● High content of acid gas is captured by absorber. The observed capture efficiencies were >99% _SO2 ; >88% _SO3 and >81% HCl; and

• All trace elements examined in the supernatant from dewatering were below water discharge limits (US: NPDES).

These same results can be achieved when the method is scaled up to a coal fired plant.

While the invention has been described in terms of various embodiments, and while these embodiments have been described in considerable detail, it is not the intention of the inventors to limit or in any way limit the scope of the invention to such detail. It is obvious to those skilled in the art that various changes and improvements can be made to the present invention without departing from the spirit and scope of the present invention. The foregoing are merely examples of variables that can be used and additional advantages and modifications will readily appear to those skilled in the art. Therefore, the invention in its broader aspects is therefore not limited to the specific details, representative embodiments and exemplary examples shown and described. Therefore, departures may be made from such details without departing from the spirit or scope of the invention. Accordingly, it should be understood that the detailed description and drawings presented herein are not intended to limit the breadth of the present invention, which should be inferred only from the following claims and their legal equivalents when properly construed.

Claims (64)

1. device that is used for gas component is transferred to liquid, described equipment comprises:

The gas access;

Be configured so that the chamber of liquids and gases contact:

In described chamber first liquid of primary importance introduce the unit and in the chamber second liquid of the second place introduce the unit, wherein liquid is introduced the unit and is configured to and inserts the liquid into described chamber so that contact with gas;

Be configured to the holder that after liquid contacts gas, comprises described liquid;

Be used for the outlet after it contacts gas of liquid, wherein said inlet, chamber, liquid are introduced unit, holder and outlet and are operably connected; With

In the following feature at least one:

I) canopy of at least one array in described chamber row, wherein said canopy row is configured to and redistributes it flow when gas enters described chamber, make and arrange interact preceding mobile compare with canopy with gas when entering described chamber, gas axially flows along the chamber on the more large tracts of land of chamber cross-section;

Ii) be configured to the froth breaking equipment that reduces the foam in the described holder;

Iii) each liquid is introduced at least one pump of unit, is used for the liquid pumping by this introducing unit;

Iv) dispose liquid and introduce the unit, the flow direction that makes liquid leave first module is different from the flow direction that liquid leaves Unit second;

V) one or more throttle orifice mechanisms (bleed valve), its be configured to liquid flow be directed to liquid introduce in the unit at least one, in the gas access or its combination; With

Vi) change liquid and introduce the zone that the unit covered, wherein liquid is introduced the atomization unit that the unit comprises the generation spraying, and wherein at least one atomization unit is configured to and produces the spraying that angle is different from other atomization unit.

2. the device of claim 1, it comprises in the described feature at least two.

3. the device of claim 2, it comprises in the described feature at least three.

4. the device of claim 3, it comprises in the described feature at least four.

5. the device of claim 4, it comprises in the described feature at least five.

6. the device of claim 5, it comprises whole described features.

7. each device among the claim 1-6, wherein said gas access are configured to accepts industrial waste gas, compression surrounding air, compression arbon dioxide, supercritical carbon dioxide or its any combination.

8. each device among the claim 1-6, wherein said gas comprises industrial waste gas, the carbon dioxide that has before separated with industrial waste gas, or its any combination.

9. the device of claim 8, wherein said gas comprises one or more in carbon dioxide, nitrogen oxide and the oxysulfide.

10. each device among the claim 1-9, wherein said first liquid are introduced the unit and are positioned at the floor level place on the gas access and are oriented as to flow into described chamber with the direction guiding liquids of gas flow direction and stream basically.

11. the device of claim 10, wherein said second liquid are introduced the unit and are oriented as to flow into described chamber with the direction guiding liquids of gas flow direction adverse current basically.

12. the device of claim 11, wherein first liquid is introduced the unit, and second liquid is introduced the unit or both comprise spout.

13. the device of claim 12, wherein spout comprises the two-fluid spout.

14. the device of claim 12, wherein spout comprises injector-jet nozzle.

15. each device among the claim 1-14 is wherein used at least one in the frequency changer control pump.

16. the device of claim 10, wherein froth breaking equipment comprises the cone that is positioned on the holder.

17. the device of claim 10, wherein froth breaking equipment further comprises towards the liquid dispenser of described cone orientation.

18. the device of claim 10, described device further comprises liquid recirculation loops, and it is configured to and liquid is directed to liquid from holder introduces one or more the unit.

19. the device of claim 10 or 18, further be included in gas leave contact before the chamber except that cloudy surface.

20. the device of claim 19, wherein demist face comprises the waveform demister, flat spray sprayer, wet electrostatic settler, packed bed, or its any combination.

21. the device of claim 19, the liquid that wherein offers except that cloudy surface comprises and the different solution of liquid that offers liquid introducing unit.

22. the device of claim 21, the liquid that wherein offers each liquid introducing unit comprises different solution.

23. the device of claim 21, the liquid that wherein offers except that cloudy surface is clear liquid.

24. the device of claim 21, the liquid that wherein offers liquid introducing unit comprises slurries.

25. the equipment of claim 24 further comprises the pulverizing platform, it is configured to acceptance and offers liquid introducing unit from the slurries of holder and with finished slurries.

26. the device of claim 25, wherein recirculation circuit comprises the pulverizing platform.

27. each device among the claim 1-26, wherein holder is located under the spout of the bottom that contacts the chamber.

28. each device among the claim 1-26 further comprises the stillpot that can be operationally connected to the contact chamber.

29. the device of claim 28, wherein stillpot comprises temperature controller, is used to add the inlet of pH conditioning agent, agitator is used for the inlet of crystal growth agent, is used for the inlet of crystal sowing agent, the inlet that is used for sedimentation agent is used for the inlet of flocculant or its any combination.

30. the device of claim 29 further comprises the precipitation outlet that can be operationally connected to stillpot.

31. the device of claim 30, solid sediment and supernatant liquor solution are collected in wherein said sediment outlet.

32. the device of claim 31, wherein said sediment outlet is from supernatant liquor solution separating solids sediment.

33. the device of claim 32 further comprises pipeline, makes platform and solid sediment is offered construction material.

34. the device of claim 33, wherein said gas access are configured to the waste gas of acceptance from industrial equipment.

35. the device of claim 34, wherein said gas access are configured to the flue gas of acceptance from the equipment of combustion of fossil fuels.

36. the device of claim 35, wherein said gas access are configured to the flue gas of acceptance from the equipment of combustion of fossil fuels, wherein flue gas has been passed through emission control systems before being provided to the gas access of described device further.

37. the device of claim 36, wherein said emission control systems comprise one or more in following:

I) be used for the electrostatic precipitator of collecting granules thing;

Ii) SOx control technology; Iii) NOx control technology;

The physical filtering technology that iv) is used for the collecting granules thing; Or

V) mercury control technology.

38. the device of claim 7, the sprayer of wherein said atomization unit comprise 60 ° sprayer and 90 ° sprayer in contacting the interior cross section of chamber near the wall of contact chamber.

39. the device of claim 7, wherein gas is vertical along the mobile of canopy row.

40. the device of claim 7 further is included in packing material, tower tray, packed bed or its any combination in the described chamber.

41. the device of claim 40 further is included at least one film or a microporous barrier in the described chamber.

42. a device, it comprises:

Absorber, described absorber comprises bubble tower;

Be operably connected to the inlet that is used for industrial gasses of absorber, wherein industrial gasses comprise when quantity equals all CO of original composition ₂, SOx, NOx, heavy metal, non-CO ₂Sour gas and/or flying dust;

Be used for the inlet of absorbent solution, wherein absorbent solution comprises alkaline solution, and it comprises salt solution, granular materials or in absorbing slurries both;

Be used to discharge the outlet of gas, described gas characteristic is its poor CO for the described original composition of described industrial waste gas ₂Reach SOx, NOx, heavy metal, non-CO ₂In sour gas and/or the flying dust at least one, wherein said outlet is operably connected to described absorber;

Be operably connected to the outlet of absorbent solution that is used for contacting industrial waste gas of described absorber; With

Can be operationally connected to the machine table of this outlet, wherein said machine table is configured to and obtains at least a in the following salable item: comprise CO ₂Bury component construction material, desalted water, drinking water, comprise CO ₂Bury the slurries of component or comprise CO ₂Bury the solution of component, wherein the bubble tower bubble that is configured to manufacture gas in absorbent solution makes the carbon dioxide of the 10wt% at least in the industrial gasses be transferred to absorbent solution.

43. a device, it comprises:

Absorber, described absorber comprise spray cloth container;

Be operably connected to the inlet that is used for industrial gasses of absorber, wherein said industrial gasses comprise when quantity equals all CO of original composition ₂, SOx, NOx, heavy metal, non-CO ₂Sour gas and/or flying dust;

Be used for the inlet of absorbent solution, wherein absorbent solution comprises alkaline solution, and it comprises salt solution, granular materials or in absorbing slurries both;

Be used to discharge the outlet of gas, described gas characteristic is its poor CO for the described original composition of described industrial waste gas ₂Reach SOx, NOx, heavy metal, non-CO ₂In sour gas and/or the flying dust at least one, wherein said outlet is operably connected to described absorber;

Be operably connected to the outlet of absorbent solution that is used for contacting industrial waste gas of absorber; With

Can be operationally connected to the machine table of this outlet, wherein said machine table is configured to and obtains at least a in the following salable item: comprise CO ₂Bury the construction material of component, desalted water, drinking water comprises CO ₂Bury the slurries of component, or comprise CO ₂Bury the solution of component, wherein spray bubble that the cloth container is configured to manufacture gas in absorbent solution and make the carbon dioxide of the 10wt% at least in the industrial gasses be transferred to absorbent solution.

44. a device, it comprises:

Absorber, described absorber comprises spray tower;

Be operably connected to the inlet that is used for industrial gasses of absorber, wherein said industrial gasses comprise when quantity equals all CO of original composition ₂, SOx, NOx, heavy metal, non-CO ₂Sour gas and/or flying dust;

The inlet that is used for absorbent solution, wherein absorbent solution comprises alkaline solution, granular materials or in absorbing slurries both;

Be used to discharge the outlet of gas, described gas characteristic is its poor CO for the described original composition of described industrial waste gas ₂Reach SOx, NOx, heavy metal, non-CO ₂In sour gas and/or the flying dust at least one, wherein said outlet is operably connected to described absorber;

Be operably connected to the outlet of absorbent solution that is used for contacting industrial waste gas of absorber; With

Can be operationally connected to the machine table of this outlet, wherein said machine table is configured to and obtains at least a in the following salable item: comprise CO ₂Bury the construction material of component, desalted water, drinking water comprises CO ₂Bury the slurries of component, or comprise CO ₂Bury the solution of component,

Wherein spray tower is configured in industrial gasses the logistics, drop or its combination that produce absorbent solution and makes the carbon dioxide of the 10wt% at least in the industrial gasses be transferred to absorbent solution, further wherein spray tower is configured at 50-5, the liquid flow rate of 000 gpm/1000 actual cubic feet and flow rate of gas ratio (L/G ratio) operation.

45. a device, it comprises:

Absorber, it comprises at least a in spray tower, packing material, packed bed, tower tray, canopy row or the microporous barrier;

Be operably connected to the inlet that is used for industrial gasses of absorber, wherein industrial gasses comprise when quantity equals all CO of original composition ₂, SOx, NOx, heavy metal, non-CO ₂Sour gas and/or flying dust;

The inlet that is used for absorbent solution, wherein absorbent solution comprises alkaline solution, granular materials or in absorbing slurries both;

Be used to discharge the outlet of gas, described gas characteristic is its poor CO for the described original composition of described industrial waste gas ₂Reach SOx, NOx, heavy metal, non-CO ₂In sour gas and/or the flying dust at least one, wherein said outlet is operably connected to described absorber;

Be operably connected to the outlet of absorbent solution that is used for contacting industrial waste gas of absorber; With

Can be operationally connected to the machine table of this outlet, wherein machine table is configured to and obtains at least a in the following salable item: comprise CO ₂Bury the construction material of component, desalted water, drinking water comprises CO ₂Bury the slurries of component, or comprise CO ₂Bury the solution of component,

Wherein absorber is configured in industrial gasses the logistics, drop or its combination that produce absorbent solution and makes the carbon dioxide of the 10wt% at least in the industrial gasses be transferred to absorbent solution, and further wherein absorber is configured at 50-5, the liquid flow rate of 000 gpm/1000 actual cubic feet and flow rate of gas ratio (L/G ratio) operation.

46. a device, it comprises:

Absorber, it comprises at least a in spray tower, packing material, packed bed, tower tray, canopy row or the microporous barrier;

Be operably connected to the inlet that is used for industrial gasses of absorber, wherein industrial gasses comprise when quantity equals all CO of original composition ₂, SOx, NOx, heavy metal, non-CO ₂Sour gas and/or flying dust;

The inlet that is used for absorbent solution, wherein absorbent solution comprises alkaline solution, granular materials or in absorbing slurries both, wherein said alkaline solution comprises salt solution, clear liquid or its any combination;

Be used to discharge the outlet of gas, described gas characteristic is its poor CO for the described original composition of described industrial waste gas ₂Reach SOx, NOx, heavy metal, non-CO ₂In sour gas and/or the flying dust at least one, wherein said outlet is operably connected to described absorber;

Be operably connected to the outlet of absorbent solution that is used for contacting industrial waste gas of absorber; With

Can be operationally connected to the machine table of this outlet, wherein machine table is configured to and obtains at least a in the following salable item: comprise CO ₂Bury the construction material of component, desalted water, drinking water comprises CO ₂Bury the slurries of component, or comprise CO ₂Bury the solution of component,

Wherein absorber is configured in industrial gasses the logistics, drop or its combination that produce absorbent solution and makes the carbon dioxide of the 10wt% at least in the industrial gasses be transferred to absorbent solution.

47. a device, it comprises:

Absorber, it comprises at least a in spray tower, packing material, packed bed, tower tray, canopy row or the microporous barrier;

Be operably connected to the inlet that is used for industrial gasses of absorber, wherein industrial gasses comprise when quantity equals all CO of original composition ₂, SOx, NOx, heavy metal, non-CO ₂Sour gas and/or flying dust;

The inlet that is used for absorbent solution, wherein absorbent solution comprises alkaline solution, granular materials or in absorbing slurries both, wherein said alkaline solution comprises salt solution;

Be used to discharge the outlet of gas, described gas characteristic is its poor CO for the described original composition of described industrial waste gas ₂Reach SOx, NOx, heavy metal, non-CO ₂In sour gas and/or the flying dust at least one, wherein said outlet is operably connected to described absorber;

Be operably connected to the outlet of absorbent solution that is used for contacting industrial waste gas of absorber; With

Can be operationally connected to the machine table of this outlet, wherein machine table is configured to the acquisition salable item,

Wherein absorber is configured in industrial gasses the logistics, drop or its combination that produce absorbent solution and makes the carbon dioxide of the 10wt% at least in the industrial gasses be transferred to absorbent solution.

48. being configured to, each device among the claim 42-47, the inlet that wherein is used for industrial gasses accept industrial waste gas, combustion flue gas, cement kiln flue gas, compression arbon dioxide, supercritical carbon dioxide or its any combination.

49. each device in the claim 48, wherein absorbent solution contact industrial gasses make absorbent solution exist with the form of floating clouds such as drop, streams, liquid column, spraying, liquid film, solution or its any combination.

50. the device of claim 49, further be included in the atomizing component in the contact chamber, comprise: pressure atomizer (spout), rotary atomizer, air-assisted atomization device, air blast atomizer, ultrasonic atomizer, ink-jet atomizer, MEMS atomizer, electrostatic atomiser, dual-flow atomizer, discharge spout or its any combination.

51. the device of claim 48, wherein the salt solution in the absorbent solution comprises the salt solution of seawater, base brine, Fuyang ion, synthetic salt solution, industrial wastewater, industrial waste salt water or its any combination.

52. each device among the claim 42-51; Further comprise recirculating system.

53. the device of claim 52, thereby wherein recirculating system comprises that absorbent solution that pipeline and pump will contact industrial gasses transfers to inlet, atomizing component or its any combination that is used for absorbent solution from the outlet of the absorbent solution that is used for contacting industrial gasses, machine table or both.

54. the device of claim 53, thereby wherein recirculating system comprises that pipeline and pump are with CO ₂The gas that reduces is transferred to inlet, bubble tower, spray cloth container or its any combination that is used for industrial gasses from the outlet that is used to discharge gas.

55. can be operationally connected to the emission control systems in power plant, power plant produce power and comprise the industrial waste gas of carbon dioxide wherein, wherein emission control systems be configured to absorption at least 50% from the carbon dioxide of waste gas and be configured to use less than 30% the energy that the power plant produced.

56. can be operationally connected to the emission control systems in power plant, power plant produce power and comprise the industrial waste gas of oxysulfide wherein, wherein emission control systems be configured to absorption at least 90% from the oxysulfide of waste gas and be configured to use less than 30% the energy that the power plant produced.

57. can be operationally connected to the emission control systems in power plant, power plant produce power and comprise the industrial waste gas of carbon dioxide and oxysulfide wherein, wherein emission control systems is configured to absorption from least 50% carbon dioxide of waste gas and at least 80% oxysulfide, and wherein said emission control systems further is configured to use less than 30% the energy that the power plant produced.

58. each emission control systems among the claim 55-57, wherein said emission control systems are configured at least 10% the industrial waste gas of acceptance from the power plant.

59. each emission control systems among the claim 55-58, wherein said emission control systems are configured to acceptance from the alkaline solution that is configured to the electro-chemical systems that produces caustic solution.

60. the emission control systems of claim 59, wherein said electro-chemical systems comprise anode, negative electrode and at least one ion-selective membrane between anode and negative electrode.

61. the emission control systems of claim 60, wherein said electro-chemical systems are configured under the 2.8V that applies at anode and negative electrode two ends or the littler voltage and operate.

Accept the pH conditioning agent 62. each emission control systems among the claim 55-58, wherein said emission control systems are configured to, wherein the pH conditioning agent comprises industrial waste, naturally occurring pH conditioning agent, the pH conditioning agent that is produced or its any combination.

63. each emission control systems among the claim 55-62, wherein said emission control systems is configured at 5-5, and the liquid flow rate of 000 gpm/1000 actual cubic feet per minutes and flow rate of gas ratio (L/G) is operation down.

64. the emission control systems of claim 63, wherein said system is configured in the liquid flow rate of 100-500 gpm/1000 actual cubic feet per minutes and flow rate of gas ratio (L/G) operation down.

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