CN101909449A

CN101909449A - Compositions and methods using substances containing carbon

Info

Publication number: CN101909449A
Application number: CN2009801016108A
Authority: CN
Inventors: B·R·康斯坦茨; J·R·奥奈尔; S·奥梅隆
Original assignee: Calera Corp
Current assignee: Arelac Inc
Priority date: 2008-09-30
Filing date: 2009-09-30
Publication date: 2010-12-08

Abstract

Methods of characterizing and producing compositions with negative d13C values are provided. Aspects of the invention include characterizing source materials and process products. Aspects of the invention also include compositions that contain carbon with negative d13C values.

Description

Use the composition and the method for carbonaceous material

Cross reference

The application requires the priority of the patent application of following common pending trial: the name of submitting on September 30th, 2008 is called the U.S. Provisional Patent Application sequence number No.61/101 of " Methods of Producing Carbon Sequestration TradableCommodities; and Systems for Transferring the Same (making the method and the conversion system thereof of carbon sequestration commodity) ", 629; The name of submitting on May 26th, 2009 is called the U.S. Provisional Patent Application sequence number No.61/181 of " Compositions and Methods Using Substanceswith Negative delta 13C Values (use has the composition and the method for the material of negative δ 13C value) ", 250; The name of submitting on November 24th, 2008 is called the U.S. Provisional Patent Application sequence number No.61/117 of " Methods of Producing Carbon Sequestration TradableCommodities; and Systems for Transferring the Same (making the method and the conversion system thereof of carbon sequestration commodity) ", 541; The name of submitting on June 22nd, 2009 is called " Compositions and Methods Using Substanceswith Negative delta 13C Values (use has the composition and the method for the material of negative δ 13C value) " U.S. Provisional Patent Application sequence number No.61/219,310; The name of submitting on August 7th, 2009 is called the U.S. Provisional Patent Application sequence number No.61/232 of " Carbon Capture and Storage (carbon captures and stores) ", 401; The name of submitting on September 2nd, 2009 is called the U.S. Provisional Patent Application sequence number No.61/239 of " Apparatus; Systems; and Methods of Treating Industrial Waste Gases (handling device, the system and method for industrial waste gas) ", 429; The name of submitting on July 30th, 2009 is called the U.S. Provisional Patent Application sequence number No.61/230 of " Apparatus; Systems; and Methods of TreatingIndustrial Waste Gases (handling device, the system and method for industrial waste gas) ", 042; The name of submitting on May 14th, 2009 is called the U.S. Provisional Patent Application sequence number No.61/178 of " Apparatus; Systems; and Methods of Treating Industrial Waste Gases (handling device, the system and method for industrial waste gas) ", 475; The name of submitting on April 16th, 2009 is called the U.S. Provisional Patent Application sequence number No.61/170 of " Apparatus; Systems; andMethods of Treating Industrial Waste Gases (handling device, the system and method for industrial waste gas) ", 086; The name of submitting on April 9th, 2009 is called the U.S. Provisional Patent Application sequence number No.61/168 of " Apparatus; Systems; and Methods of Treating IndustrialWaste Gases (handling device, the system and method for industrial waste gas) ", 166; The name of submitting on March 10th, 2009 is called the U.S. Provisional Patent Application sequence number No.61/158 of " Apparatus; Systems; and Methods of Treating Industrial Waste Gases (handling device, the system and method for industrial waste gas) ", 992; The name of submitting on September 30th, 2008 is called " CO ₂Sequestration (CO ₂Seal up for safekeeping) " U.S. Provisional Patent Application sequence number No.61/101,631; The name of submitting on September 30th, 2008 is called " HighYield CO ₂Sequestration Product Production (high yield CO ₂Seal the production of product up for safekeeping) " U.S. Provisional Patent Application sequence number No.61/101,626; And be the continuation-in-part application of the application of following common pending trial: the name of submitting on September 10th, 2009 is called " CO ₂Commodity Trading System and Method (CO ₂The trade in commodities system and method) " u.s. patent application serial number No.12/557,492; The name of submitting on May 29th, 2009 is called the u.s. patent application serial number No.12/475 of " Rocks and Aggregate, and Methods of Making and Using the Same (rock and gather materials and production and preparation method thereof) ", 378; The name of submitting on December 24th, 2008 is called " Methods of Sequestering CO ₂(seal CO up for safekeeping ₂Method) " u.s. patent application serial number No.12/344,019; The name of submitting on July 10th, 2009 is called the u.s. patent application serial number No.12/501 of " Production of Carbonate-Containing Compositions fromMaterial Comprising Metal Silicates (making carbonato composition by the material that comprises metal silicate) ", 217; Be called the u.s. patent application serial number No.12/486 of " Methods and Systems for Utilizing Waste Sources ofMetal Oxides (utilizing the method and system of metal oxide source of waste) ", 692 with the name of submitting on June 17th, 2009; All these are incorporated herein by this reference.

Background technology

Relative isotopics value, for example relative carbon isotope composition value (δ ¹³The C value) can be used for verifying the material source of composition in many ways.Other material in the said composition also can be used for verifying the source of this material.These technology can be used for for example confirming that given composition contains from particular source, for example in the fossil fuel, and the material of sealing up for safekeeping, and this based composition may have high value.

Summary of the invention

In some embodiments, the invention provides the composition that comprises carbonate, bicarbonate or its combination, wherein the carbon in the said composition has the relative carbon isotope composition (δ less than-26.10 ‰ ¹³C) value.In some embodiments, the invention provides composition, wherein said composition is a synthetic composition.In some embodiments, the invention provides composition, wherein said carbonate, bicarbonate or carbonate and bicarbonate constitute at least 50% of said composition.In some embodiments, the invention provides composition, wherein said composition has the quality greater than double centner.In some embodiments, the invention provides composition, wherein the CO of said composition ₂Content is at least 10%.In some embodiments, the invention provides composition, wherein said composition has negativity carbon footprint (negative carbon footprint).In some embodiments, the invention provides the composition that further comprises boron, sulphur or nitrogen, wherein the relative isotopics of this boron, sulphur or nitrogen show the fossil fuel source.In some embodiments, the invention provides composition, the combination of wherein said carbonate, bicarbonate or carbonate and bicarbonate comprises the combination of calcium, magnesium or calcium and magnesium.In some embodiments, the invention provides composition, wherein calcium/magnesium (Ca/Mg) mol ratio is 1/200 to 200/1.In some embodiments, the invention provides composition, wherein calcium/magnesium (Ca/Mg) mol ratio is 12/1 to 1/15.In some embodiments, the invention provides composition, wherein calcium/magnesium (Ca/Mg) mol ratio is 5/1 to 1/10.In some embodiments, the invention provides the composition that further comprises SOx or SOx derivative.In some embodiments, the invention provides composition, wherein said composition comprises the SOx derivative, and wherein this SOx derivative is sulphite, sulphate or its combination.In some embodiments, the invention provides the composition that further comprises metal.In some embodiments, the invention provides the composition that comprises metal, wherein this metal comprises lead, arsenic, mercury or cadmium, or its combination.

In some embodiments, the invention provides the construction material that comprises carbonate, bicarbonate or its combination, the carbon in wherein said carbonate, bicarbonate or its combination has the relative carbon isotope composition (δ less than-10.00 ‰ ¹³C) value.In some embodiments, the invention provides construction material, is neutral carbon (carbonneutral) or carbon negativity (carbon negative) comprising the component of carbonate, bicarbonate or its combination.In some embodiments, the invention provides construction material, the wherein said component of carbonate, bicarbonate or its combination that comprises is synthesized.In some embodiments, the invention provides construction material, wherein said carbonate, bicarbonate or its constitute at least 50% of the described component that comprises carbonate, bicarbonate or its combination.In some embodiments, the invention provides construction material, the wherein said CO that comprises the component of carbonate, bicarbonate or its combination ₂Content is at least 10%.In some embodiments, the invention provides the construction material that further comprises boron, sulphur or nitrogen, wherein the relative isotopics of this boron, sulphur or nitrogen show the fossil fuel source.In some embodiments, the invention provides construction material, wherein said carbonate, bicarbonate or its combination comprise the combination of calcium, magnesium or calcium and magnesium.In some embodiments, the invention provides construction material, wherein calcium/magnesium (Ca/Mg) mol ratio is 1/200 to 200/1.In some embodiments, the invention provides construction material, wherein calcium/magnesium (Ca/Mg) mol ratio is 12/1 to 1/15.In some embodiments, the invention provides construction material, the wherein said component of carbonate, bicarbonate or its combination that comprises constitutes at least 20% of this construction material.In some embodiments, the invention provides construction material, wherein this construction material is a cementitious material.In some embodiments, the invention provides the cementaceous construction material, wherein this construction material is cement or concrete.In some embodiments, the invention provides construction material, wherein this construction material is non-cementitious material.In some embodiments, the invention provides construction material, wherein this construction material is to gather materials.In some embodiments, the invention provides construction material, wherein this construction material is a pavement material.In some embodiments, the invention provides construction material, wherein this construction material be brick, plate, conduit, beam, basin, post, watt, fibre wall panel products, base, soundproof wall, gypsum, drywall, plaster, soil fixation composition or barrier material or their combination.In some embodiments, the invention provides construction material, the wherein said component of carbonate, bicarbonate or its combination that comprises further comprises the SOx or derivatives thereof.In some embodiments, the invention provides construction material, the wherein said component that comprises carbonate, bicarbonate or its combination and comprise the SOx or derivatives thereof comprises that sulphate, sulphite or its combination are as the SOx derivative.In some embodiments, the invention provides construction material, the wherein said component that comprises carbonate, bicarbonate or its combination further comprises metal.In some embodiments, the invention provides the construction material that comprises metal, wherein this metal comprises lead, arsenic, mercury or cadmium or its combination.

In some embodiments, but the invention provides the flow composition of the combination that comprises carbonate, bicarbonate or carbonate and bicarbonate, the carbon in the combination of wherein said carbonate, bicarbonate or carbonate and bicarbonate has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value, and the viscosity of said composition is 1 to 2000cP.In some embodiments, but the invention provides flow composition, wherein its viscosity is 10 to 1000cP.In some embodiments, but the invention provides flow composition, wherein said composition is a synthetic composition.In some embodiments, but the invention provides flow composition, wherein said carbonate, bicarbonate or its constitute at least 10% of said composition.In some embodiments, but the invention provides flow composition, wherein the CO of said composition ₂Content is at least 10%.In some embodiments, but the invention provides flow composition, wherein said composition has negativity carbon footprint.In some embodiments, but the invention provides the flow composition that further comprises boron, sulphur or nitrogen, wherein the relative isotopics of this boron, sulphur or nitrogen show the fossil fuel source.In some embodiments, but the invention provides flow composition, wherein said carbonate, bicarbonate or its combination comprise calcium, magnesium or its combination.In some embodiments, but the invention provides flow composition, wherein calcium/magnesium (Ca/Mg) mol ratio is 1/200 and 200/1.In some embodiments, but the invention provides flow composition, wherein calcium/magnesium (Ca/Mg) mol ratio is 12/1 to 1/15.In some embodiments, but the invention provides flow composition, wherein calcium/magnesium (Ca/Mg) mol ratio is 5/1 to 1/10.In some embodiments, but the invention provides the flow composition that further comprises the SOx or derivatives thereof.In some embodiments, but the invention provides the flow composition that further comprises metal.In some embodiments, but the invention provides the flow composition that comprises metal, wherein this metal comprises lead, arsenic, mercury or cadmium, or its combination.

In some embodiments, the invention provides the synthetic composition of the combination that comprises carbonate, bicarbonate or carbonate and bicarbonate, wherein the carbon in the said composition has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value and said composition are the carbon negativity.In some embodiments, the invention provides synthetic composition, wherein said carbonate, bicarbonate or its constitute at least 50% of said composition.In some embodiments, the invention provides synthetic composition, wherein said composition has the quality greater than double centner.In some embodiments, the invention provides synthetic composition, wherein the CO of said composition ₂Content is at least 10%.In some embodiments, the invention provides the synthetic composition that further comprises boron, sulphur or nitrogen, wherein the relative isotopics of this boron, sulphur or nitrogen show the fossil fuel source.In some embodiments, the invention provides synthetic composition, wherein said carbonate, bicarbonate or its combination comprise calcium, magnesium or its combination.In some embodiments, the invention provides synthetic composition, wherein calcium/magnesium (Ca/Mg) mol ratio is 1/200 to 200/1.In some embodiments, the invention provides synthetic composition, wherein calcium/magnesium (Ca/Mg) mol ratio is 12/1 to 1/15.In some embodiments, the invention provides synthetic composition, wherein calcium/magnesium (Ca/Mg) mol ratio is 5/1 to 1/10.In some embodiments, the invention provides the synthetic composition that further comprises the SOx or derivatives thereof.In some embodiments, the invention provides the synthetic composition that further comprises metal.In some embodiments, the invention provides the synthetic composition that further comprises metal, wherein this metal comprises lead, arsenic, mercury, or cadmium or its combination.

In some embodiments, the invention provides the method that characterizes synthetic composition, it comprises the relative carbon isotope composition (δ that determines said composition ¹³C) value.In some embodiments, the invention provides the method that characterizes synthetic composition, wherein said composition is a construction material, or underground storage material.In some embodiments, the invention provides the method that characterizes synthetic composition, wherein said composition is cementitious composition or gathers materials.In some embodiments, the invention provides the method that characterizes synthetic composition, wherein said composition is to be used to store CO ₂Composition.In some embodiments, the invention provides the method that characterizes synthetic composition, it further comprises the CO that determines said composition ₂Discharge stability.In some embodiments, the invention provides the method that characterizes synthetic composition, it further comprises the carbon content of measuring said composition.In some embodiments, the invention provides the method that characterizes synthetic composition, it further comprises the δ of comparison said composition ¹³C value and another δ ¹³The C value.In some embodiments, the invention provides the method that characterizes synthetic composition, it further comprises the δ of comparison said composition ¹³C value and another δ ¹³The C value, wherein said another δ ¹³The C value is benchmark δ ¹³The C value.In some embodiments, the invention provides the method that characterizes synthetic composition, it further comprises the δ of comparison said composition ¹³C value and another δ ¹³The C value, wherein said another δ ¹³The C value is the possible raw-material value of said composition.In some embodiments, the invention provides the method that characterizes synthetic composition, it further comprises the δ of comparison said composition ¹³C value and another δ ¹³The C value, wherein said another δ ¹³The C value is the value of fossil fuel, the flue gas derived from fossil fuel, water source or its combination.In some embodiments, the invention provides the method that characterizes synthetic composition, it further comprises the δ according to said composition ¹³C value and benchmark δ ¹³Whether relatively more definite said composition of C value comprises the CO that seals up for safekeeping from fossil fuel source ₂In some embodiments, the invention provides the method that characterizes synthetic composition, it further comprises the amount of carbon dioxide of sealing up for safekeeping in the quantification said composition.

In some embodiments, the invention provides the fingerprint analysis method for compositions, it ratio that comprises the stable isotope of multiple element in the value of the stable isotope of determining multiple element or the said composition is to determine the isotope element finger print of said composition, and wherein said composition comprises the combination of carbonate, bicarbonate or carbonate and bicarbonate.In some embodiments, the invention provides the fingerprint analysis method for compositions, wherein said stable isotope comprises the isotope of carbon, sulphur, nitrogen or boron or its combination.In some embodiments, the invention provides the fingerprint analysis method for compositions, wherein said composition is construction material or underground storage material.In some embodiments, the invention provides the fingerprint analysis method for compositions, wherein said composition is to store thus the composition that the compound of at least two kinds of isotopic elements determining is used.In some embodiments, the invention provides the fingerprint analysis method for compositions, it further comprises more at least two stable isotope values or at least two stable isotope ratios or its combination.In some embodiments, the invention provides the fingerprint analysis method for compositions, it further comprises may the originating of one or more components of determining said composition according to the isotope element finger print of this material.

In some embodiments, the invention provides whether definite composition contains the element of sealing up for safekeeping from fossil fuel source method; This method comprises isotope value or the isotope value ratio of determining this element, and the value that relatively records is with benchmark isotope value or isotope value ratio and determine whether said composition contains the element of sealing up for safekeeping from fossil fuel source.In some embodiments, the invention provides whether definite composition contains the element of sealing up for safekeeping from fossil fuel source method, wherein this element is carbon, sulphur, nitrogen or boron.In some embodiments, the invention provides whether definite composition contains the element of sealing up for safekeeping from fossil fuel source method, wherein this element is a carbon, and this relatively is δ ¹³The C value.

The synthetic composition with neutrality or negativity carbon footprint that comprises carbonate or bicarbonate or its combination is provided, and wherein the carbon in the said composition has-5.00 ‰ or lower relative carbon isotope composition (δ ¹³C) value.

The synthetic composition that comprises carbonate or bicarbonate or its combination is provided, and wherein the carbon in the said composition has-22.00 ‰ or lower relative carbon isotope composition (δ ¹³C) value.In some embodiments, this based composition has neutrality or negativity carbon footprint.In some embodiments, this carbonate and/or bicarbonate comprise the carbonate and/or the bicarbonate of beryllium, magnesium, calcium, strontium, barium or radium or its combination.In some embodiments, this carbonate and/or bicarbonate comprise the carbonate and/or the bicarbonate of calcium or magnesium or its combination.In some embodiments, said composition contains calcium and magnesium, and calcium/magnesium (Ca/Mg) mol ratio is 1/200 to 200/1.In some embodiments, calcium/magnesium (Ca/Mg) mol ratio is 12/1 to 1/15.In some embodiments, calcium/magnesium (Ca/Mg) mol ratio is 5/1 to 1/10.In some embodiments, calcium/magnesium (Ca/Mg) mol ratio is 1/9 to 2/5.In some embodiments, said composition further comprises the particle from industrial process.In this type of embodiment, this industrial process comprises combustion of fossil fuel.In this type of embodiment, this fossil fuel comprises coal.In some embodiments, described particle from industrial process comprises flying dust.In some embodiments, said composition further comprises NO _xOr derivatives thereof.In some embodiments, said composition further comprises SO _xOr derivatives thereof.In some embodiments, said composition further comprises the VOC or derivatives thereof.In some embodiments, said composition further comprises metal.In this type of embodiment, this metal comprises lead, arsenic, mercury or cadmium or its combination.

The construction material that comprises the component that comprises carbonate or bicarbonate or its combination is provided, and wherein the carbon in this carbonate and/or the bicarbonate has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value.In some embodiments, the component that comprises carbonate and/or bicarbonate in this construction material constitutes at least 5% of this construction material.In some embodiments, this construction material is a cementitious material.In some embodiments, this construction material is mortar, pozzolanic materials or auxiliary water earthy material or its combination.In some embodiments, this construction material is cement or concrete.In some embodiments, this construction material is non-cementaceous.In some embodiments, this construction material is to gather materials.In some embodiments, this to gather materials be coarse aggregate.In some embodiments, this to gather materials be fine aggregate.In some embodiments, this to gather materials be that reactivity is gathered materials.In some embodiments, this to gather materials be non-reacted or unreactive aggregate.In some embodiments, this to gather materials be to be shaped or casting is gathered materials.In some embodiments, this construction material is a pavement material.In some embodiments, this pavement material is a roadbed.In some embodiments, this pavement material is a paving material.In some embodiments, this material be the construction material of non-cementitious material and this non-cementaceous be brick, plate, conduit, beam, basin, post, watt, fibre wall panel products, base, soundproof wall, gypsum, drywall, plaster, soil fixation composition or barrier material or their combination.In some embodiments, said composition further comprises the particle from industrial process.In this type of embodiment, this industrial process comprises combustion of fossil fuel.In this type of embodiment, this fossil fuel comprises coal.In some embodiments, described particle from industrial process comprises flying dust.In some embodiments, said composition further comprises NO _xOr derivatives thereof.In some embodiments, said composition further comprises SO _xOr derivatives thereof.In some embodiments, said composition further comprises the VOCs or derivatives thereof.In some embodiments, said composition further comprises metal.In this type of embodiment, this metal comprises lead, arsenic, mercury or cadmium or its combination.

The non-construction material that comprises the component that comprises carbonate or bicarbonate or its combination is provided, and wherein the carbon in this carbonate and/or the bicarbonate has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value.In some embodiments, the component that comprises carbonate and/or bicarbonate in this non-construction material is neutral carbon or carbon negativity.In some embodiments, the component that comprises carbonate and/or bicarbonate in this non-construction material constitute this non-construction material more than 5%.In some embodiments, this non-construction material is the product of family expenses or commercial ceramic product, paper product, polymerization product, lubricant, adhesive, rubber product, chalk, lacquer, personal care product, cleaning products, personal hygiene products, cosmetics, edible product, liquid edible product, solid-state edible product, animal edible product, agricultural product, soil melioration product, insecticide, environment remediation product, forest soil reparation product or the sour water that neutralized.

The synthetic composition that comprises carbonate or bicarbonate or its combination is provided, and wherein the carbon in the said composition has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value and said composition do not discharge more than its total CO at least when being exposed to normal temperature and damp condition and have in the rainwater of normal pH 1 year ₂1%.In some embodiments, said composition has neutrality or negativity carbon footprint.In some embodiments, said composition is a solid sediment.In some embodiments, this carbonate and/or bicarbonate comprise the carbonate and/or the bicarbonate of beryllium, magnesium, calcium, strontium, barium or radium or its combination.In some embodiments, this carbonate and/or bicarbonate comprise the carbonate and/or the bicarbonate of calcium or magnesium or its combination.In some embodiments, said composition contains calcium and magnesium, and calcium/magnesium (Ca/Mg) mol ratio is 1/200 to 200/1.In some embodiments, calcium/magnesium (Ca/Mg) mol ratio is 12/1 to 1/15.In some embodiments, calcium/magnesium (Ca/Mg) mol ratio is 5/1 to 1/10.In some embodiments, calcium/magnesium (Ca/Mg) mol ratio is 1/9 to 2/5.In some embodiments, said composition further comprises the particle from industrial process.In this type of embodiment, this industrial process comprises combustion of fossil fuel.In this type of embodiment, this fossil fuel comprises coal.In some embodiments, described particle from industrial process comprises flying dust.In some embodiments, said composition further comprises NO _xOr derivatives thereof.In some embodiments, said composition further comprises SO _xOr derivatives thereof.In some embodiments, said composition further comprises the VOCs or derivatives thereof.In some embodiments, said composition further comprises metal.In this type of embodiment, this metal comprises lead, arsenic, mercury or cadmium or its combination.

The construction material that comprises the synthetic composition that comprises carbonate or bicarbonate or its combination is provided, and wherein the carbon in the said composition has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value and said composition do not discharge more than its total CO at least when being exposed to normal temperature and damp condition and have in the rainwater of normal pH 1 year ₂1%.In some embodiments, this construction material is neutral carbon or carbon negativity.In some embodiments, this construction material is a cementitious material.In some embodiments, this construction material is cement or concrete.In some embodiments, this construction material is mortar, pozzolanic materials or auxiliary water earthy material or its combination.In some embodiments, this construction material is non-cementaceous.In some embodiments, this construction material is to gather materials.In some embodiments, this to gather materials be coarse aggregate.In some embodiments, this to gather materials be fine aggregate.In some embodiments, this to gather materials be that reactivity is gathered materials.In some embodiments this to gather materials be non-reacted or unreactive aggregate.In some embodiments, this to gather materials be to be shaped or casting is gathered materials.In some embodiments, this construction material is a pavement material.In some embodiments, this pavement material is a roadbed.In some embodiments, this pavement material is a paving material.In some embodiments, this material be the construction material of non-cementitious material and this non-cementaceous be brick, plate, conduit, beam, basin, post, watt, fibre wall panel products, base, soundproof wall, gypsum, drywall, plaster, soil fixation composition or barrier material or their combination.

The non-construction material that comprises the component that contains synthetic composition is provided, and this synthetic composition comprises carbonate or bicarbonate or its combination, and wherein the carbon in the said composition has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value, and said composition does not discharge more than its total CO at least when being exposed to normal temperature and damp condition and have in the rainwater of normal pH 1 year ₂1%.In some embodiments, carbonate in this non-construction material and/or bicarbonate are neutral carbon or carbon negativity.In some embodiments, the non-construction material of this of at least 5% has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value, and said composition does not discharge more than its total CO at least when being exposed to normal temperature and damp condition and have in the rainwater of normal pH 1 year ₂1%.

The synthetic composition that includes but not limited to magnesium carbonate and/or magnesium bicarbonate is provided, and wherein the carbon in the said composition has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value, and said composition includes but not limited to mineral facies: magnesite, nesquehonite, hydromagnesite, huntite, magnesian calcite, dolomite, former dolomite or unordered dolomite or its combination.In some embodiments, said composition does not discharge more than its total CO at least when being exposed to normal temperature and damp condition and have in the rainwater of normal pH 1 year ₂1%.

The synthetic composition that includes but not limited to magnesium carbonate and/or magnesium bicarbonate is provided, and wherein the carbon in the said composition has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value, and said composition is in hydrated state or its combination of 1,2,3,4,5 or 6 hydrate water.In some embodiments, said composition does not discharge more than its total CO at least when being exposed to normal temperature and damp condition and have in the rainwater of normal pH 1 year ₂1%.

The synthetic composition that comprises calcium carbonate or calcium bicarbonate or their any combination is provided, and wherein the carbon in the said composition has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value, and said composition includes but not limited to mineral facies amorphous calcium carbonate, calcite, aragonite or vaterite or its combination.In some embodiments, said composition does not discharge more than its total CO at least when being exposed to normal temperature and damp condition and have in the rainwater of normal pH 1 year ₂1%.

The synthetic composition that comprises calcium carbonate or calcium bicarbonate or their any combination is provided, and wherein the carbon in the said composition has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value, and said composition is in hydrated state or its combination of 1,2,3 or 4 hydrate water.In some embodiments, said composition does not discharge more than its total CO at least when being exposed to normal temperature and damp condition and have in the rainwater of normal pH 1 year ₂1%.

Provide and produce double centner at least every day by carbon sequestration and have relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) method of Zhi carbonaceous material.In some embodiments, this product has neutrality or negativity carbon footprint.

Provide by determining the relative carbon isotope composition (δ of said composition ¹³C) value characterizes the method for synthetic composition.In some embodiments, this synthetic composition is construction material or underground storage material.In some embodiments, this synthetic composition is cementitious composition or gathers materials.In some embodiments, this synthetic composition is to be used to store CO ₂Composition.In some embodiments, this method comprises the CO that determines said composition ₂Discharge the step of stability.In some embodiments, this method comprises the step of the carbon content of determining said composition.In some embodiments, this method comprises the δ of comparison said composition ¹³C value and another δ ¹³The step of C value, in some cases, described another δ ¹³The C value is standard δ ¹³The C value in other cases, is the possible raw-material δ that is used to make said composition ¹³The C value.In some cases, described another δ that is used for comparison ¹³The C value is raw material---may be the δ of fossil fuel, flue gas, water source or its combination derived from fossil fuel ¹³The C value.In some embodiments, this method further comprises according to comparing δ ¹³The C value determines whether said composition comprises the CO that seals up for safekeeping from fossil fuel source ₂In some embodiments, the amount of the carbonic acid gas of sealing up for safekeeping in the quantification said composition.

The fingerprint analysis method for compositions is provided, and the ratio that comprises the stable isotope of multiple element in the value of the stable isotope of determining multiple element or the said composition is to determine the isotope element finger print of said composition.In some embodiments, this stable isotope comprises the isotope of carbon, sulphur, nitrogen or boron or its combination.In some embodiments, said composition is construction material or underground storage material.In some embodiments, this method comprises the step of more at least two stable isotope values or at least two stable isotope ratios or its combination.In some embodiments, this method comprises the step that may originate of determining one or more components of said composition according to the isotope element finger print of this material.In some embodiments, may originating of these one or more components is fossil fuel.

Provide and determine that whether composition contains the method for the element of sealing up for safekeeping from fossil fuel source, comprise isotope value or the isotope value ratio of determining this element.In some embodiments, this element is carbon, sulphur, nitrogen or boron.In some embodiments, this method further comprise this isotope value relatively or isotope value than with the step of standard value.In some embodiments, this element is that carbon and this relatively are δ ¹³The C value.

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All open source literatures, patent and the patent application of mentioning in this specification is incorporated herein by this reference just as each open source literature, patent or patent application clearly also are specified one by one and is incorporated herein by this reference.

Description of drawings

Concrete elaboration novel feature of the present invention in claims.As detailed below and accompanying drawing with reference to illustrated example embodiment (wherein having utilized principle of the present invention) are understood the features and advantages of the present invention better, in the accompanying drawings:

Fig. 1 provides exemplary carbon sequestration method.

Fig. 2 provides by being used to obtain δ ¹³The preparation method figure of the sample that the table top Instrumental Analysis of C value is used.

Fig. 3 is provided at the figure that is made deposited material in the laboratory scale by carbonated gas and shepardite mine tailing.Indicated the material (gas, liquid and solid) that characterizes among this figure.

Fig. 4 is provided at the figure that is made deposited material in 250,000 gallon cans by carbonated gas and shepardite mine tailing on a large scale.Indicated the material (gas, liquid and solid) that characterizes among this figure.

Fig. 5 is provided at the figure that is made deposited material in the continuity method by carbonated gas and shepardite mine tailing.Indicated the material (gas, liquid and solid) that characterizes among this figure.

Fig. 6 is provided at the figure that is made deposited material in the laboratory scale method by carbonated gas and flying dust.Indicated the material (gas, liquid and solid) that characterizes among this figure.

Fig. 7 provides from document, from the δ that uses the shepardite mine tailing as carbonated gas source, industrial waste, sediment and the supernatant of the laboratory scale method of industrial waste ¹³The comparison of C data.

Fig. 8 provides from document, from the δ that uses the shepardite mine tailing as carbonated gas source, industrial waste, sediment and the supernatant of the large-scale methods of industrial waste ¹³The comparison of C data.

Fig. 9 provides from document, from the δ that uses the shepardite mine tailing as carbonated gas source, industrial waste, sediment and the supernatant of the continuation method of industrial waste ¹³The comparison of C data.

Figure 10 provides from document, from the δ that uses flying dust as carbonated gas source, industrial waste, sediment and the supernatant of the laboratory scale method of industrial waste ¹³The comparison of C data.

Detailed Description Of The Invention

The invention provides composition that contains element and the method for determining composition levels with relative element isotope value (one or more) with specific relative element isotopics value (one or more).In some embodiments, the invention provides to contain and have negative carbon isotope composition (δ ¹³C) composition of Zhi carbon, for example the carbon in synthetic composition and the analysed composition is to determine δ ¹³The C value for example verifies that some or all of carbon in the said composition are from the method for carbon sequestration method.In some embodiments, other element may exist similarly and/or characterizes according to their isotopic content or isotope ratio as sulphur, boron or nitrogen, in addition, other material also may be present in the said composition and can analyze as sulphite, sulphate or heavy metal.Said composition and method can be used on to be needed to use in the purposes of following material: this material is the material that is not suitable for being discharged in the environment, as the product of sealing up for safekeeping of carbonic acid gas, oxysulfide, nitrogen oxide, heavy metal and other material of for example producing in the combustion of fossil fuel, and verify the source of carbon in this class material etc.

Before more detailed description the present invention, it being understood that to the invention is not restricted to described specific embodiments, therefore variable certainly.What it is also understood that is that term used herein only is used to describe specific embodiments and is not restrictive, because scope of the present invention only is subjected to the restriction of appended claims.

When number range is provided, should be understood that, any other designated value between the upper and lower bound of this scope and in this specified scope or between two parties each between the value between two parties value (unless indicate separately clearly in the literary composition, to the unit of lower limit 1/10) be included in the present invention.Except that any boundary value of in this specified scope, clearly getting rid of, these upper and lower bounds more among a small circle can be included in independently these more among a small circle in and be also contained in the present invention.If this specified scope comprises one of boundary value or both, get rid of the arbitrary of these boundary values that comprise or both scopes are also included among the present invention.

For some scope herein, modify with term " approximately " before the numerical value.Term " approximately " be used in this article thereafter definite numerical value and with this term after numerical value near or approximate numerical value literal support is provided.Determine numerical value whether near or during the approximate numerical value of clearly enumerating, near or the approximate numerical value of not enumerating can be in its statement background with the numerical value of the basic equivalence of the numerical value of clearly enumerating.

Unless indicate separately, all technology used herein have the implication identical with those skilled in the art's common sense with scientific and technical terminology.Although in practice of the present invention or test, also can use and those similar or equivalent any method and materials described herein, describe representational exemplary method and material now.

All open source literatures and the patent quoted in this specification all are incorporated herein by this reference, clear and definite and be specified one by one and be incorporated herein by this reference just as each open source literature or patent, and be incorporated herein by this reference for the disclosure and description method relevant with the open source literature of quoting and/or material.Any open source literature quote be at it in the disclosure of submitting to a few days ago, and should not be regarded as admitting that the present invention haves no right with invention formerly prior to the disclosure document.In addition, what provided may be different from actual open day open day, and this may need independent affirmation.

It is to be noted that unless indicate separately clearly in the literary composition, used singulative in this paper and the claims " certain (a, an) ", " should, described (the) " comprise plural object.To be pointed out that further that claims can be drafted and in a row remove any optional key element.Therefore, this statement is intended to serve as the basis in advance as the use of the use of " only ", " only's " and so on exclusiveness term or " negativity " restriction of enumerating coupling with the claim key element.

Those skilled in the art can find out after reading the disclosure, each of each embodiment that this paper describes and exemplifies has discrete component and feature, they can easily separate or unite with the feature of any other several embodiments, and do not deviate from scope of the present invention or spirit.Any method of enumerating can be carried out with cited incident order or carry out with feasible in logic any other order.

Foreword

When further describing theme of the present invention, statement is used for measuring the isotopic ratio of composition, for example δ ¹³C value, and constituent content, carbon content for example, method.Also described follow the tracks of or the checking composition in the method in the source of carbon for example.Describe to contain subsequently and have specific isotope ratio, for example δ ¹³The composition of the element of C value.

Determine the method for relative isotope value (relative isotopic value)

On the one hand, the invention provides by determining that its relative isotopics ratio comes the method for characterize combinations.Although can use various isotopes (all these have can with standard than the isotope ratio that compares)-for example carbon, oxygen, sulphur, boron and nitrogen, following description is primarily aimed at carbon and relative carbon isotope ratio or δ ¹³The C value.It being understood that this argumentation is applicable to the element that other is suitable too.In some embodiments, also determine the constituent content of said composition, for example carbon content.In some embodiments, this method for example further comprises by relatively carbon content and relative carbon isotope composition being waited than the value that records and standard value or raw material value and verifies that said composition contains from CO ₂Carbon, this CO ₂From particular source, fossil fuel source for example.Said composition can be the carbon that has wherein stored from fossil fuel source, for example the composition of carbonic acid gas.In some cases, this based composition desirably has precedence over other material and for example is used in structure or the road, carbonic acid gas and optional other not desirable material is sealed up for safekeeping in architectural environment guaranteeing.In some cases, desirably use this based composition, for example slurry or solution, as be used for the long term storage carbonic acid gas and optional other not desirable material seal medium up for safekeeping.Therefore, in some embodiments, this method further comprises the carbon dioxide storage stability of determining said composition, for example determines the carbonic acid gas rate of release under imposing a condition.

In some embodiments, this method comprises measures multiple element, two or more in carbon, sulphur, nitrogen, oxygen and the boron for example, isotope value, as relative isotopic ratio, thus can isotope " fingerprint analysis " particular composition.

Method of the present invention can be used for for example verifying in the composition some or substantially all carbon and, in some cases, other element source is from fossil fuel.

Stable isotope and isotope fractionation

Many elements have stable isotope, and in various processes, for example preferentially use these isotopes in the bioprocess.Example is a carbon, and it is used to illustrate most methods as herein described, still, recognize, these methods also are applicable to other element with stable isotope, as long as their ratio can be to measure with the similar mode of carbon; This dvielement comprises nitrogen, oxygen, sulphur and boron.The method of measuring the isotope ratio of these elements is known.

With ‰ (every mil) is the relative carbon isotope composition (δ of unit ¹³C) value is with respect to fossilisation belemnite (fossilized belemnite) standard (PDB standard), two kinds of stable isotopes of carbon, promptly ¹²C and ¹³The tolerance of the concentration ratio of C.

δ ¹³C ‰=[( ¹³C/ ¹²C _Sample- ¹³C/ ¹²C _{The PDB standard})/( ¹³C/ ¹²C _{The PDB standard})] * 1000

¹²C since its than low quality in the photosynthesis process and utilizing in other bioprocess of DIC and preferentially drawn by plant. ¹²C makes the limited reaction of dynamics than using than low quality ¹³Carry out more efficiently during C.Therefore, derived from the material of vegetable material, for example fossil fuel has than derived from the little relative carbon isotope composition value of the material of inorganic source.The relative carbon isotope composition value that reflects the organic material of fossilisation by the carbonic acid gas in the flue gas of combustion of fossil fuel generation.Table 1 is listed the relative carbon isotope composition value scope of the relevant carbon source that is used for comparison.

The material bodies that comprises from the carbon of combustion of fossil fuel reveals more as plant-derived materials, promptly less than the δ that comprises from the material with carbon element in atmosphere or source, non-plant ocean ¹³The C value.The material that checking is made by the carbonic acid gas method of sealing up for safekeeping is made of the δ that comprises measurement gained material the carbon from combustion of fossil fuel ¹³The C value also confirms the value of its not similar atmospheric carbon dioxide and ocean carbon source.

Relative carbon isotope composition (the δ of the carbon source that table 1. is paid close attention to ¹³C) value

Carbon source	δ ¹³C scope [‰]	δ ¹³C mean value [‰]
			C3 plant (most of higher plant)	-23 to-33	-27
C4 plant (most of torrid zones and limnocryptophyte)	-9 to-16	-13
			Atmosphere	-6 to-7	-6
Marine carbon hydrochlorate (CO ₃)	-2 to+2	0
			Ocean bicarbonate (HCO ₃)	-3 to+1	-1

Coal from Yallourn Seam in Australia ¹	-27.1 to-23.2	-25.5
			From Dean Coal Bed in Kentucky, the coal of USA ²	-24.47 to-25.14	-24.805

1.Holdgate, people such as G.R., Global and Planetary Change, 65 (2009) 89-103 pages or leaves.

2.Elswick, people such as E.R., Applied Geochemistry, 22 (2007) 2065-2077 pages or leaves.

In some embodiments, the invention provides the method for characterize combinations, comprise and measure its relative carbon isotope composition (δ ¹³C) value.In some embodiments, said composition is to contain carbonate, for example the composition of magnesium carbonate and/or calcium carbonate.Can use any suitable method to measure this δ ¹³The C value is as mass spectrometry or from axle integration chamber output spectrum method (from axle ICOS).

A difference between the carbon isotope is their quality.Can use responsive definite to any mass discrimination technology that is enough to measure the carbon amount ¹³C with ¹²The ratio of C isotopes concentration.Mass spectrometry is usually used in determining δ ¹³The C value.Also can buy and to determine δ ¹³The table top of C value is from axle integration chamber output spectrum (from axle ICOS) instrument.These values are passed through ¹²C and ¹³Energy difference in the two keys of carbon-oxygen that the C isotope produces in carbonic acid gas obtains.δ from the carbonate sediment of carbon sequestration method ¹³The C value is served as CO ₂The fingerprint of gas source, because should value can become with the source, but in most of carbon sequestration situations, δ ¹³C is generally-9 ‰ to-35 ‰.

In some embodiments, this method comprises the measurement of the carbon amount in the said composition.Can use any suitable carbon measuring technique, as coulometry.Can use carbon to measure the amount of the carbonic acid gas of sealing up for safekeeping in the quantification composition in some cases.Isotope measure can be used for verifying that the carbon source in the composition is the carbon source of being claimed.

Another feature of embodiments more of the present invention comprises the δ of comparison said composition ¹³C value and another δ ¹³The C value; This another δ ¹³The C value can be a standard value---in the said composition possible raw material (for example coal, oil, natural gas or flue gas) value or provide can be for any other value of relatively useful information.In some embodiments, with the δ of said composition ¹³C value and fixed value or number range, as-1 ‰ to-50 ‰, or-5 ‰ to-40 ‰, or-5 ‰ to-35 ‰, or-7 ‰ to-40 ‰, or-7 ‰ to-35 ‰, or-9 ‰ to-40 ‰, or-9 ‰ to-35 ‰ value compares, or with-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 ‰ value compares.In some embodiments, show that less than the value of fixed value some or all substantially carbon source in the said composition is from fossil fuel, the value of any value that provides less than this paper for example, as less than-7 ‰ value, or less than-10 ‰ value, or less than-15 ‰ value, or less than-20 ‰ value, or less than-25 ‰ value, or less than-30 ‰ value, or less than-35 ‰ value, value less than-40 ‰.

In some embodiments, with the δ of said composition ¹³The possible raw-material value of C value and said composition compares.For example, the δ of said composition ¹³The C value can with fossil fuel, as the coal of natural gas, oil, coal or particular type, or as the δ of the flue gas that produces by the burning of coal of natural gas, oil, coal or particular type ¹³C value, or δ ¹³C value scope compares.This is particularly useful for verifying that said composition contains from fossil fuel and/or from the CO of combustion of fossil fuel ₂Only as an example, if the δ of coal ¹³The C value is for-34 ‰ and claim the CO that seals up for safekeeping from coal combustion ₂The δ of composition ¹³The C value equals-34 ‰ or (this can be any suitable scope in-34 ‰ certain limit, depend on the variation of measuring condition, coal, from variation of the flue gas of coal etc., for example ± 1 ‰, or ± 2 ‰, or ± 3 ‰, or ± 4 ‰, ± 5 ‰), this can be regarded as confirming wholly or in part that carbon source in the said composition is from this fossil fuel.In above-mentioned example, if acceptable scope for ± 3 ‰ and said composition have-32 ‰ δ ¹³C value, then this δ ¹³The C value can be regarded as consistent with the source from the carbon of this particular coal in the said composition.Other factors with due regard in this checking.In some embodiments, this δ ¹³The C value is unique Consideration.

Some embodiments further comprise in the quantized sets compound from CO ₂Source, for example CO that seals up for safekeeping in the fossil fuel source ₂Amount.For example, can use coulometry to determine the relative quantity of carbon in the composition, and can use isotopic ratio to verify that this carbon is derived from fossil fuel wholly or in part.Follow and determine the CO that seals up for safekeeping in the said composition by simple computation ₂The amount of (or carbon) is if provide the carbon that is derived from fossil fuel and the relative quantity of total carbon.

Other embodiments of the present invention comprise that (itself and standard compare, and are similar to δ for the isotope value of the non-carbon determined in the composition or the element beyond the de-carbon or isotope ratio ¹³The C value).This dvielement includes but not limited to oxygen, nitrogen, sulphur and boron.Can be by measuring the isotope value of any these dvielements or element combinations with those similar techniques that are used for carbon.This class technology and the method for comparatively representing isotope ratio with standard are well known in the art, for example the δ of boron ¹¹The δ of B value and sulphur ³⁴The S value.Therefore, in some embodiments, the invention provides multiple isotope value by determining said composition or isotopic ratio or it makes up the method for isotope element finger print analysed composition.In some embodiments, also determine this element or the amount of its compound in said composition.In some embodiments, quantification with the elements of this isotope representative uses one or more isotope compositions with isotope element finger print to determine having particular source in the said composition, for example has the total amount of the elements in fossil fuel source.In addition, isotope ratio may change (for example for boron and/or sulphur) in the burning of fossil fuel and other process, and these changes can count consideration in some embodiments with further refinement checking and/or quantitative analysis.

In some embodiments, determine two or more isotope value or isotopic ratio or its combination in carbon, sulphur, oxygen, nitrogen and the boron.In some embodiments, determine the isotope element finger print of carbon and sulphur, for example the δ of carbon ¹³The δ of C value and sulphur ³⁴The S value.In some embodiments, determine the isotope element finger print of carbon and boron, for example the δ of carbon ¹³The δ of C value and boron ¹¹The B value.In some embodiments, determine the isotope element finger print of carbon, sulphur and boron, for example the δ of carbon ¹³The δ of C value, sulphur ³⁴The δ of S value and boron ¹¹The B value.

Isotope element finger print can be used for verifying the source of element in the said composition, for example is used in the checking said composition and contains in the rules of the element that is derived from fossil fuel.This is useful, because many elements, for example carbon and sulphur or their oxide or other compound are subjected to control in all parts of the world, as total amount control and discharging transaction system or other regulations system.Therefore, for example in this type systematic, can use the capture of technical identification of the present invention and/or quantification element and/or their compound.This checking and/or quantification can be used for confirming the compliance with regulations, seal this element or compound up for safekeeping with calculating, for example carbonic acid gas, oxysulfide, nitrogen oxide and be subjected to any other element of control or the credit and the punishment of compound (can carry out their isotope measure) and be used for conspicuous any other the suitable purposes of those skilled in the art.

For example, in order to show that in a process carbonic acid gas takes place to be sealed up for safekeeping, the total amount of carbon dioxide that comes from a process is according to the show less than the total amount of the carbon dioxide that enters this process; In addition, the source of discharging the carbonic acid gas in the gas may be shown as with the product of identical and/or this process of the gas that enters this process and seal CO from this gas according to the show up for safekeeping ₂" fingerprint analysis " material is by measuring and relatively carbon and/or other element, recently makes carbon contained in this material and/or other element interrelated with the source as the stable isotope of nitrogen and sulphur.Because the material user attempts to obtain carbon credit when using material, this method can be used for confirming that carbonic acid gas seals up for safekeeping and show that a material is the carbon negativity.

Show among Fig. 1 that the carbonic acid gas with three kinds of possible carbon sources seals method up for safekeeping.They are: contain CO ₂Air-flow [100], the air above the solution of the method for sealing up for safekeeping [105] and shown in seal the water or the solution [110] of method up for safekeeping, for example seawater, salt solution or other solion.Carbon amount in can measuring separately.The CO that contains for input ₂Air-flow [100], for example use commercial gas probe measurement CO well known by persons skilled in the art ₂The dividing potential drop of gas.Also measure or regulate and contain CO ₂The flow velocity of gas.CO in know gas volume and known this gas by flow velocity ₂Under the situation of concentration, enter the CO of this process ₂Total amount be known.Air is oxygen (O ₂), nitrogen (N ₂), CO ₂, water vapour, ozone and other gas mixture.Be similar to CO to input ₂It is such that air-flow records, and for the air in the characterization system [105], for example uses commercially available probe measurement CO ₂Dividing potential drop, and know volume of air according to the size of reactor.These values of air in this system are told the carbon amount of our this air contribution.Use any suitable method, for example coulometry is measured the concentration of carbon in the water [110].Inorganic and organic carbon content can use coulometry to measure by changing digestive juice.Therefore generally speaking, organic carbon does not participate in this reaction and is not counted in carbon in the method for sealing up for safekeeping.

CO by example [115] ₂The method of sealing up for safekeeping obtains to contain four kinds of components of carbon.These components are: eluting gas [120], required product [130], trickle [135] and the air [125] that contacts with trickle with this product after reaction takes place.As mentioned above, use commercially available probe to determine that the carbon amount in the gas component determines partial pressure of carbon dioxide with the gas volume in this system.Use the carbon amount in coulometry measurement liquid and the solid constituent.Also use mass spectrometry or from the δ of axle ICOS by them ¹³The C value characterizes these materials.δ with product ¹³The CO of C value [130] and input ₂The fingerprint value of air-flow [100] compares.CO near input ₂, for example still very negative product δ ¹³C shows that carbon in this product is not from the fact of water [110] or air [105].Water and air has the only negative slightly δ that records usually in this material and technology characterizing method ¹³The C value is not less than-8 ‰.

Whether the carbon amount of input in the component has any carbon not count with comparison shows that of carbon amount in the component of sealing method from this up for safekeeping.With δ ¹³This mass balance of C fingerprint analysis coupling shows, a part of CO ₂Leave the input air-flow, be not present in the effluent stream, and incorporate in the product.

Illustrative methods shown in Fig. 1 is method [115], in this process from the input gas CO ₂Dissolving [100] in solution, but with solution in ionic reaction and the form that is formed for maybe can changing into this form with the long term storage form from input gas, remove CO ₂Material.This method can produce solution, deposited material, or slurry, as long as end product is fit to long term storage.Can be at isotopic content or ratio, for example δ of any component of any phase measuring of this method ¹³The C value is to obtain original CO ₂Final situation quantitatively and/or observational measurement.In addition, the carbon that is undertaken by for example coulometry is measured and is allowed precise quantification CO ₂Final situation.Under the situation of any measurement, can be from material or in time through obtaining a plurality of samples, for example can obtain and analyze 1,2,3,4,5,6,7,8,9,10 or more than 10 samples.Therefore, for large quantities of products of making and/or making continuously, the sample that can get suitable quantity is with total δ of the material of indicating all amounts ¹³C value and/or carbon content.In the example shown in Fig. 1, CO ₂Can be from containing CO ₂The gas flue gas of combustion of fossil fuel (for example from), from containing CO with this ₂Gas be dissolved in the air [105] of water contact wherein and enter this method from water itself [110].Measure a kind of, two kinds or all δ in these ¹³The C value also can be measured CO separately ₂Concentration and flow velocity.Can carry out similar measurement to eluting gas [120], the air [125] that contacts with the desciccate and/or the liquid efflunent of settling step, product (liquid slurry of for example carbonato solid material or carbonate and/or bicarbonate) [130] and liquid efflunent [135].Can test and consider any additional CO similarly ₂Source or CO ₂Converge.At known each CO ₂Source or CO ₂Flow velocity in the remittance, volume, flowing time, δ ¹³C value and CO ₂Under the situation of concentration/amount, direct calculated mass balance and confirm for example CO ₂Seal up for safekeeping the product from original flue gas, and quantize the CO seal up for safekeeping ₂Amount.Recognize, the separate sources of flue gas, for example different fossil fuels as the coal from various places, may have different δ ¹³The C value, and can be according to this δ ¹³The product that identification of C value or affirmation use given raw material to make in given place.Although this a kind of mode of doing is to infer the δ of product ¹³The CO that C and fossil fuel (this product it is said from this fossil fuel) or described combustion of fossil fuel produce ₂δ ¹³The C value compares, the product of each batch of also can taking a sample, and many batches representative sample perhaps is to use the δ that is derived by product itself by rule of thumb ¹³C.Can adopt arbitrary method or combinatorial test and discriminating counterfeit materials.

Also to recognize, other element that exists in this fossil fuel, the fossil fuel that may have particular type as sulphur, boron and/or nitrogen is distinctive, the coal in for example used particular type and geology source distinctive and may in addition distinctive their isotopic ratio of the particular batch of coal.If with δ ¹³The C value combines with one or more these values, can obtain the uniqueness " fingerprint " of material source, and this can seal carbon up for safekeeping and/or compare from the fingerprint of the composition of other material of fossil fuel with claiming.Therefore, in some embodiments, the invention provides by determining the δ of said composition ¹³The isotopics value of one or more in C value and sulphur, boron or the nitrogen is verified the method in composition source.The combination of these isotope values or value can be used separately, maybe can use the amount of each element and/or its source than (for example carbon/boron, or carbon/sulphur, or the ratio of sulphur/boron, or the like) checking said composition.About isotope ratio, when using the amount of element itself, can promptly seal ground up for safekeeping with the amount in the said composition and in the supposition source points, the actual sample of extraction compares to determine whether coupling.The combination of amount and isotope ratio provides the extremely strong method of precise classification and checking one composition, and comprises in embodiments of the invention.

Optional other material of sealing up for safekeeping in precipitated composition or in the solution comprises oxysulfide (SO _x, SO for example ₂And SO ₃), nitrogen oxide (NO _x, for example NO or NO ₂), in heavy metal such as mercury, radioactive substance and the VOC one or more.In the composition of analyzing, also can measure and quantize these materials, or their derivative in some cases, and numerical value and reality or theoretical value compared the amount (being used for control and/or trade purposes) of removing to determine from flue gas, if or said composition is the unknown combination thing or claims the composition that comes from specialization stone fuel that source is like this really to verify it.Therefore, in some embodiments, the present invention includes the method for analytic sample, comprise the δ that determines this sample ¹³C value and determine SO _xOr derivatives thereof, as sulphate or sulphite, for example sulphate of calcium or magnesium or sulphite, NO _xThe content value of one or more in or derivatives thereof or mercury or derivatives thereof such as the mercury chloride also compares these values and a reference value (it can be by rule of thumb derived by the actual sample in known source, the theoretical derivation, or derive with any other suitable manner).In some embodiments, the present invention includes the method for analytic sample, it comprises the δ that determines this sample ¹³The C value is determined one or more similar isotopic ratio and the definite SO in boron, sulphur or the nitrogen _xOr derivatives thereof, as sulphate or sulphite, for example sulphate of calcium or magnesium or sulphite, NO _xThe content value of one or more in or derivatives thereof or mercury or derivatives thereof such as the mercury chloride also compares these values and a reference value (it can be by rule of thumb derived by the actual sample in known source, the theoretical derivation, or derive with any other suitable manner).

If desired, can use mass spectrometry for example or from the relative carbon isotope composition value of axle ICOS monitoring this solution in this procedure.Can measure by total alkalinity and calculate the CO that is dissolved in this solution ₂Concentration.The measurement of the total alkalinity of the solution of known volume causes calculating carbon dioxide content.Monitoring is dissolved into the CO in this solution in the process of this method ₂Allow to regulate making the required product of sealing up for safekeeping, and be the optional part of this method.

Can recognize that this method is equally applicable to multiple other products, include but not limited to fuel, environment analyte, food and lacquer.Can characterize any following material by this method---wherein source material stable isotope content can with the comparing of product.For example, also can for example use mass spectrometry measure oxygen ( ¹⁶O and ¹⁸O), nitrogen ( ¹⁴N and ¹⁵N), sulphur ( ³²S and ³⁴S), hydrogen ( ¹H and ²H) and/or boron ( ¹⁰B and ¹¹The ratio of stable isotope B).Also can recognize, can use various standard laboratory analytical technologies to measure the amount of these and any other suitable element.These values can be used for following the trail of other component in the product.For example can be in product, to follow the trail of sulphur from flue gas with the similar mode of carbon.Similarly, also can follow the trail of nitrogen.Thus, can produce " fingerprint " of specific product.Under the simplest situation, this fingerprint is the ratio (δ for example of stable isotope in the product ¹³The C value).In other embodiments, can use a plurality of isotope ratios, for example 2,3,4,5,6 or more than 6.In some embodiments, the fingerprint of product comprises the value or the ratio of stable carbon isotope.In some embodiments, the fingerprint of product comprises the value or the ratio of stable sulfur isotope.In some embodiments, the fingerprint of product comprises the value or the ratio of stable nitrogen isotope.In some embodiments, the fingerprint of product comprises the value or the ratio of stable boron istope.In some embodiments, use combination more than the ratio of a kind of value of stable isotope of element or value.In some embodiments, provide the concentration value of stable isotope of carbon and sulphur or the combination of concentration ratio.In some embodiments, use combination more than the ratio of a kind of value of stable isotope of element or value.In some embodiments, provide the concentration value of stable isotope of carbon and nitrogen or the combination of concentration ratio.In some embodiments, use combination more than the ratio of a kind of value of stable isotope of element or value.In some embodiments, provide the concentration value of stable isotope of carbon, nitrogen and sulphur or the combination of concentration ratio.In some embodiments, the fingerprint of product comprises δ ¹³The C value.In some embodiments, fingerprint comprises δ ¹³C value and δ ³⁴The S value.In some embodiments, fingerprint comprises δ ¹³C value and δ ¹¹The B value.In some embodiments, fingerprint comprises δ ¹³C value and δ ¹⁵The N value.In some embodiments, fingerprint comprises δ ¹³C value, δ ³⁴S value and δ ¹⁵The N value.In some embodiments, fingerprint comprises δ ¹³C value, δ ³⁴S value and δ ¹¹The B value.In some embodiments, fingerprint comprises δ ¹³C value, δ ¹¹B value and δ ¹⁵The N value.

Carbonaceous composition

In some embodiments, the invention provides to contain and have negative relative carbon isotope composition (δ ¹³C) composition of Zhi carbon, for example synthetic composition.This value may show plant base source, for example from the flue gas of combustion of fossil fuel, and can be used for verifying in this said composition carbon part or fully from the burning of fossil fuel.Might contain component, for example CO from the flue gas burning ₂With optional other component, as sulfur-bearing-, nitrogen-and/or heavy metal-the composition of component can be used as and from environment, seal the carrier that this class material is used up for safekeeping, and also can have other purposes, as be used in the architectural environment.In some embodiments, said composition is a synthetic composition.The synthetic composition that provides in some embodiments of the present invention contains by generation usually and has negative δ ¹³Any synthetic method of the product of the carbon of C value forms, and still, they can pass through CO ₂Gas is sealed up for safekeeping in this synthetic composition and is formed, and for example, said composition can be by to the CO that wherein introduces from for example combustion of fossil fuel ₂Deposited material forms in the aqueous solution of gas.Other possible composition of the present invention, for example synthetic composition comprises containing for example have negative δ ¹³The carbonate of C value and/or the aqueous solution of bicarbonate, or not only contained the slurry of solid but also property of water-bearing liquid---this solid and/or waterborne liquid can contain and for example have negative δ ¹³The carbonate of C value and/or bicarbonate.Said composition can be with greater than 1 kilogram, as greater than 10 kilograms, for example, greater than double centner, greater than 1000 kilograms, greater than 100,000 kilograms, greater than 1,000,000 kilogram or even greater than 10,000,000 kilogram amount exists.Said composition can for example have 1 kilogram to 10,000,000 kilogram, or 10 kilograms to 10,000,000 kilogram, or double centner to 10,000,000 kilogram, or 1000 kilograms to 10,000,000 kilogram, or 10,000 kilograms to 10,000,000 kilogram, or 1 kilogram to 1,000,000 kilogram, or 10 kilograms to 1,000,000 kilogram, or double centner to 1,000,000 kilogram, or 1000 kilograms to 1,000,000 kilogram, or 10,000 kilograms to 1,000,000 kilogram, or 1 kilogram to 100,000 kilograms, or 10 kilograms to 100,000 kilograms, or double centner to 100,000 kilogram, or 1000 kilograms to 100,000 kilograms, or 10,000 kilograms to 100,000 kilograms, or 1 kilogram to 10,000 kilogram, or 10 kilograms to 10,000 kilograms, or double centner to 10,000 kilogram, or 1000 kilograms to 10,000 kilograms, or 1 kilogram to 1000 kilograms, or 10 kilograms to 1000 kilograms, or the quality of double centner to 1000 kilogram.In some cases, said composition can be a solid block.In some cases, said composition can be made of particle, wherein each particle is less relatively, 0.1-1000 micron average diameter for example, or in some cases, even 1000 microns to several centimetres or bigger diameter, or its combination, in this case, said composition is regarded as the total particle material in single batch, single heap or single container etc.Under the situation of more substantial composition, what possibility was desirable is to extract a plurality of samples to determine for example δ ¹³The exact value of C value and/or carbon content.Composition of the present invention can also have the averag density in the certain limit of dropping on, and for example, in some embodiments, composition of the present invention has 501b/ft ³To 2001b/ft ³Volume density (bulk density) and 75lb/ft in certain embodiments ³To 125lb/ft ³Volume density.Composition of the present invention can also have the average hardness in the certain limit of dropping on, and as in some embodiments, composition of the present invention has puts on 1 to 7 average hardness in Mohs' hardness.In some embodiments, composition of the present invention has on Mohs (Mohs) hardness ga(u)ge at least 3 average hardness.In some embodiments, composition of the present invention has and puts at least 4 average hardness in Mohs' hardness.In some embodiments, composition of the present invention has and puts at least 5 average hardness in Mohs' hardness.In some embodiments, composition of the present invention has puts on 1 to 6 average hardness in Mohs' hardness, as put on 1 to 5 in Mohs' hardness, as 2 to 5, as 1 to 4, as 2 to 6, as 2 to 4.

In some embodiments, composition of the present invention comprises δ ¹³The C value is less than-5.00 ‰ ,-6 ‰ ,-7 ‰ ,-8 ‰ ,-9 ‰ ,-10 ‰ ,-11 ‰ ,-12 ‰ ,-15 ‰ ,-17 ‰ ,-20 ‰ ,-21.0 ‰ ,-21.7 ‰ ,-21.8 ‰ ,-21.9 ‰ ,-22.0 ‰ ,-23.0 ‰ ,-24.0 ‰ ,-25.0 ‰ ,-26.0 ‰ ,-27.0 ‰ ,-28.0 ‰ ,-29.0 ‰ ,-30.0 ‰ ,-31.0 ‰ ,-32.0 ‰ ,-35.0 ‰ or-40.0 ‰ carbon.In some of these embodiments, said composition can further have 1%w/w at least, as 10%w/w at least, for example, 20%w/w at least, in some embodiments, at least 30%w/w, 40%w/w or even the carbon dioxide content of 50%w/w (for example, in some embodiments, be carbonate, bicarbonate, or the form of the combination of carbonate and bicarbonate).Can determine carbon dioxide content by any suitable analysis known in the art and/or computing method.In some embodiments, the invention provides composition, the slurry of solid composite or solid and the aqueous solution for example, this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value is less than-5 ‰, in certain embodiments this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value less than-5 ‰ and carbon dioxide content be at least 10%.In some embodiments, this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value is less than-10 ‰, in certain embodiments this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value less than-10 ‰ and carbon dioxide content be at least 10%.In some embodiments, this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value is less than-15 ‰, in certain embodiments, and this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value less than-15 ‰ and carbon dioxide content be at least 10%.In some embodiments, this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value is less than-20.0 ‰, in certain embodiments this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value less than-20 ‰ and carbon dioxide content be at least 10%.In some embodiments, this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value is less than-22.0 ‰, in certain embodiments, and this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value less than-22 ‰ and carbon dioxide content be at least 10%.In some embodiments, this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value is less than-23.0 ‰, in certain embodiments, and this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value less than-23 ‰ and carbon dioxide content be at least 10%.In some embodiments, this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value is less than-24.0 ‰, in certain embodiments, and this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value less than-24 ‰ and carbon dioxide content be at least 10%.In some embodiments, this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value is less than-25.0 ‰, in certain embodiments, and this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value less than-25 ‰ and carbon dioxide content be at least 10%.In some embodiments, this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value is less than-27.0 ‰, in certain embodiments, and this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value less than-27 ‰ and carbon dioxide content be at least 10%.In some embodiments, this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value is less than-30.0 ‰, in certain embodiments, and this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value less than-30 ‰ and carbon dioxide content be at least 10%.In some embodiments, this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value is less than-40.0 ‰, in certain embodiments, and this carbonaceous composition, for example δ of He Cheng carbonaceous composition ¹³The C value less than-40 ‰ and carbon dioxide content be at least 10%.

In some embodiments of the present invention, provide except that having negative δ as described herein ¹³C value outer still (carbon neutral) or (carbon negative) carbonaceous composition of carbon negativity, for example He Cheng carbonaceous composition of neutral carbon.Neutral carbon is that expression is compared the term of the carbon dioxide gas scale of construction that discharges in this product production with stoped the amount of carbon dioxide that enters atmosphere (promptly sealing up for safekeeping) by this product with the carbon negativity.The as many carbonic acid gas of amount that product prevention and this product of neutral carbon discharges in producing arrives earth atmosphere.The product of carbon negativity stops the carbonic acid gas of Duoing than the amount that discharges in this product production process to arrive earth atmosphere.For example, the flue gas of spontaneous power plant in the future inject can not saturating underground storage storehouse carbonic acid gas seal method up for safekeeping, the carbonic acid gas that contrast produces to the mechanical system supplying power of implementing this flue gas injection is weighed by this and is sealed the actual carbonic acid gas that enters atmosphere that stops of technology up for safekeeping.Seal the carbonic acid gas that mechanical system discharges if enter this carbonic acid gas that can not store the storehouse thoroughly up for safekeeping more than this, then this method is the carbon negativity.In patent application US 12/344,019 (specifically being the 7th page) that is incorporated herein by this reference in full and application US 61/117,541 (specifically being 1 and 2 page), elaborate the notion of carbon negativity product or method.

In some embodiments, composition of the present invention contains strontium, 0.001% to 5%w/w/ strontium for example, or 0.00001% to 1%w/w strontium, or 0.001% to 0.1%w/w strontium, or 0.01% to 5%w/w strontium, or 0.01% to 1%w/w strontium, or 0.01% to 0.1%w/w strontium, or 0.1% to 5%w/w strontium, or 0.1% to 1%w/w strontium.In some embodiments, composition of the present invention contains boron, 0.000001% to 2.0%w/w boron for example, or 0.00001% to 1%w/w boron, or 0.0001% to 0.1%w/w boron, or 0.001% to 1%w/w boron, or 0.001% to 0.1%w/w boron, or 0.1% to 5%w/w boron, or 0.1% to 1%w/w boron.In some embodiments, composition of the present invention contains selenium, 0.000001% to 2.0%w/w selenium for example, or 0.00001% to 1%w/w selenium, or 0.0001% to 0.1%w/w selenium, or 0.001% to 1%w/w selenium, or 0.001% to 0.1%w/w selenium, or 0.1% to 5%w/w selenium, or 0.1% to 1%w/w selenium.

In some embodiments, provide carbonaceous composition, He Cheng carbonaceous composition for example, wherein said composition contains and has negative δ as described herein ¹³The carbon of C value, wherein the described carbon of at least a portion is carbonate and/or bicarbonate, for example the form of the carbonate of beryllium, magnesium, calcium, strontium, barium or radium or its combination and/or bicarbonate.The mol ratio of carbonate and bicarbonate can be any suitable ratio of the desired use of the manufacture method that is fit to said composition and/or said composition, as: carbonate than for greater than 100/1, less than 1/100, greater than 50/1,25/1,10/1,9/1,8/1,7/1,6/1,5/1,4/1,3/1,2/1,1/1,1/2,1/3, or 1/4; Less than 50/1,25/1,10/1,9/1,8/1,7/1,6/1,5/1,4/1,3/1,2/1,1/1,1/2,1/3, or 1/4; Or be carbonate substantially entirely or be bicarbonate substantially entirely.In some embodiments, this carbonate ratio can be 100/1 to 1/100, or 50/1 to 1/50 or 25/1 to 1/25, or 10/1 to 1/10, or 5/1 to 1/5, or 2/1 to 1/2, or 100/11/10, or 100/1 to 1/1, or 50/1 to 1/10, or 50/1 to 1/1, or 25/1 to 1/10, or 25/1 to 1/1, or 10/1 to 1/1, or 1/100 to 10/1, or 1/100 to 1/1, or 1/50 to 10/1, or 1/50 to 1/1, or 1/25 to 10/1, or 1/25 to 1/1, or 1/10 to 1/1.In some embodiments, the invention provides carbonate and/or the carbonaceous composition of bicarbonate, for example He Cheng carbonaceous composition that contains calcium or magnesium or its combination.In some embodiments, the invention provides the carbonate of calcic only or magnesium or its combination and potassium-containing hydrogen salt not, or only contain the carbonaceous composition of trace bicarbonate, for example He Cheng carbonaceous composition.Other embodiments provide the carbonaceous composition of the bicarbonate that only comprises calcium or magnesium or its combination, for example He Cheng carbonaceous composition.Not only providing calcium but also provide in embodiment of the present invention of magnesium, various embodiments comprise carbonaceous composition, for example the calcium of the certain limit in the He Cheng carbonaceous composition/magnesium atom ratio.In some embodiments of the present invention, this calcium/magnesium mol ratio (Ca/Mg) scope is to greater than 200/1 less than 1/200.In some embodiments, the Ca/Mg ratio is 1/1.In some embodiments, Ca/Mg is 2/1 to 1/2,3/2 to 2/3 than scope, or 5/4 to 4/5.In some embodiments, Ca/Mg is 1/7 to 200/1,1/15 to 12/10,1/10 to 5/1,1/7 to 1/2 than scope, or 1/9 to 2/5.In some embodiments, Ca/Mg is 1/200 to 1/7,1/70 to 1/7 or 1/65 to 1/40 than scope.In some embodiments, the Ca/Mg scope is 1/3 to 3/1 or 1/2 to 2/1.In some embodiments, the Ca/Mg scope is 2/1 to full calcium, 3/1 to 200/1,5/1 to 200/1, or 10/1 to 200/1.

In some embodiments, in carbonaceous composition, comprise removing carbon dioxide or be derived from other component outside the titanium dioxide carbon compound (for example carbonate and/or bicarbonate).For example, in some embodiments, the carbon that exists in the said composition to small part is derived from the burning of fossil fuel and the generation of flue gas, and for example in industrial process, and other component of this fossil fuel also may provide the annexing ingredient of this carbonaceous composition.Exemplary compositions comprises burning gases, for example nitrogen oxide (NO _x); Oxysulfide (SO _x) and sulphide; Halide is as hydrogen chloride and hydrogen fluoride; Particle as flying dust, cement flue Dust, other dust and metal, comprises arsenic, beryllium, boron, cadmium, chromium, chromium VI, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium or vanadium; And organic matter, as hydrocarbon and VOC (VOC), radioactive material, bioxin and PAH compound.PAH (polycyclic aromatic hydrocarbon) is the organic compound of making when the material of burning carbonaceous and hydrogen.Nitrogen oxide (NO used herein _x) be meant nitrogen oxide, for example nitric oxide (NO) and nitrogen dioxide (NO ₂); Oxysulfide (SO _x) be meant sulfur oxide, for example sulphur dioxide (SO ₂) and sulfur trioxide (SO ₃).In all these embodiments, can recognize, these components may interact with other participant in the reaction that forms this synthetic carbonaceous composition, so that these components are present in the product (synthetic carbonaceous composition) with the derivative form of original components.

In some embodiments, composition of the present invention can comprise flying dust.In some embodiments, composition of the present invention contains 0.001%w/w-10.0%, as 0.01%w/w-5.0%w/w, as 0.1%w/w-5.0%w/w, as 1.0%w/w-5.0%w/w, as 1.0%w/w-4.0%w/w, as 1.0%w/w-3.0%w/w, as 1.0%w/w-2.5%w/w, as the flying dust of the amount of 0.1%w/w to 2.5%w/w flying dust.In some embodiments, composition of the present invention contains 0.0000001-0.1%w/w, 0.000001-0.1%w/w for example, or 0.00001-0.1%, or 0.0000001-0.01%, or 0.0000001-0.001%, or 0.0000001-0.001%, or 0.0000001-0.00001%, or 0.000001-0.1%, or 0.000001-0.01%, or 0.000001-0.001%, or 0.000001-0.0001%, or 0.000001-0.00001%, or 0.00001-0.01%, or 0.00001-0.001%, or one or more mercury compounds of the amount of 0.00001-0.0001w/w, for example mercury chloride and/or other mercury compound.In some embodiments, composition of the present invention contains 0.01-30%w/w, for example 0.01-20%w/w, or 0.01-10%w/w, or 0.01-1%w/w, or 0.1-30%w/w, for example 0.1-20%w/w, or 0.1-10%w/w, or 0.1-1%, or 1-30%w/w, 1-20%w/w for example, 1-10%w/w, or one or more sulphur compounds of the amount of 1-5%w/w, for example one or more sulphate, sulphite, or the combination of sulphate and sulphite.In some embodiments, composition of the present invention contains 0.01-30%w/w, for example 0.01-20%w/w, or 0.01-10%w/w, or 0.01-1%w/w, or 0.1-30%w/w, 0.1-20%w/w for example, or 0.1-10%w/w, or 0.1-1%, or 1-30%w/w, for example 1-20%w/w, 1-10%w/w, or one or more nitrogenous compounds of the amount of 1-5%w/w, the derivative of NOx for example is as nitrate or nitrite.As can be seen, composition can contain one or more in flying dust, mercury compound, sulphur compound or the nitrogenous compound in above-mentioned weight percentage ranges, for example one or more mercury, sulphur or nitrogenous compound.

In some embodiments, the invention provides and contain δ ¹³The C value is less than-5 ‰, or less than-10 ‰, or less than-15 ‰, or less than-20 ‰, or less than the composition of-25 ‰ carbon, as synthetic composition, its also comprise following one or more: SO _xNO _xMetal comprises: arsenic, beryllium, boron, cadmium, chromium, chromium VI, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium or vanadium; VOCs; Particle is as flying dust; Or radioactive compound or derivatives thereof.In some embodiments, the invention provides δ ¹³The C value is less than-5 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises SO _xOr derivatives thereof.In some embodiments, the invention provides δ ¹³The C value is less than-5 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises particle, for example flying dust.In some embodiments, the invention provides δ ¹³The C value is less than-5 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises metal, for example arsenic, beryllium, boron, cadmium, chromium, chromium VI, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium and vanadium, or derivatives thereof.In some embodiments, the invention provides δ ¹³The C value is less than-5 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises SO _xOr derivatives thereof and particle, for example flying dust.In some embodiments, the invention provides δ ¹³The C value is less than-5 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises SO _xOr derivatives thereof and heavy metal, for example arsenic, beryllium, boron, cadmium, chromium, chromium VI, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium and vanadium, or derivatives thereof; In some embodiments, this heavy metal is the derivative compound of mercury or mercury.In some embodiments, the invention provides δ ¹³The C value is less than-5 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises particle, for example flying dust, and heavy metal, for example arsenic, beryllium, boron, cadmium, chromium, chromium VI, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium and vanadium or derivatives thereof; In some embodiments, this heavy metal is the derivative compound of mercury or mercury.In some embodiments, the invention provides δ ¹³The C value is less than-5 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises NO _xOr derivatives thereof.In some embodiments, the invention provides δ ¹³The C value is less than-5 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises the VOC or derivatives thereof.In some embodiments, the invention provides δ ¹³The C value is less than-15 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises SO _xOr derivatives thereof.In some embodiments, the invention provides δ ¹³The C value is less than-15 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises particle, for example flying dust.In some embodiments, the invention provides δ ¹³The C value is less than-15 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises metal, for example arsenic, beryllium, boron, cadmium, chromium, chromium VI, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium and vanadium, or derivatives thereof.In some embodiments, the invention provides δ ¹³The C value is less than-15 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises SO _xOr derivatives thereof and particle, for example flying dust.In some embodiments, the invention provides δ ¹³The C value is less than-15 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises SO _xOr derivatives thereof and heavy metal, for example arsenic, beryllium, boron, cadmium, chromium, chromium VI, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium and vanadium, or derivatives thereof; In some embodiments, this heavy metal is the derivative compound of mercury or mercury.In some embodiments, the invention provides δ ¹³The C value is less than-15 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, it further comprises particle, for example flying dust, and heavy metal, for example arsenic, beryllium, boron, cadmium, chromium, chromium VI, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium and vanadium, or derivatives thereof; In some embodiments, this heavy metal is the derivative compound of mercury or mercury.In some embodiments, the invention provides δ ¹³The C value is less than-15 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises NO _xOr derivatives thereof.In some embodiments, the invention provides δ ¹³The C value is less than-15 ‰ carbonaceous composition, He Cheng carbonaceous composition for example, and it further comprises the VOC or derivatives thereof.In the patent application US 61/156,809 (specifically at 1-2,19-24 and 32-39 page or leaf) that is incorporated herein by this reference in full, provide the more details that comprise about the industrial process accessory substance.

As described herein, in some embodiments, the carbon that exists in the said composition to small part is derived from fossil fuel, for example the generation of burning of coal and flue gas, for example in industrial process, and other component of this fossil fuel also may provide the annexing ingredient of this synthetic carbonaceous composition.Except that the component that above describes in detail, for example there is other element in fossil fuel in the coal, and they are by fractionating process, also as method partly in more abundant description and have the isotope ratio that can compare with standard as known in the art.For example, for example also can use mass spectrometry measure oxygen ( ¹⁶O and ¹⁸O), nitrogen ( ¹⁴N and ¹⁵N), sulphur ( ³²S and ³⁴S), hydrogen ( ¹H and ²H) and boron ( ¹⁰B and ¹¹The ratio of stable isotope B).Therefore, in some embodiments, the invention provides and comprise δ ¹³The C value is less than the composition of-5 ‰ carbon, and it further comprises δ ¹¹The B value is less than-2 ‰, less than-5 ‰, less than-7 ‰, less than-10 ‰, less than-12 ‰, less than-14 ‰, less than-15 ‰, less than-17 ‰; Less than-20 ‰, less than-22 ‰, less than-25 ‰ or less than-30 ‰ boron; δ ³⁴The S value is less than-5 ‰ or 0 to+10 ‰ sulphur, or its combination.These compositions can further contain SO as further described herein _x-derivative compound, NO _xIn-derivative compound or the mercury-derivative compound one or more.

In some embodiments of the present invention, this carbonaceous composition, for example He Cheng carbonaceous composition comprises magnesium carbonate or calcium carbonate or its combination.In some embodiments, this carbonaceous composition comprises dolomite, has chemical formula Ca _0.5Mg _0.5CO ₃Calcic and the carbonate and/or the former dolomite (calcium/magnesium ratio departs from 1: 1 amorphous dolomite) of magnesium.Other embodiments contain the CaCO of form of the combination of one or more or they in mineral calcite, aragonite or the vaterite ₃Some embodiments have calcium carbonate hydration form, comprising: six hydroconite (CaCO ₃6H ₂O), amorphous calcium carbonate (CaCO ₃H ₂O) or single hydroconite (CaCO ₃H ₂O) or its combination.Some embodiments contain the magnesium carbonate of various hydration levels, and wherein hydrate water comprises 1,2,3,4 or greater than 4 hydrate waters or its combination, as no hydration, as magnesite (MgCO ₃) or three hydrations, as nesquehonite (MgCO ₃3H ₂O).Other embodiments comprise more complicated magnesium carbonate form, and it comprises hydrate water and hydroxide, as artinite (MgCO ₃Mg (OH) ₂3H ₂O), ball carbon magnesite (Mg ₅(CO ₃) ₄(OH) ₂5H ₂O) or hydromagnesite (Mg ₅(CO ₃) ₄(OH) ₂3H ₂O) or its combination.Some embodiments comprise the calcium that presents all or some various hydrated state as herein described and/or the carbonate of magnesium.

In some embodiments, the invention provides the carbonaceous composition that comprises carbonate or bicarbonate or its combination, He Cheng carbonaceous composition for example, wherein the carbon in this carbonate or the bicarbonate has less than-5 ‰ or less than-10 ‰ or less than-15 ‰ or less than-20 ‰ or less than-25 ‰ or less than-30 ‰ or less than-35 ‰ δ ¹³The C value, wherein said composition is being exposed to normal temperature and the damp condition that is used for its desired use, comprises in the rainwater with normal pH at least 1,2,5,10 or 20 year, or more than 20 years, does not discharge more than its total CO during for example more than 100 years ₂1%, or 5%, or 10%.In some embodiments, said composition is being exposed to normal temperature and the damp condition that is used for its desired use, does not discharge more than its total CO when comprising in the rainwater with normal pH at least 1 year ₂1%.In some embodiments, said composition is being exposed to normal temperature and the damp condition that is used for its desired use, does not discharge more than its total CO when comprising in the rainwater with normal pH at least 1 year ₂5%.In some embodiments, said composition is being exposed to normal temperature and the damp condition that is used for its desired use, does not discharge more than its total CO when comprising in the rainwater with normal pH at least 1 year ₂10%.In some embodiments, said composition is being exposed to normal temperature and the damp condition that is used for its desired use, does not discharge more than its total CO when comprising in the rainwater with normal pH at least 10 years ₂1%.In some embodiments, said composition is being exposed to normal temperature and the damp condition that is used for its desired use, does not discharge more than its total CO when comprising in the rainwater with normal pH at least 100 years ₂1%.In some embodiments, said composition is being exposed to normal temperature and the damp condition that is used for its desired use, does not discharge more than its total CO when comprising in the rainwater with normal pH at least 1000 years ₂1%.But can use any suitable surrogate markers or the test of this stability of rational prediction; Can use temperature condition or the pH condition that for example may reasonably in accelerated test, indicate the rising of long-time stability.For example, desired use and environment according to said composition, the sample that can make said composition exposes 1,2,5,25,50,100,200 or 500 day under 50,75,90,100,120 or 150 ℃ and 10% to 50% relative moisture, and the loss less than 1%, 2%, 3%, 4%, 5%, 10%, 20%, 30% or 50% of its carbon can be regarded as in given period, for example 1,10,100,1000 or more than the ample evidence of the stability in 1000.Can be by any suitable method, for example coulometry is monitored the CO of this material ₂Content.Can still regulate other condition, comprise pH, pressure, ultraviolet radiation etc. according to expection or possible fitness of environment.Recognize, can use those skilled in the art rationally to be estimated as any appropriate condition of the essential stability of indication in designated period of time.In addition, show that said composition has the essential stability in designated period of time if generally acknowledge chemical knowledge, this also can replenish or replace actual measurement to use.For example, some carbonate compounds (for example being the polymorph form of appointment) that can become the part of composition of the present invention can be known and known tolerance normal climate decades on the geology, a few century or even several thousand and obviously do not decompose, therefore have essential stability.

In some embodiments, the invention provides the construction material that contains the component that comprises carbonate or bicarbonate or its combination, wherein the carbon in this carbonate and/or the bicarbonate has less than-5.00 ‰, for example less than-10 ‰, as and in some embodiments less than-15 ‰, the δ less than-20 ‰ ¹³The C value.Term used herein " construction material " comprises performance or can be used for any material of building occupancy, for example, but be not limited to work and family place, industrial structure and transportation dependency structure, as highway, parking lot and parking structure, and environmental structure, as dam, flood bank etc.In some of these embodiments, this construction material further contains SO as mentioned above _xNO _xMetal comprises: arsenic, beryllium, boron, cadmium, chromium, chromium VI, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium or vanadium; VOC; Particle is as flying dust; Or radioactive compound or derivatives thereof, or its combination.In addition, in some embodiments, also as mentioned above, this construction material is being exposed to normal temperature and the damp condition that is used for its desired use, comprise in the rainwater with normal pH at least 1,2,5,10 or 20 year, or, do not discharge more than its total CO during for example more than 100 years more than 20 years ₂1%, or 5%, or 10%.In some embodiments, the invention provides and contain gathering materials of the component that comprises carbonate or bicarbonate or its combination, synthetic aggravation for example, wherein the carbon in this carbonate or the bicarbonate has less than-5 ‰, for example less than-10 ‰, as less than-15 ‰ with in some embodiments less than-20 ‰ δ ¹³The C value.In some embodiments, of the present invention gather materials be that fine aggregate, coarse aggregate, reactivity gather materials, inertia or non-reacted gathering materials, or be shaped or casting is gathered materials.Reactivity is gathered materials and chemical reaction is taken place so that it is attached to gathering materials on the material around when being hydration.Some embodiments provide the cementaceous construction material that contains the component that comprises carbonate or bicarbonate or its combination, wherein the carbon in this carbonate or the bicarbonate has less than-5 ‰, for example less than-10 ‰, as less than-15 ‰ with in some embodiments less than-20 ‰ δ ¹³The C value.Some embodiments provide cement or the concrete that contains the component that comprises carbonate or bicarbonate or its combination, wherein the carbon in this carbonate or the bicarbonate has less than-5 ‰, for example less than-10 ‰, as less than-15 ‰ with in some embodiments less than-20 ‰ δ ¹³The C value.In some embodiments, the invention provides other cementaceous construction material that contains the component that comprises carbonate or bicarbonate or its combination, as: mortar, pozzolanic materials or auxiliary water earthy material or its combination, wherein the carbon in this carbonate or the bicarbonate has less than-5 ‰, for example less than-10 ‰, as less than-15 ‰ with in some embodiments less than-20 ‰ δ ¹³The C value.In some embodiments, the invention provides the non-cementaceous construction material that contains the component that comprises carbonate or bicarbonate or its combination, as: pavement material, brick, plate, conduit, beam, basin, post, watt, fibre wall panel products, base, soundproof wall, gypsum, drywall, plaster, soil fixation composition or barrier material or their combination, wherein the carbon in this carbonate or the bicarbonate has less than-5 ‰, for example less than-10 ‰, as less than-15 ‰ with in some embodiments less than-20 ‰ δ ¹³The C value.In some embodiments, this pavement material can be pitch or paving material.

Embodiments more of the present invention provide the non-construction material that contains the component that comprises carbonate or bicarbonate or its combination, wherein the carbon in this carbonate and/or the bicarbonate has less than-5 ‰, for example less than-10 ‰, as less than-15 ‰ with in some embodiments less than-20 ‰ δ ¹³The C value.In some embodiments, this non-construction material comprises: family expenses or commercial ceramic product; Paper product; Polymerization product; Lubricant; Adhesive; Rubber product; Chalk; Lacquer; The personal care product; Cosmetics; Edible product; Agricultural product; Or environment remediation product.In some embodiments, the invention provides the personal care product, comprise cleaning products or personal hygiene products.In some embodiments, the invention provides the edible product that contains the component that comprises carbonate or bicarbonate or its combination, comprise liquid, solid-state or animal edible product, wherein the carbon in this carbonate and/or the bicarbonate has less than-5 ‰, for example less than-10 ‰, as less than-15 ‰ with in some embodiments less than-20 ‰ δ ¹³The C value.Embodiments more of the present invention provide the agricultural product that contain the component that comprises carbonate or bicarbonate or its combination, comprise soil melioration product or insecticide, wherein the carbon in this carbonate and/or the bicarbonate has less than-5 ‰, for example less than-10 ‰, as less than-15 ‰ with in some embodiments less than-20 ‰ δ ¹³The C value.Embodiments more of the present invention provide the environment remediation product that contains the component that comprises carbonate or bicarbonate or its combination, the product that comprises the forest soil reparation product or the sour water that neutralized, wherein the carbon in this carbonate and/or the bicarbonate has less than-5 ‰, for example less than-10 ‰, as less than-15 ‰ with in some embodiments less than-20 ‰ δ ¹³The C value.In some embodiments, the invention provides the paper product that contains the component that comprises carbonate or bicarbonate or its combination, wherein the carbon in this carbonate and/or the bicarbonate has less than-5 ‰, for example less than-10 ‰, as less than-15 ‰ with in some embodiments less than-20 ‰ δ ¹³The C value.Embodiments more of the present invention provide the lubricant that contains the component that comprises carbonate or bicarbonate or its combination, and wherein the carbon in this carbonate and/or the bicarbonate has the δ less than-5 ‰ ¹³The C value.In some embodiments, the invention provides the lacquer that contains the component that comprises carbonate or bicarbonate or its combination, wherein the carbon in this carbonate and/or the bicarbonate has the δ less than-5 ‰ ¹³The C value.Construction material of the present invention also can have the average hardness in the certain limit of dropping on, and as in some embodiments, construction material of the present invention has puts on 1 to 7 average hardness in Mohs' hardness.In some embodiments, construction material of the present invention has and puts at least 3 average hardness in Mohs' hardness.In some embodiments, construction material of the present invention has and puts at least 4 average hardness in Mohs' hardness.In some embodiments, construction material of the present invention has and puts at least 5 average hardness in Mohs' hardness.In some embodiments, construction material of the present invention has puts on 1 to 6 average hardness in Mohs' hardness, as put on 1 to 5 in Mohs' hardness, as 2 to 5, as 1 to 4, as 2 to 6, as 2 to 4.

In some embodiments, but the invention provides flow composition.In some embodiments, but should flow composition be pseudoplastic (but viscosity that promptly should flow composition improve reduce) with shear rate.In some embodiments, but should flow composition be thixotropic (be viscosity under constant shearing in time through and reduce).In some embodiments, viscosity and non-newtonian behaviour improve with solid concentration.In some embodiments, but slurry form should have at 20 ℃ greater than 1cP (centipoise) by flow composition, as greater than 5cP, greater than 10cP, greater than 15cP, greater than 20cP, greater than 25cP, greater than 30cP, greater than 35cP, greater than 40cP, greater than 45cP, greater than 50cP, greater than 75cP, greater than 100cP, greater than 250cP, greater than 500cP, greater than the viscosity of 750cP, or 20 ℃ of viscosity greater than 1000cP.In some embodiments, but flow composition has 2000cP to 1cP, as 100cP to 1000cP, comprises 150cP to 500cP, for example the viscosity of 200cP to 400cP.For example, but should can have 300cP to 400cP by flow composition, as the viscosity of about 380cP.But consider the pseudoplastic behavior of this flow composition, viscosity may improve with shear rate and reduce.In addition, but consider the thixotropy of some flow compositions, viscosity may be under constant shearing in time through and reduce.In some embodiments, but should flow composition be to comprise from the solid sediment of carbon sequestration method and the slurry of trickle.In this type of embodiment, this solid sediment includes, but not limited to any combination of carbonate, bicarbonate and carbonate and bicarbonate.In some embodiments that this solid sediment is generated by the carbon sequestration method of using from the flue gas of combustion of fossil fuel process, this sediment has negative δ ¹³The C value.In this type of embodiment, the carbonate that comprises in this sediment, any combination of bicarbonate or carbonate and bicarbonate has less than (promptly more negative)-5 °/00, as less than-6 °/00, less than-7 °/00, less than-8 °/00, less than-9 °/00, less than-10 °/00, less than-15 °/00, less than-20 °/00, less than-21 °/00, less than-22 °/00, less than-23 °/00, less than-24 °/00, less than-25 °/00, less than-26 °/00, less than-27 °/00, less than-28 °/00, less than-29 °/00, less than-30 °/00, less than-35 °/00, δ less than-40 °/00 ¹³The C value.In some embodiments, but be somebody's turn to do other composition that flow composition comprises industrial flue gas, such as but not limited to: carbon monoxide, nitrogen oxide (NOx), oxysulfide (SOx), sulphide, halide, particle such as flying dust and dust; Metal and metallic compound, radioactive material and organic matter.In some embodiments, but with flow composition place the storage storehouse.In some embodiments, but flow composition is placed the subsurface geology rock stratum.In some embodiments, this geological formations is not suitable for storing supercritical carbon dioxide.In some embodiments, but this geological formations is the carbonic acid gas that is used to form the component of this flow composition seals the component source of method up for safekeeping.In some embodiments, but but should flow composition be the pumping composition.But the pumping composition is to use conduit and pump to transport the composition on another ground to from a ground.In some embodiments, but the invention provides the flow composition that comprises carbonate, bicarbonate or its combination, wherein the carbon in this carbonate, bicarbonate or its combination has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) viscosity of value and said composition is 1 to 2000cP, and for example 10 to 1000cP.In some embodiments, said composition is a synthetic composition.In some embodiments, this carbonate, bicarbonate or its constitute the 10%w/w at least of said composition.In some embodiments, the CO2 content of said composition is at least 10%.In some embodiments, said composition has negativity carbon footprint.In some embodiments, said composition further comprises boron, sulphur or nitrogen, and wherein the relative isotopics of this boron, sulphur or nitrogen show the fossil fuel source.In some embodiments, this carbonate, bicarbonate or its combination comprise calcium, magnesium or its combination, and for example wherein calcium and magnesium (Ca/Mg) mol ratio is 1/200 to 200/1, or 12/11/15, or 5/1 to 1/10.Other appropriate C a/Mg is such as described herein.Said composition can further comprise the SOx or derivatives thereof, as sulphate, sulphite or its combination.Said composition can further comprise metal, as lead, arsenic, mercury or cadmium or its combination.

Composition of the present invention can be used for for example needing to use and contains the carbon that maybe may contain plant origin, and the carbon in fossil fuel source for example is for example as the purposes of the material of the carbon of the part of the carbonic acid gas that will discharge into the atmosphere originally.In some cases, can provide Economic Stimulus for using this class material, for example the carbon compensatory payment.In some cases, the use of this class material can meet the management and/or the incentive plan of government.

Making method for compositions of the present invention comprises and can have essential δ by its manufacturing ¹³Any suitable method of the carbon of C value.These class methods for example are described in U.S.'s publication application Nos.2009/0020044 and 2009/0001020 and U.S. Patent application No.12/344, and in 019, their disclosure is incorporated herein by this reference in full.For example, the water that contains bivalent cation is exposed to from industrial source, for example from coal-fired power plant or other source, flue gas in, wherein this flue gas contains CO ₂, this CO ₂Contain the carbon that is derived from fossil fuel mainly or fully.This water that contains bivalent cation can be for example seawater, salt solution and/or the water of enrichment bivalent cation.As U.S. publication application Nos.2009/0020044 and 2009/0001020 and U.S. Patent application No.12/344, what be described in further detail in 019 is such, by adding alkali (hydroxide for example, as sodium hydroxide or from industrial waste, salt solution, mineral, or the alkali in other source) and/or by electrochemical method, from this water, remove deprotonation, trend towards carbonate to order about reaction, for example magnesium carbonate and/or calcium carbonate, it can be stayed in the solution and maybe can precipitate from solution.Can described in above-mentioned publication application, further handle this sediment, for example by drying, pressurization, crushing, shaping etc.In above-mentioned patent application, also describe negative carbon autofrettage, for example utilized low voltage electrochemical to remove alkaline process, for example need be less than 2.0V, or less than 1.5V or in some embodiments less than the method for the electrochemical method of the voltage of 1.0V.

The more detailed below certain methods of making composition of the present invention that provides still, can be used any suitable method.As described further below such, this method and system utilizes CO ₂Said composition is made in source, proton free agent source (and/or proton free method) and bivalent cation source.

Carbonic acid gas

Method comprises the bivalent cation aqueous solution and the CO that makes certain volume ₂The source contact under the sedimentary situation of needs, imposes the condition that promotes precipitation to gained solution; In some cases, need to make solution or slurry, but flow composition for example, and can correspondingly cancel or regulate deposition condition.Therefore method of the present invention may further include the bivalent cation aqueous solution and the CO that makes certain volume ₂The source contact also imposes the condition that promotes precipitation to the described aqueous solution simultaneously.This contains the deposited material (for example from seawater or salt solution) that carbonic acid gas in the solution of bivalent cation may be enough to precipitate the potassium-containing hydrogen salt and/or the carbonate of significant quantity; But, use the carbonic acid gas that appends usually.This CO ₂The source can be to contain to have essential δ ¹³Any CO easily of the carbon of C value ₂The source.This CO ₂The source can be gas, liquid, solid (for example dry ice), supercritical fluid, or is dissolved in the CO in the liquid ₂In some embodiments, this CO ₂The source is gaseous state CO ₂The source.This air-flow can be the CO of substantially pure ₂, or comprise multicomponent---comprise CO ₂With one or more additional gas and/or other material, as ash content and other particle.In some embodiments, this gaseous state CO ₂The source is a waste gas stream (being the accessory substance of the active procedure of factory), as the exhaust of factory.The character of factory can not wait, and this factory includes but not limited to power plant, chemical processing plant (CPP), machining factory, refinery, cement plant, steel mill and the accessory substance of act as a fuel burning or another procedure of processing (for example calcining in cement plant) produces CO ₂Other factory.

Comprise CO ₂Waste gas stream both comprised reducing condition stream (for example synthesis gas of synthesis gas, conversion, natural gas, hydrogen etc.), comprise oxidizing condition stream (for example burning produce flue gas) again.For the purpose of the present invention may specific easily waste gas stream comprise boiler product gas, the coal gasification product gas of oxygen containing burning factory's flue gas (for example from coal or another carbon-based fuel, this flue gas almost or does not fully have preliminary treatment), gas turbine supercharging, coal gasification product gas, anaerobic digester product gas, well head natural gas flow, reformation natural gas or the methane hydrate etc. of conversion.In method and system of the present invention, can use burning gases from any convenient source.In some embodiments, use factory, as the burning gases in the after-combustion blowdown stack of power plant, cement plant and coal processing factory.

Therefore, this waste streams can be produced by various dissimilar factories.Usually, the waste streams that is used for this method comprises the waste gas stream that the factory of combustion of fossil fuels (for example coal, oil, natural gas) and the sedimental artificial fuel's product of naturally occurring organic-fuel (for example tar sand, heavy oil, oil shale etc.) produces.In some embodiments, be applicable to that the waste streams of system and method for the present invention is derived from coal-fired power plant, as fine coal power plant, overcritical coal power generation factory, mass burn coal power generation factory, fluidized bed coal power plant; In some embodiments, this waste streams is derived from combustion gas or oil burning boiler and water vapour turbine power plant, combustion gas or oil burning boiler simple cycle gas turbine engine power plant, or combustion gas or oil burning boiler combined cycle gas turbine power plant.In some embodiments, the waste streams of using the power plant of burning synthesis gas (promptly by organic matter, for example the gas made of the gasification of coal, living beings etc.) to produce.In some embodiments, use is from the waste streams of integrated form gasification combination circulation (IGCC) factory.In some embodiments, system and a method according to the invention is used the waste streams that Waste Heat Recovery steam boiler (HRSG) factory produces.

The waste streams that the cement plant produces also is applicable to system and method for the present invention, as long as the δ of this flue gas ¹³The C value has essential δ with generation within the required range ¹³The product of C value.The cement plant waste streams is from wet method and dry method waste from a factory stream, and these factories can use shaft furnace or rotary kiln, and can comprise the precalcining stove.These factories are the incendivity single-fuel separately, or can be in succession or two or more fuel that burn simultaneously.Other factory also is the available source that comprises the waste streams of carbonic acid gas as smeltery and refinery.

Industrial waste gas stream can contain carbonic acid gas as main non-air compositions derived therefrom, or especially can contain annexing ingredient under the situation of coal-fired power plant, as nitrogen oxide (NOx), oxysulfide (SOx) and one or more additional gas.Additional gas and other component can comprise CO, mercury and other heavy metal, and powder dust particle (for example from calcining and combustion process).Annexing ingredient in this air-flow also may comprise halide, as hydrogen chloride and hydrogen fluoride; Particle as flying dust, dust and metal, comprises arsenic, beryllium, boron, cadmium, chromium, chromium VI, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium and vanadium; And organic matter, as hydrocarbon, bioxin and PAH compound.Accessible suitable gaseous state waste streams has in some embodiments with 200ppm to 1, and 000,000ppm, as 200,000ppm to 1000ppm comprises 200,000ppm to 2000ppm, for example 180,000ppm to 2000ppm, or 180,000ppm to 5000ppm, also comprise 180,000ppm to 10, the carbonic acid gas that the amount of 000ppm exists.The various waste streams of this waste streams, particularly burning gases can comprise one or more annexing ingredients, for example, and water, NOx (single nitrogen oxide: NO and NO ₂), SOx (single oxysulfide: SO, SO ₂And SO ₃), VOC (VOC), heavy metal such as mercury, and particle (being suspended in solid or liquid particle in the gas).Effluent gas temperature does not wait yet.In some embodiments, comprise CO ₂The temperature of flue gas be 0 ℃ to 2000 ℃, as 60 ℃ to 700 ℃, comprise 100 ℃ to 400 ℃.

In some embodiments, one or more annexing ingredients or common product (promptly are being used for CO ₂Change into the product of making by other source material [for example SOx, NOx etc.] under the same terms of bicarbonate and/or carbonate) precipitate or be trapped in that (alkaline-earth metal ions for example is as Ca with comprising bivalent cation by making the waste gas stream that comprises these annexing ingredients ²⁺And Mg ²⁺) aqueous solution contact and in the deposited material or solution or slurry that form.The sulphate of calcium and/or magnesium, sulphite etc. can precipitate or be trapped in by comprising SOx (SO for example ₂) waste gas the stream deposited material or solution or slurry (bicarbonate and/or the carbonate that further comprise calcium and/or magnesium) made in.Magnesium and calcium may react respectively and form MgSO ₄, CaSO ₄, and other contains the compound (for example sulphite) of magnesium and calcic, thus need not desulfurized step, as flue gas desulfurization (" FGD "), from this flue gas stream, effectively remove desulfuration.In addition, can additionally not discharge CO ₂And formation CaCO ₃, MgCO ₃And related compound.Contain at this bivalent cation aqueous solution under the situation of sulphur compound (for example sulfate radical) of high-load, can make this aqueous solution enrichment calcium and magnesium so that calcium and magnesium can be for forming CaSO ₄, MgSO ₄With after the related compound or except that forming CaSO ₄, MgSO ₄With formation bicarbonate and/or carbonate compound outside the related compound.In some embodiments, desulfurized step can stageization with synchronous with the precipitation of the deposited material of potassium-containing hydrogen salt and/or carbonate, or this desulfurized step can stageization before precipitation, to carry out.In some embodiments, collect multiple product (MgCO for example in different phase ₃, CaCO ₃, CaSO ₄, aforesaid mixture etc.), and in other embodiments, collect single reaction product (deposited material that for example, comprises carbonate, bicarbonate, sulphate and/or sulphite etc.).In using the step of these embodiments, other component may be trapped in the deposited material of potassium-containing hydrogen salt and/or carbonate or may precipitate (if the precipitation of use) independently as heavy metal (for example mercury, mercury salt, mercurous compound).

Can use a part of gaseous state waste streams (promptly not being whole gaseous state waste streams) to make solution, slurry or deposited material from factory.In these embodiments, be used for this method this part gaseous state waste streams can for this gaseous state waste streams 75% or lower, as 60% or lower, comprise 50% and lower.In other embodiments, basic (for example 80% or more) all gaseous state waste streams of using in the precipitation of deposited material, solution or slurry that this factory produces.In these embodiments, 80% or more, as 90% or more, comprise that gaseous state waste streams (for example flue gas) that this source of 95% or more, maximum 100% generates can be used for the precipitation of deposited material.Method of the present invention can be from given CO ₂Remove signal portion in the source, or all substantially CO ₂, for example surpass this CO ₂CO in the source ₂30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, or even surpass 99.9%.

Bivalent cation

Method of the present invention comprises the bivalent cation aqueous solution and the CO that makes certain volume ₂Source contact and the optional condition that promotes precipitation that gained solution is imposed.In some embodiments, make the bivalent cation aqueous solution and the CO of certain volume ₂The optional simultaneously condition that promotes precipitation that the described aqueous solution is imposed of source contact.Bivalent cation can according in the availability of locality from many different bivalent cation sources.This class source comprises industrial waste, seawater, salt solution, hard water, rock and mineral (for example lime, periclase, the material that comprises metal silicate such as serpentine and olivine) and any other suitable source.

In some places, provide the facility source of bivalent cation (and in some cases, available other material in this method is as metal hydroxides) from the industrial waste stream of various industrial process.This class waste streams includes but not limited to, the mining waste material; Combustion of fossil fuel ash (for example combustion ash of flying dust, bottom ash, slag and so on); Slag (for example scum, phosphorus slag); The cement kiln waste material; Oil plant/petrochemical refinery factory waste material (for example oil field and methane layer salt solution); Coal seam waste material (for example gas production salt solution and coal seam salt solution); The paper conversion waste material; Water softening effluent brine (for example ion exchange effluent); The silicon processing waste material; Agricultural residue; The metal finishing waste material; High pH textile waste; And alkaline residue.Combustion of fossil fuel ash, cement flue Dust and slag---be referred to as the waste sources of metal oxide, further describe the U.S. Patent application No.12/486 that submits on June 17th, 2009, in 692, its disclosure is incorporated herein by this reference in full.Recognize, some in these sources, for example coal seam waste material, flying dust itself are to have negative δ ¹³The carbon source of C value; Other may give the carbon of this value a little more than the value in the fossil fuel, but the uninevitable δ that significantly changes end product of their interpolation ¹³The C value for example makes it depart from value as herein described (detail is seen embodiment).Enforcement the present invention can be mixed and be applicable in any bivalent cation as herein described source.For example, the material (for example serpentine, olivine) that comprises metal silicate---further describe the U.S. Patent application No.12/501 that submits on July 10th, 2009, in 217, this application is incorporated herein by this reference---and can be used to implement any bivalent cation of the present invention source and combine with described herein.

In some places, the source of bivalent cation easily that is used to prepare composition of the present invention is water (for example, comprising the aqueous solution of bivalent cation, as seawater or face of land salt solution), and this can become with implementing locality of the present invention.The available suitable bivalent cation aqueous solution comprises and comprises one or more bivalent cations, and alkaline earth metal cation for example is as Ca ²⁺And Mg ²⁺, solution.In some embodiments, this water-based bivalent cation source comprises alkaline earth metal cation.In some embodiments, this alkaline earth metal cation comprises calcium, magnesium or its mixture.In some embodiments, this bivalent cation aqueous solution comprises 50 to 50,000ppm, and 50 to 40,000ppm, 50 to 20,000ppm, 100 to 10,000ppm, 200 to 5000ppm, or the calcium of 400 to 1000ppm amount.In some embodiments, this bivalent cation aqueous solution comprises 50 to 40,000ppm, and 50 to 20,000ppm, 100 to 10,000ppm, 200 to 10,000ppm, 500 to 5000ppm, or the magnesium of 500 to 2500ppm amount.In some embodiments, if Ca ²⁺And Mg ²⁺All there is Ca in this bivalent cation aqueous solution ²⁺With Mg ²⁺Ratio (be Ca ²⁺: Mg ²⁺) be 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 its scope.For example, in some embodiments, Ca in this bivalent cation aqueous solution ²⁺With Mg ²⁺Ratio be 1: 1 to 1: 10; 1: 5 to 1: 25; 1: 10 to 1: 50; 1: 25 to 1: 100; 1: 50 to 1: 500; Or 1: 100 to 1: 1000.In some embodiments, Mg in this bivalent cation aqueous solution ²⁺With Ca ²⁺Ratio (be Mg ²⁺: Ca ²⁺) be 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 its scope.For example, in some embodiments, Mg in this bivalent cation aqueous solution ²⁺With Ca ²⁺Ratio be 1: 1 to 1: 10; 1: 5 to 1: 25; 1: 10 to 1: 50; 1: 25 to 1: 100; 1: 50 to 1: 500; Or 1: 100 to 1: 1000.

This bivalent cation aqueous solution can comprise derived from fresh water, brackish water, seawater or salt solution (for example naturally occurring salt solution or artificial salt solution, as underground heat power plant effluent, desalter waste water) and salinity greater than the bivalent cation of other brackish water (salines) of fresh water, wherein any all may be naturally occurring or artificial.Brackish water is more salty but not as the salty water of seawater than fresh water.Brackish water has about 0.5 salinity to about 35ppt (thousand/umber).Seawater is that it has about salinity of 35 to about 50ppt from the water of sea, ocean or any other body of salt.Salt solution is salt loading or approaching saturated water.Salt solution has about 50ppt or bigger salinity.In some embodiments, the water source as the bivalent cation source is the freshwater source that is rich in mineral (for example rich calcium and/or rich magnesium).In some embodiments, the water source as the bivalent cation source is the naturally occurring salt water source that is selected from sea, ocean, lake, marsh, river mouth, lagoon, face of land salt solution, deep layer salt solution, alkali lake or inland sea etc.In some embodiments, the water source as the bivalent cation source is the artificial salt solution that is selected from underground heat power plant effluent or desalination waste water.

Fresh water normally easily bivalent cation (cation of alkaline earth metal for example is as Ca ²⁺And Mg ²⁺) source.Can use any of many suitable freshwater sources, comprise from the freshwater source in the barren relatively source of being rich in mineral relatively of originating.The rich ore freshwater source may be naturally occurring, comprises any hard water source, lake or inland sea.Some rich ore freshwater sources also provide the pH modifier source as alkali lake or inland sea (for example Lake Van of Turkey).The rich ore freshwater source also can be artificial.For example, can make lean ore (soft) water and bivalent cation source, as alkaline earth metal cation (Ca for example ²⁺, Mg ²⁺Deng) contact is applicable to the rich ore water of method and system as herein described with manufacturing.Can use any program easily (for example adding solid, suspension or solution) that bivalent cation or its precursor (for example salt, mineral) are added in the fresh water (or water of any other type as herein described).In some embodiments, will be selected from Ca ²⁺And Mg ²⁺Bivalent cation add in the fresh water.In some embodiments, will be selected from Na ⁺And K ⁺Monovalent cation add in the fresh water.In some embodiments, will comprise Ca ²⁺Fresh water merge with combustion ash (for example flying dust, bottom ash, slag) or its product or form processing, thereby produce the solution that comprises calcium and magnesium cation.

In some embodiments, the bivalent cation aqueous solution can be available from the factory that combustion-gas flow also is provided.For example, in water-cooled factory, in the factory as cooled with seawater, the water that factory has been used to cool off can be subsequently as the water of making solution, slurry or solid precipitation material.If desired, this water can cool off before entering system of the present invention.These class methods can for example be used with once-through cycle.For example, can use city or agricultural to supply water as the once-through cycle of factory.Water from this factory can be used to make solution, slurry or deposited material subsequently, and wherein Shu Chu glassware for drinking water has the hardness of reduction and the purity of Geng Gao.

Proton free agent and proton free method

Method of the present invention comprises the bivalent cation aqueous solution and the CO that makes certain volume ₂The source contact is (with dissolving CO ₂) and the optional condition that promotes precipitation that gained solution is imposed.In some embodiments, make the bivalent cation aqueous solution and the CO of certain volume ₂The source contact is (with dissolving CO ₂) and the optional simultaneously condition that promotes precipitation that the aqueous solution is imposed.CO ₂Be dissolved in the bivalent cation aqueous solution to produce carbonic acid---with the thing class of bicarbonate and carbonate eqrilibrium.For Production Example contains the especially material of carbonate of bicarbonate as what be fit to precipitation, from containing various thing classes (for example carbonic acid, bicarbonate, hydrogen ion etc.) the solution of bivalent cation, this removes deprotonation so that this balance is shifted to carbonate.Along with removing deprotonation, more CO ₂Enter solution.In some embodiments, make the aqueous solution and the CO that contains bivalent cation ₂In contact time, use proton free agent and/or method to improve one of this reaction CO in mutually ₂Absorb, wherein pH can remain unchanged, improve or even reduce, proton free (for example by adding alkali) rapidly subsequently is so that carbonato deposited material precipitates rapidly.Can from various thing classes (for example carbonic acid, bicarbonate, hydrogen ion etc.), remove deprotonation by any method easily, include but not limited to: chemical proton free agent, the artificial waste streams of recovery and the use electrochemical means using naturally occurring proton free agent, use microorganism and fungi, use to synthesize.

Naturally occurring proton free agent is included in any proton free agent of finding in the wideer environment that may create or have alkaline local environment.Some embodiments are provided at the naturally occurring proton free agent of creating alkaline environment when adding in the solution, comprise mineral.These class mineral include but not limited to, lime (CaO); Periclase (MgO); Iron hydroxide mineral (for example goethite and limonite); And volcanic ash.This paper provides these class mineral and has comprised the digestion method of the rock of these class mineral.Some embodiments provide uses natural alkaline water body as naturally occurring proton free agent.The example of natural alkaline water body includes but not limited to earth surface water source (for example alkali lake, as the MonoLake of California) and underground water source (for example alkaline aquifer, as be positioned at the deep layer geology alkalescence aquifer of the Searles Lake of California).Other embodiments use the sediments of the alkaline water body of self-desiccation, as the earth's crust along the Lake Natron of Africa ' s Great Rift Valley.In some embodiments, use the organism of in their eubolism secreted alkaline molecule or solution as the proton free agent.The organic example of this class is that the bacterium of the fungi that produces alkali protease (the deep-sea fungi aspergillus ustus that for example has 9 optimal pH) and the alkaline molecule of manufacturing is (for example from the cyanobacteria of the Atlin wetland of Bristish Columbia, as Lyngbyasp., it improves the pH value by the photosynthesis accessory substance).In some embodiments, use organism to produce the proton free agent, wherein the organism Bacillus pasteurii of urea hydrolysis ammonification (for example with) produces the proton free agent with pollutant (for example urea) metabolism or comprises the solution of proton free agent (for example ammonia, ammonium hydroxide).In some embodiments, separate with reactant mixture and to cultivate organism, wherein proton free agent or the solution that comprises the proton free agent are used for adding to this reactant mixture.In some embodiments, unite natural existence of use or artificial enzyme with the proton free agent.Carbonic anhydrase (it is the enzyme that plant and animal generates) quickens carbonic acid and changes into bicarbonate in Transfer in Aqueous Solution.Therefore, carbonic anhydrase can be used for strengthening CO ₂Dissolving and for example quicken the precipitation (if use precipitation) of deposited material.

The chemical reagent that is used for proton free typically refers to mass-produced commercially available synthetic chemistry reagent.For example, the chemical reagent that is used for proton free includes but not limited to, hydroxide, organic base, super base, oxide, ammonia and carbonate.Hydroxide is included in the chemical species that hydroxide radical anion is provided in the solution, comprises for example sodium hydroxide (NaOH), potassium hydroxide (KOH), slaked lime (Ca (OH) ₂) or magnesium hydroxide (Mg (OH) ₂).Organic base is a carbon-containing molecules, it typically is nitrogenous alkali, comprises primary amine, as methylamine, and secondary amine, as diisopropylamine, tertiary amine, as diisopropylethylamine, arylamine, as aniline, heteroaromatics is as pyridine, imidazoles and benzimidazole and their various forms.In some embodiments, use the organic base be selected from pyridine, methylamine, imidazoles, benzimidazole, histidine and phosphine nitrile (phophazene) to remove deprotonation from the various thing classes (for example carbonic acid, bicarbonate, hydrogen ion etc.) of the precipitation that for example is used for deposited material.In some embodiments, use ammonia pH to be risen to the level that is enough to by bivalent cation solution and industrial waste stream precipitation deposited material.The super base that is suitable as the proton free agent comprises caustic alcohol, sodium amide (NaNH ₂), sodium hydride (NaH), butyl lithium, diisopropylaminoethyl lithium, diethylamino lithium and two (trimethyl silyl) lithium amide.Oxide for example comprises, calcium oxide (CaO), magnesia (MgO), strontium oxide strontia (SrO), beryllium oxide (BeO) and barium monoxide (BaO) also are available suitable proton free agent.Be used for carbonate of the present invention and include but not limited to sodium carbonate.

Except comprising target cation and other suitable metallic forms, can provide the proton free agent from the waste streams of various industrial process.This class waste streams includes but not limited to, the mining waste material; Combustion of fossil fuel ash (for example combustion ash, as flying dust, bottom ash, slag); Slag (for example scum, phosphorus slag); The cement kiln waste material; Oil plant/petrochemical refinery factory waste material (for example oil field and methane layer salt solution); Coal seam waste material (for example gas production salt solution and coal seam salt solution); The paper conversion waste material; Water softening effluent brine (for example ion exchange effluent); The silicon processing waste material; Agricultural residue; The metal finishing waste material; High pH textile waste; And alkaline residue.The mining waste material comprises by extract any waste material that metal or another expensive or useful mineral produce from the soil.In some embodiments, use the waste material from mining to change change pH values, wherein this waste material is selected from the red mud from Bayer aluminium extraction method; The waste material that extracts from the magnesium of seawater (for example, at Moss Landing, the Mg that finds among the California (OH) ₂); With waste material from the mining codes that comprise lixiviate.For example, red mud can be used to change change pH values described in the U.S. Provisional Patent Application No.61/161369 that submits to the 18 days March in 2009 that is incorporated herein by this reference in full.Combustion of fossil fuel ash, cement flue Dust and slag---be referred to as the waste sources of metal oxide, further describe in the U.S. Patent application No.12/486692 that submitted on June 17th, 2009, its disclosure is incorporated herein by this reference in full---can use so that for the invention provides the proton free agent separately or with other proton free agent.Agricultural residue (by animal waste or excessively use fertilizer produce) may contain potassium hydroxide (KOH) or ammonia (NH ₃) or both.Therefore, agricultural residue can be used as the proton free agent in some embodiments of the present invention.This agricultural residue is collected in the pond usually, but it also may infiltrate in the aquifer, can obtain it and uses at this.

Electrochemical method is an another way of removing deprotonation in the various thing classes from solution, by removing deprotonation (for example carbonic acid or bicarbonate take off proton) or remove deprotonation (for example hydrogen ion or water take off proton) from solute from solvent.For example, if CO ₂The proton that dissolving causes generates coupling or surpasses electrochemistry proton free from solute molecule, may cause the proton that takes off of solvent.In some embodiments, use low voltage electrochemical method proton free, for example, with CO ₂When being dissolved in the precursor solution (that is, may contain or not contain the solution of bivalent cation) of reactant mixture or this reactant mixture.In some embodiments, handle the CO that is dissolved in the aqueous solution that does not contain bivalent cation by the low voltage electrochemical method ₂With from carbonic acid, bicarbonate, hydrogen ion or by CO ₂Remove deprotonation in any thing class that dissolving produces or its combination.The low voltage electrochemical method is 2,1.9,1.8,1.7 or 1.6V or lower, as 1.5,1.4,1.3,1.2,1.1V or lower, as 1V or lower, as 0.9V or lower, 0.8V it is or lower, 0.7V or lower, 0.6V or lower, 0.5V or lower, 0.4V it is or lower, 0.3V or lower, 0.2V or lower, or 0.1V or the operation down of lower average voltage.The low voltage electrochemical method that does not generate chlorine is convenient to use in the system and method for the present invention.The low voltage electrochemical proton free method that does not generate oxygen also is convenient to use in the system and method for the present invention.In some embodiments, the low voltage electrochemical method generates hydrogen and it is delivered to anode at the negative electrode place, at this this hydrogen is changed into proton.The electrochemical method that does not generate hydrogen also can be easily.In some cases, electrochemistry proton free method does not generate any gaseous by-product.Electrochemistry proton free method further describes the U.S. Patent application No.12/344 that submits on December 24th, 2008,019; The U.S. Patent application No.12/375 that on December 23rd, 2008 submitted to, 632; The international patent application No.PCT/US08/088242 that on December 23rd, 2008 submitted to; The international patent application No.PCT/US09/32301 that on January 28th, 2009 submitted to; In the international patent application No.PCT/US09/48511 that submitted on June 24th, 2009, they are incorporated herein by this reference separately in full.

Perhaps, electrochemical method can be used for producing caustic alkali molecule (for example hydroxide) by for example chlor-alkali or its variant.Contain the aqueous solution of bivalent cation or be filled with the gaseous state waste streams and (for example be filled with CO holding this ₂) the device of solution in may have electrode (being negative electrode and anode), the selectivity dividing plate can separate electrode as film.Be used for may producing accessory substance (for example hydrogen) except that the electro-chemical systems and the method for deprotonation, it can collect and be used for other purposes.Other available electrochemical method includes but not limited to the U.S. Provisional Patent Application No.61/081 that on July 16th, 2008 submitted in the system and method for the present invention, 299 and U.S. Provisional Patent Application No.61/091, those that describe in 729, their disclosure is incorporated herein by this reference.Can use the combination of above-mentioned proton free agent source and proton free method.

Merge and process the method for reactant

Can use various method to prepare composition of the present invention.Interested program includes but not limited to, the u.s. patent application serial number Nos.12/126 that on May 23rd, 2008 submitted to, 776; 12/163,205 of submission on June 27th, 2008; 12/344,019 of submission on December 24th, 2008; With the U.S. Provisional Patent Application sequence number Nos.61/017 that submits to 28,12/475,378 and 2007 on the December of submitting on May 29th, 2009,405; 61/017,419 of submission on December 28th, 2007; 61/057,173 of submission on May 29th, 2008; 61/056,972 of submission on May 29th, 2008; 61/073,319 of submission on June 17th, 2008; 61/079,790 of submission on July 10th, 2008; 61/081,299 of submission on July 16th, 2008; 61/082,766 of submission on July 22nd, 2008; On August 13rd, 2008 submitted 61/088347 to; 61/088,340 of submission on August 12nd, 2008; 61/101,629 of submission on September 30th, 2008; With submitted on September 30th, 2008 61/101,631 in those disclosed; Their disclosure is incorporated herein by this reference.

Composition of the present invention comprises can be in solution or slurry or by the bicarbonate of precipitated calcium and/or magnesium from bivalent cation solution or bicarbonate and the carbonate composition that carbonate composition is made.This bicarbonate and/or the carbonate compound composition that constitute component of the present invention comprise metastable carbonate compound, its can as hereinafter in greater detail from bivalent cation solution, as precipitation in the salt water (saltwater).Bicarbonate of the present invention and/or carbonate compound composition comprise crystallization and/or the amorphous bicarbonate and the carbonate compound of precipitation.

Bicarbonate of the present invention that salt water is derived and/or carbonate compound composition (promptly derived from salt water and constituted and contained or do not contain the composition of one or more hydroxide crystalline state or amorphous compound by one or more different carbonate crystalline state and/or amorphous compound) are the compositions derived from salt water.Therefore, they are in a certain way available from the composition of salt water, for example by to be enough to be handled by the mode that the salt water of initial volume is made required bicarbonate and/or carbonate compound composition the salt water of certain volume.The bicarbonate of some embodiment and/or carbonate compound composition are by for example from comprising alkaline earth metal cation, make as precipitation in the bivalent cation solution (for example salt water) of calcium and magnesium etc., wherein this class bivalent cation solution can be referred to as the water of alkaline including earth metal.

The salt water of using in this method can be different.As above summarize, interested salt water comprises brackish water, seawater and salt solution, and salinity is greater than other brackish water (salines) of fresh water (it has the salinity less than the salt of 5ppt dissolving).In some embodiments, rich calcium water can with the magnesium silicate mineral, as olivine or serpentine, in solution, merge, described solution owing to add carbonic acid gas form carbonic acid become acid, this carbonic acid dissolving magnesium silicate, thus form aforesaid silicic acid miemite compound.

In making bicarbonate of the present invention and/or carbonate compound method for compositions, optional water to certain volume imposes the bicarbonate/carbonate compound precipitation condition of the solution that is enough to produce potassium-containing hydrogen salt and/or carbonate, if desired, this solution can be used for making deposited material and mother liquor (i.e. the water section that stays from this salt water post precipitation at bicarbonate and/or carbonate compound) subsequently.Gained deposited material and mother liquor can constitute bicarbonate of the present invention together and/or carbonate compound composition (for example with slurry form) maybe can be separated into sediment and mother liquor, separately or both also can be used as composition of the present invention (for example solid and liquid composite).Can use any deposition condition easily, this condition causes producing the bicarbonate/carbonate compound composition.

For the compound of precipitation, promote that the condition (being deposition condition) of precipitation can be different.For example, water temperature can be in the scope of the precipitation that is fit to the required mineral of generation.In some embodiments, water temperature can be 5 to 70 ℃, as 20 to 50 ℃, comprises 25 to 45 ℃.Therefore, although a given group precipitation condition can have 0 to 100 ℃ temperature, may have to regulate water temperature in certain embodiments to produce required deposited material.

For carbonate compound, in normal seawater, the CO of 93% dissolving ₂Be bicarbonate ion (HCO ₃ ^-) form, and 6% be carbanion (CO ₃ ^-2) form.When calcium carbonate precipitates, discharge CO from normal seawater ₂PH greater than 10.33 fresh water in, the carbonate more than 90% is the carbanion form, and does not discharge CO in the precipitation of calcium carbonate process ₂In seawater, under near the lower slightly pH of pH 9.7 this transformation takes place.Although the pH value of used water can be 5 to 14 in this method in given precipitation process, in certain embodiments the pH value is risen to alkaline level to order about carbonate compound and other compound, for example precipitation of hydroxide on demand.In some these embodiment, the pH value is risen to as far as possible the CO that reduces in (if not the words of eliminating) precipitation process ₂The level that generates is so that the CO of dissolving ₂For example be trapped in this deposited material with carbonate and bicarbonate form.In these embodiments, the pH value can be risen to 10 or higher, as 11 or higher.

Can use any method easily to improve the pH value of water.In certain embodiments, use the proton free agent, wherein the example of this class reagent comprises oxide, the hydroxide (calcium oxide in the flying dust for example; Potassium hydroxide, sodium hydroxide, shepardite (Mg (OH ₂) etc.), carbonate (for example sodium carbonate) etc., wherein as mentioned above many.A kind of such method of the pH value of raising precipitation reaction mixture or its precursor (solution that for example contains bivalent cation) is to use the coal ash from coal-fired power plant, and it contains many oxides.Other coal technology (as coal gasification to produce synthesis gas) also produces hydrogen and carbon monoxide, and also can serve as hydroxide source.Some naturally occurring mineral as serpentine, contain hydroxide and can dissolve the generation hydroxide source.The interpolation of serpentine also is discharged into silica and magnesium in the solution, thereby forms silica containing deposited material.The amount of adding the proton free agent in reactant mixture or its precursor to depends on the volume of the special properties of this proton free agent and the reactant mixture that just is being modified or its precursor, and is enough to the pH value of this reactant mixture or its precursor is increased to required pH value.Perhaps, can the pH value of this reactant mixture or its precursor be increased to desired level by aforesaid electrochemical method.Can use other electrochemical method under certain conditions.For example, can use electrolysis, wherein use mercury cell method (being also referred to as the Castner-Kellner method); Diaphragm cell method, film battery method or their some combinations.If desired, can collect the accessory substance of hydrolysate, for example H ₂, sodium metal etc. and be used for other purposes on demand.In other embodiments, can use the U.S. Provisional Application sequence number Nos.61/081 that submitted on July 16th, 2008, submitted on August 25th, 299 and 2008 61/091,729 described in pH rising method; Their disclosure is incorporated herein by this reference.

Also the additive beyond the pH elevating agents can be introduced the character of the material made from influence in the water.Therefore, some embodiment of this method be included in to this water impose before the deposition condition or among in this water, provide additive.Can facilitate some calcium carbonate polycrystalline type thing with some additive of trace.For example, the lanthanum of the lanthanum chloride form by comprising trace in calcium carbonate oversaturated solution can obtain vaterite---CaCO with high yield ₃The unsettled polymorph of height, it is with various form precipitation and change into calcite rapidly.Interested other additive except that lanthanum includes but not limited to transition metal etc.For example, the known unordered dolomite (former dolomite) that forms otherwise can not form that impels of interpolation ferrous or positive iron ion.

Also can recently influence the character of deposited material by selecting suitable leading ion.Leading ion is than also appreciable impact polymorph formation.For example, along with the magnesium in the water: calcium is than improving, and aragonite is better than low-Mg calcite and becomes preferential calcium carbonate polycrystalline type thing.At low magnesium: calcium than under, low-Mg calcite is preferred polymorph.Therefore, can use the magnesium of wide region: the calcium ratio, comprise for example 100: 1,50: 1,20: 1,10: 1,5: 1,2: 1,1: 1,1: 2,1: 5,1: 10,1: 20,1: 50,1: 100, or any above-mentioned ratio.In certain embodiments, this magnesium: calcium is than depending on water source used in these precipitation method (for example seawater, salt solution, brackish water, fresh water), and in other embodiments, and with magnesium: the calcium ratio is adjusted to and drops in the certain limit.

Settling rate also greatly influences compound and forms mutually.By with required this solution of inoculating mutually, can realize precipitating the most fast.Under situation about not inoculating, can realize rapid precipitation by the pH value of quick raising seawater, this produces more amorphous composition.When having silica, reaction rate is fast more, and many more silica are incorporated in the carbonato deposited material.PH value is high more, precipitates fast more and deposited material amorphous state more.

Correspondingly, a group precipitation condition of being made required deposited material by bivalent cation solution comprises water temperature and pH value in certain embodiments, comprises the concentration of additive and ionic species in this water in some cases.Deposition condition also can comprise the factors such as existence as mixing rate, whipped form (as ultrasonic) and crystal seed, catalyzer, film or substrate.In some embodiments, deposition condition comprises supersaturated condition, temperature, pH and/or concentration gradient, or circulation or change any of these parameter.The program that is used to prepare the deposited material of carbonate containing of the present invention and/or bicarbonate can be a program in batches or continuously.Recognize, for making given deposited material, deposition condition in continuous-flow system may with batch system in different.

In certain embodiments, this method further comprises and makes this water body and the CO that stands the mineral precipitation condition ₂The source contact.Water and CO ₂The contact in source can impose CO to this water ₂Before the deposition condition and/or among take place.Correspondingly, embodiment of the present invention are included in this salt water body imposed and make this water body and CO before the mineral precipitation condition ₂The method of source contact.Embodiment of the present invention make this salt water body and CO when being included in this salt water body imposed bicarbonate and/or carbonate compound deposition condition ₂The method of source contact.Embodiment of the present invention are included in this salt water body are imposed before bicarbonate and/or the carbonate compound deposition condition and make this water body and CO when this salt water body is imposed bicarbonate and/or carbonate compound deposition condition ₂The method of source contact.In some embodiments, this identical water can circulate more than once, wherein the first precipitation cycle mainly removed calcium carbonate and magnesium carbonate mineral and stayed residual alkaline water, can be to wherein adding other source of alkaline earth metal, more CO2 are cycled through wherein, thereby precipitate more multi-carbonate compound.

In these embodiments, the CO that contacts with this salt water body ₂The source can be any essential δ that has easily ¹³The CO of C value ₂The source, and contact procedure can be any program easily.Work as CO ₂When being gas, interested contact procedure includes, but are not limited to: direct contact procedure, for example this gas bubbling is passed through this salt water body, and the stream way of contact, the i.e. gas phase of one-way flow and the contact between the liquid phase stream, convection type, the i.e. gas phase that flows of subtend and the contact between the liquid phase stream etc.Therefore, can look convenient injector, bubbler, fluid venturi reactor, sprayer, pneumatic filter, nozzle, tower tray or the packed column reactor etc. of using and realize contact.About being used to make bivalent cation solution and CO ₂The example system and the method for source contact are referring to the U.S. Provisional Patent Application No.61/158 that submitted on March 10th, 2009,992; 61/168,166 of submission on April 9th, 2009; 61/170,086 of submission on April 16th, 2009; 61/178,475 of submission on May 14th, 2009; 61/228,210 of submission on July 24th, 2009; 61/230,042 of submission on July 30th, 2009; With 61/239,429 of submission on September 2nd, 2009, they are incorporated herein by this reference separately.

Said procedure produces the slurry of deposited material and mother liquor.If desired, should can store a period of time at post precipitation and further first being processed by the composition that deposited material and mother liquor constitute, or can further not process or bottom line processing, and as store with, throw aside with or be used for the slurry of other purposes, but for example with the flow composition form.If desired, but should flow composition can be pumped to underground so that contained CO in that seal this precipitation for a long time up for safekeeping and/or the soluble component ₂Perhaps, can store this slurry for later use.For example, said composition can be at 1 to 40 ℃, as storing 1 to 1000 day or more of a specified duration under 20 to 25 ℃ the temperature, as 1 to 10 day or more of a specified duration.

Further handle if desired, subsequently the separating slurry component.Embodiment can comprise the processing mother liquor, and wherein this mother liquor may be present in the identical composition with product, or can be not like this.For example, if send mother liquor back to ocean, can make this mother liquor and gaseous state CO ₂The source contacts in the mode that is enough to improve the carbon acid ion concentration that exists in the mother liquor.Can use any program easily, as above-mentioned those, implement contact.In certain embodiments, this mother liquor has alkaline pH value and and CO ₂The contact in source to be to be enough to that pH is reduced to 5 to 9, and for example 6 to 8.5, comprise that 7.5 to 8.2 mode is carried out.In certain embodiments, this salt solution of handling can with aforesaid CO ₂The source contact is further to seal CO up for safekeeping ₂For example, if send mother liquor back to ocean, can make this mother liquor and gaseous state CO ₂The source contacts in the mode that is enough to improve the carbon acid ion concentration that exists in the mother liquor.Can use any program easily, as above-mentioned those, implement contact.In certain embodiments, this mother liquor has alkaline pH value and and CO ₂The contact in source to be to be enough to that pH is reduced to 5 to 9, and for example 6 to 8.5, comprise that 7.5 to 8.2 mode is carried out.

The gained reaction mother liquor can itself be the composition of the present invention of solution form.In some embodiments, this mother liquor can use any program easily to throw aside.In certain embodiments, it can be sent to tailing pit so that throw aside.In certain embodiments, it can be thrown aside at naturally occurring water body, for example ocean, sea, lake or korneforos.In certain embodiments, send mother liquor the charging water source of method of the present invention back to, for example ocean or extra large.Perhaps, can be as US application serial No. No.12/163, this mother liquor of such further processing that further describes in 205 (its disclosure is incorporated herein by this reference) for example imposes the desalination program.

In certain embodiments, after product is made, products therefrom is separated the product that separates with generation with mother liquor.Can use any mode easily to realize that product separates, comprise mechanical system, for example wherein from product drop remove most of excessive water (for example only by gravity or be aided with vacuum), machinery pressurization, by filtration product from mother liquor to produce filtrate etc.The separation of most of water produces wet dehydration deposited material in certain embodiments.In some embodiments, this dehydration deposited material is greater than 5% water, greater than 10% water, greater than 20% water, greater than 30% water, greater than 50% water, greater than 60% water, greater than 70% water, greater than 80% water, greater than 90% water, or greater than 95% water.

Gained dehydration deposited material can be dry on demand subsequently to produce desciccate.Can realize drying by air-dry this moist precipitate material.Under the situation of air-dry moist precipitate material, air-dry can be under the temperature of room temperature or rising.In an embodiment again, with moist precipitate material spray drying with dry this deposited material, wherein come drying to contain the liquid of deposited material, for example wherein this liquid feed pump is delivered in the main drying room and transmitted hot gas with atomizer direction and stream or convection current ground via atomizer by making it pass hot gas (the gaseous state waste streams of the spontaneous power plant of Tathagata).According to the specific drying program of this system, dry station can comprise filter element, freeze-drying structure, atomized drying structure etc.If desired, this dehydration deposited material product can wash before drying.This deposited material can be washed with fresh water, for example to remove desalt (as NaCl) from this dehydration deposited material.

In certain embodiments, this deposited material refining in some way before follow-up use (i.e. processing).Make with extra care and to comprise various program.In certain embodiments, this product is imposed machine finish, for example grind, to obtain to have required physical property, the product of granularity etc. for example.

Embodiment

Embodiment 1. solid sediments and raw-material δ ¹³The measurement of C value

This embodiment verifies and uses canned carbonic acid gas (CO ₂) and the industrial waste of rich magnesium from saline solution, precipitate carbonate material and measure material and the δ of product ¹³The C value.In the container that opens wide to atmosphere, implement this program.

Raw material are commercially available canned CO ₂Gas, seawater and as the industrial waste source of alkali shepardite mine tailing from the magnesium hydroxide place of production.The Rietveld of the X-ray diffraction figure of the dry aliquot by mine tailing analyzes and records this shepardite mine tailing is about 85%Mg (OH) ₂, 12%CaCO ₃And 3%SiO ₂

Near the seawater (at Santa Cruz, the CA) that this locality can get of in container, packing into.The shepardite mine tailing is added in the seawater, and it provides pH (alkalescence) and the bivalent cation concentration that is fit to carbonate deposition, and with CO ₂Gas blasts this alkalescence sea water solution.Reserve time enough so that reactive component interacts, after this deposited material is separated with residual seawater solution (being also referred to as supernatant).This sediment carbonate material in air 40 ℃ of dryings.See Fig. 3.The gained powder is fit to further processing for use, for example as the material in the architectural environment, as is used in gathering materials in roadbed or the concrete etc.This powder also can store as the carbon sequestration material with the state of making.Perhaps, this material can be stayed in the supernatant, and chooses wantonly after with atmospheric equilibrium and store with slurry form, and wherein carbonate in this sediment and the solution and bicarbonate all serve as the carbon sequestration material.Other purposes of this material is as described herein, and is that those skilled in the art are conspicuous.Use δ ¹³C analyzes, X-ray diffraction (XRD) is analyzed and scanning electron microscopy (SEM) characterizes this carbonate material.

Measure the δ of technology raw material, precipitation carbonate material and supernatant ¹³The C value.Do not measure the δ of atmosphere ¹³The C value, but in table 2, provide value from document.Used analytical system is made and is used direct absorption spectrometry to provide by Los GatosResearch and contains 2% to 20%CO ₂The δ of dry gas ¹³C and concentration data.Use has the standard 5%CO of known isotopics ₂This instrument of gas calibration, the CO that calcareous tufa that digests in 2M perchloric acid and IAEA marble #20 sample discharge ₂Measurement produce the value in the measure error of allowing of the value found in the literature.Use syringe to extract this CO ₂The sample of source gas.Make this CO ₂Gas by gas-drying apparatus (Perma PureMD Gas Dryer, model MD-110-48F-4, by

Polymer is made), enter the commercially available carbon isotope analysis of table top system subsequently.Solid sample is as shepardite mine tailing and sediment, earlier with perchloric acid (the 2M HClO that heats ₄) digestion.From the digestive system of this sealing, discharge CO ₂Gas is sent into gas-drying apparatus subsequently.Collect this gas from here, and inject analytical system, thereby produce δ ¹³The C data.This digestion process is presented among Fig. 2.Similarly, digest this supernatant to discharge CO ₂Gas, its subsequent drying and be sent to this analytical instrument, thus produce δ ¹³The C data.

From CO ₂The measurement result of the analysis of source, industrial waste (shepardite mine tailing), carbonate sediment and supernatant is listed in table 2 and is presented among Fig. 7.The δ of this sediment and supernatant ¹³The C value is respectively-31.98 ‰ and-38.59 ‰.The δ of two kinds of products of this of this reaction ¹³The C value has all reflected CO ₂The source incorporate (δ into ¹³C=-41.39 ‰) and the influence (δ that comprises the shepardite mine tailing of some calcium carbonate ¹³C=-6.73 ‰).This embodiment shows, δ ¹³The C value can be used for confirming in the carbonate composition and the solution made by this carbonic acid gas in the main source of carbon.

Table 2

Be used for isotope fractionation experiment source material that characterizes and the value that records

Embodiment	Atmosphere δ ¹³C value [‰] ³	CO ₂The source	CO ₂Source δ ¹³C value [‰]	Alkali source	Alkali δ ¹³C value [‰]	Supernatant δ ¹³C value [‰]	Sediment δ ¹³C value [‰]
								1	-8	Bottled gas, source 1	-41.39	Mg(OH) ₂ + Ca(CO) ₃Mine tailing	-6.73	-38.59	-31.98
2	-8	Bottled gas meets NIST RM8563 ⁴	-41.56	Mg(OH) ₂ + Ca(CO) ₃Mine tailing	-6.73	-34.16	-30.04
								3	-8	Flue gas from propane burner	-25.00	Mg(OH) ₂ + Ca(CO) ₃Mine tailing	-6.73	-24.8	-19.92
4	-8	SO ₂/CO ₂The bottled gas mixture	-12.45	Flying dust	-17.46	-11.70	-15.88

3.Zeebe, R.E. and Wolf-Galdrow, E, CO ₂ In Seawater:Equilibrium, Kinetics, Isotopes(2005) Elsevier, San Diego, g.169.

4.FROM?NIST?SPECIFICATION?RM8563，CO ₂Light?Isotopic?GasStandard

Embodiment 2: solid sediment and raw-material δ ¹³The measurement of C value

In 250,000 gallon container, carry out this precipitation.Raw material are commercially available canned CO ₂Gas, near seawater (from Santa Cruz, the CA), 50%NaOH solution and as the shepardite mine tailing of industrial waste.The Rietveld of the X-ray diffraction figure of the dry aliquot by mine tailing analyzes and records this shepardite mine tailing is about 85%Mg (OH) ₂, 12%CaCO ₃And 3%SiO ₂The part seawater that this locality can get of packing in this 250,000 gallon container.By the diffuser that is positioned at this container bottom carbon dioxide is blasted seawater.At CO ₂After blasting, the pH value of seawater reaches about 5.5.The shepardite mine tailing is added in this seawater, be fit to precipitation carbonate solid and not with CO thereby provide ₂The magnesium density of discharging into the atmosphere and the raising of basicity.Stop CO ₂The interpolation of gas bubbling and shepardite mine tailing.Add sodium hydroxide solution subsequently to realize about 9.5 pH value.Reserve time enough so that reactive component interacts, after this deposited material is separated with residual seawater solution (being also referred to as supernatant).Dry this material of the dry air of the heat of use in spray-drying installation.Produce and surpass 500 kg of material.See Fig. 4.The gained powder is fit to further processing for use, for example as the material in the architectural environment, as is used in gathering materials in roadbed or the concrete etc.This powder also can store as the carbon sequestration material with the state of making.Perhaps, this material can be stayed in the supernatant, and chooses wantonly after with atmospheric equilibrium and store with slurry form, and wherein carbonate in this sediment and the solution and bicarbonate all serve as the carbon sequestration material.Other purposes of this material is as described herein, and is that those skilled in the art are conspicuous.Use δ ¹³C analyzes, X-ray diffraction (XRD) is analyzed and scanning electron microscopy (SEM) characterizes this carbonate material.

Measure the δ of technology raw material, gained material and supernatant ¹³The C value.Do not measure the δ of atmosphere ¹³The C value, but in table 2, provide value from document.Used analytical system is made by Los Gatos Research as described in example 1 above.

From CO ₂The measurement result of the analysis of source, industrial waste (shepardite mine tailing), carbonate sediment and supernatant is listed in table 2 and is presented among Fig. 8.The δ of this sediment and supernatant ¹³The C value is respectively-30.04 ‰ and-34.16 ‰.The δ of two kinds of products of this reaction ¹³The C value has all reflected CO ₂The source incorporate (δ into ¹³C=-41.56 ‰) and comprise the influence (δ of the shepardite mine tailing of some calcium carbonate ¹³C=-6.73 ‰).The carbonate material of precipitation more may be in conjunction with calcium carbonate from the shepardite mine tailing than supernatant, therefore this sedimentary δ ¹³The C value reflects this point by cannot not compare negatively with supernatant (lessnegative).This embodiment shows, δ ¹³The C value can be used for confirming in the carbonate composition and the solution made by this carbonic acid gas in the main source of carbon.

Embodiment 3: solid sediment and raw-material δ ¹³The measurement of C value

Use is implemented this experiment by flue gas and rich magnesium industry waste material that burning propane produces.In the container that opens wide to atmosphere, implement this program.

Raw material be from propane burner flue gas, near seawater (from Santa Cruz, the CA) and as the shepardite mine tailing of industrial waste.The Rietveld of the X-ray diffraction figure of the dry aliquot by mine tailing analyzes and records this shepardite mine tailing is about 85%Mg (OH) ₂, 12%CaCO ₃And 3%SiO ₂

The seawater that this locality can get of in container, packing into.The shepardite mine tailing is added in this seawater, be fit to precipitation carbonate and not with CO thereby provide ₂PH that discharges into the atmosphere (alkalescence) and bivalent cation concentration.Blast flue gas with speed and the time that is fit to precipitation carbonate material from this alkalescence sea water solution.Reserve time enough so that reactive component interacts, after this deposited material is separated with residual seawater solution (being also referred to as supernatant) and atomized drying.See Fig. 5.The gained powder is fit to further processing for use, for example as the material in the architectural environment, as is used in gathering materials in roadbed or the concrete etc.This powder also can store as the carbon sequestration material with the state of making.Perhaps, this material can be stayed in the supernatant, and chooses wantonly after with atmospheric equilibrium and store with slurry form, and wherein carbonate in this sediment and the solution and bicarbonate all serve as the carbon sequestration material." CO used herein ₂Seal up for safekeeping " and " carbon sequestration " synonym.Other purposes of this material is as described herein, and is that those skilled in the art are conspicuous.

Measure the δ of technology raw material, gained precipitation carbonate material and supernatant ¹³The C value.Do not measure the δ of atmosphere ¹³The C value, but in table 2, provide and in Fig. 9, show value from document.Describe in detail among used analytical system such as the embodiment 1 by Los Gatos Research and make, and use direct absorption spectrometry to provide to contain 2% to 20%CO ₂The δ of gas ¹³C and concentration data.

Measurement result from the analysis of flue gas, industrial waste (shepardite mine tailing), carbonate sediment and supernatant is listed in the table 2.The δ of this sediment and supernatant ¹³The C value is respectively-19.92 ‰ and-24.8 ‰.The δ of two kinds of products of this of this reaction ¹³The C value has reflected flue gas CO ₂The source incorporate (δ into ¹³C=-25.00 ‰) and comprise the influence (δ of the shepardite mine tailing of some calcium carbonate ¹³C=-6.73 ‰).This embodiment shows, δ ¹³The C value can be used for confirming in the carbonate composition (as the CO of this carbonate ₂The source is when burning) and the solution made by this carbonic acid gas in the main source of carbon.

Embodiment 4. solid sediments and raw-material δ ¹³The measurement of C value

Canned SO is used in this experiment ₂And carbonic acid gas (CO ₂) gas mixture and from the aqueous solution, precipitate the carbonating material as the flying dust of industrial waste.In closed container, implement this program.

Raw material are commercially available canned SO ₂And CO ₂Gas (SO ₂/ CO ₂Gas) mixture, deionized water and as the flying dust of industrial waste.

The deionized water of in container, packing into.After slaking, flying dust is added in this deionized water, be fit to precipitation carbonate and not with CO thereby provide ₂PH that discharges into the atmosphere (alkalescence) and bivalent cation concentration.Blast SO with speed and the time that is fit to precipitation carbonate material from this alkaline solution ₂/ CO ₂Gas.Reserve time enough so that reactive component interacts, after this deposited material is separated with surplus solution (being also referred to as supernatant) and atomized drying.See Fig. 6.The gained powder is fit to further processing for use, for example as the material in the architectural environment, as is used in gathering materials in roadbed or the concrete etc.This powder also can store as the carbon sequestration material with the state of making.Perhaps, this material can be stayed in the supernatant, and chooses wantonly after with atmospheric equilibrium and store with slurry form, and wherein carbonate in this sediment and the solution and bicarbonate all serve as the carbon sequestration material.Other purposes of this material is as described herein, and is that those skilled in the art are conspicuous.

As describing in detail among the embodiment 1, measure the δ of technology raw material, precipitation carbonate material and supernatant ¹³The C value.

From SO ₂/ CO ₂The measurement result of the analysis of gas, industrial waste (flying dust), carbonate sediment and supernatant is listed in table 2 and is presented among Figure 10.The δ of this sediment and supernatant ¹³The C value is respectively-15.88 ‰ and-11.70 ‰.The δ of two kinds of products of this of this reaction ¹³The C value has reflected SO ₂/ CO ₂Gas incorporate (δ into ¹³C=-12.45 ‰) with comprise some do not have completing combustion become gas carbon flying dust incorporate (δ into ¹³C=-17.46 ‰).Because flying dust (itself being the combustion product of fossil fuel) has than used CO ₂More negative δ ¹³C, this sedimentary total δ ¹³The C value is passed through than CO ₂The more negative this point that reflects of itself.This embodiment shows, δ ¹³The C value can be used for confirming comprising SO when using _x(SO ₂) and CO ₂Admixture of gas the time, the main source of the carbon in the carbonate composition.

Although showed and described the preferred embodiments of the invention, it should be apparent to those skilled in the art that this class embodiment only provides as an example.Those skilled in the art can expect many changes, modification in the case of without departing from the present invention and substitute.It should be understood that and to use the various replacement schemes of embodiment of the present invention as herein described to implement the present invention.Method and structure in the scope that following claim is intended to determine scope of the present invention and be encompassed in these claims and counterpart thereof thus.

Claims

1. the composition that comprises carbonate, bicarbonate or its combination, wherein the carbon in the said composition has the relative carbon isotope composition (δ less than-26.10 ‰ ¹³C) value.

2. the composition of claim 1, wherein said composition is a synthetic composition.

3. the composition of claim 1, wherein said carbonate, bicarbonate or its constitute at least 50% of said composition.

4. the composition of claim 1, wherein said composition has the quality greater than double centner.

5. the composition of claim 1, the wherein CO of said composition ₂Content is at least 10%.

6. the composition of claim 1, wherein said composition has negativity carbon footprint.

7. the composition of claim 1 further comprises boron, sulphur or nitrogen, and wherein the relative isotopics of this boron, sulphur or nitrogen show the fossil fuel source.

8. the composition of claim, wherein said carbonate, bicarbonate or its combination comprise calcium, magnesium or its combination.

9. the composition of claim 8, wherein calcium/magnesium (Ca/Mg) mol ratio is 1/200 to 200/1.

10. the composition of claim 8, wherein calcium/magnesium (Ca/Mg) mol ratio is 12/1 to 1/15.

11. the composition of claim 8, wherein calcium/magnesium (Ca/Mg) mol ratio is 5/1 to 1/10.

12. the composition of claim 1 further comprises the SOx or derivatives thereof.

13. the composition of claim 12, wherein said composition comprise the SOx derivative and wherein this SOx derivative be sulphite, sulphate or its combination.

14. the composition of claim 1 further comprises metal.

15. the composition of claim 14, wherein this metal comprises lead, arsenic, mercury or cadmium or its combination.

16. comprise the construction material of the component that comprises carbonate, bicarbonate or its combination, the carbon in wherein said carbonate, bicarbonate or its combination has the relative carbon isotope composition (δ less than-10.00 ‰ ¹³C) value.

17. the construction material of claim 16, the wherein said component that comprises carbonate, bicarbonate or its combination be neutral carbon or the carbon negativity.

18. the construction material of claim 16, the wherein said component that comprises carbonate, bicarbonate or its combination is synthesized.

19. the construction material of claim 16, wherein said carbonate, bicarbonate or its constitute at least 50% of the described component that comprises carbonate, bicarbonate or its combination.

20. the construction material of claim 16, the wherein said CO that comprises the component of carbonate, bicarbonate or its combination ₂Content is at least 10%.

21. the construction material of claim 16 further comprises boron, sulphur or nitrogen, wherein the relative isotopics of this boron, sulphur or nitrogen show the fossil fuel source.

22. the construction material of claim 16, wherein said carbonate, bicarbonate or its combination comprise calcium, magnesium or its combination.

23. the construction material of claim 22, wherein calcium/magnesium (Ca/Mg) mol ratio is 1/200 to 200/1.

24. the construction material of claim 22, wherein calcium/magnesium (Ca/Mg) mol ratio is 12/1 to 1/15.

25. the construction material of claim 16, the wherein said component that comprises carbonate, bicarbonate or its combination constitutes at least 20% of this construction material.

26. the construction material of claim 16, wherein this construction material is a cementitious material.

27. the cementaceous construction material of claim 26, wherein this construction material is cement or concrete.

28. the construction material of claim 16, wherein this construction material is non-cementitious material.

29. the construction material of claim 28, wherein this construction material is to gather materials.

30. the construction material of claim 28, wherein this construction material is a pavement material.

31. the construction material of claim 28, wherein this construction material be brick, plate, conduit, beam, basin, post, watt, fibre wall panel products, base, soundproof wall, gypsum, drywall, plaster, soil fixation composition or barrier material or their combination.

32. the construction material of claim 16, the wherein said component that comprises carbonate, bicarbonate or its combination further comprises the SOx or derivatives thereof.

33. the construction material of claim 32, wherein this component comprise the SOx derivative and wherein this derivative be sulphate, sulphite or its combination.

34. the construction material of claim 16, the wherein said component that comprises carbonate, bicarbonate or its combination further comprises metal.

35. the construction material of claim 32, wherein this metal comprises lead, arsenic, mercury or cadmium or its combination.

But 36. comprising the flow composition of carbonate, bicarbonate or its combination, the carbon in wherein said carbonate, bicarbonate or its combination has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value, and the viscosity of said composition is 1 to 2000cP.

37. the composition of claim 36, wherein this viscosity is 10 to 1000cP.

38. the composition of claim 36, wherein said composition is a synthetic composition.

39. the composition of claim 36, wherein said carbonate, bicarbonate or its constitute the 10%w/w at least of said composition.

40. the composition of claim 36, the wherein CO of said composition ₂Content is at least 10%.

41. the composition of claim 36, wherein said composition has negativity carbon footprint.

42. the composition of claim 36 further comprises boron, sulphur or nitrogen, wherein the relative isotopics of this boron, sulphur or nitrogen show the fossil fuel source.

43. the composition of claim 36, wherein said carbonate, bicarbonate or its combination comprise calcium, magnesium or its combination.

44. the composition of claim 43, wherein calcium/magnesium (Ca/Mg) mol ratio is 1/200 to 200/1.

45. the composition of claim 43, wherein calcium/magnesium (Ca/Mg) mol ratio is 12/1 to 1/15.

46. the composition of claim 43, wherein calcium/magnesium (Ca/Mg) mol ratio is 5/1 to 1/10.

47. the composition of claim 36 further comprises the SOx or derivatives thereof.

48. the composition of claim 36 further comprises metal.

49. the composition of claim 48, wherein this metal comprises lead, arsenic, mercury or cadmium or its combination.

50. comprise the synthetic composition of carbonate, bicarbonate or its combination, wherein the carbon in the said composition has the relative carbon isotope composition (δ less than-5.00 ‰ ¹³C) value and said composition are the carbon negativity.

51. the composition of claim 50, wherein said carbonate, bicarbonate or its constitute at least 50% of said composition.

52. the composition of claim 50, wherein said composition has the quality greater than double centner.

53. the composition of claim 50, the wherein CO of said composition ₂Content is at least 10%.

54. the composition of claim 50 further comprises boron, sulphur or nitrogen, wherein the relative isotopics of this boron, sulphur or nitrogen show the fossil fuel source.

55. the composition of claim 50, wherein said carbonate, bicarbonate or its combination comprise calcium, magnesium or its combination.

56. the composition of claim 55, wherein calcium/magnesium (Ca/Mg) mol ratio is 1/200 to 200/1.

57. the composition of claim 55, wherein calcium/magnesium (Ca/Mg) mol ratio is 12/1 to 1/15.

58. the composition of claim 55, wherein calcium/magnesium (Ca/Mg) mol ratio is 5/1 to 1/10.

59. the composition of claim 50 further comprises the SOx or derivatives thereof.

60. the composition of claim 50 further comprises metal,

61. the composition of claim 60, wherein this metal comprises lead, arsenic, mercury or cadmium or its combination.

62. characterize the method for synthetic composition, comprise the relative carbon isotope composition (δ that determines said composition ¹³C) value.

63. the method for claim 62, wherein said composition is construction material or underground storage material.

64. the method for claim 62, wherein said composition is cementitious composition or gathers materials.

65. the method for claim 62, wherein said composition is to be used to store CO ₂Composition.

66. the method for claim 62 further comprises the CO that determines said composition ₂Discharge stability.

67. the method for claim 62 further comprises the carbon content of measuring said composition.

68. the method for claim 62 further comprises the δ of comparison said composition ¹³C value and another δ ¹³The C value.

69. the method for claim 68, wherein said another δ ¹³The C value is benchmark δ ¹³The C value.

70. the method for claim 69, wherein said another δ ¹³The C value is the possible raw-material value of said composition.

71. the method for claim 69, wherein said another δ ¹³The C value is the value of fossil fuel, the flue gas derived from described fossil fuel, water source or its combination.

72. the method for claim 69 further comprises according to this and determines relatively whether said composition comprises the CO that seals up for safekeeping from fossil fuel source ₂

73. the method for claim 62 further comprises the amount that quantizes the carbonic acid gas sealed up for safekeeping in the said composition.

74. fingerprint analysis method for compositions, the ratio that comprises the stable isotope of multiple element in the value of determining the stable isotope of multiple element in the said composition or the said composition, to determine the isotope element finger print of said composition, wherein said composition comprises carbonate, bicarbonate or its combination.

75. the method for claim 74, wherein said stable isotope comprises the isotope of carbon, sulphur, nitrogen or boron or its combination.

76. the method for claim 74, wherein said composition is construction material or underground storage material.

77. the method for claim 74, wherein said composition is to store thus the composition that the compound of at least two kinds of described isotopic elements determining is used.

78. the method for claim 74 further comprises more at least two stable isotope values or at least two stable isotope ratios or its combination.

79. the method for claim 74 further comprises may the originating of one or more components of determining said composition according to the isotope element finger print of this material.

Whether contain the method for the element of from fossil fuel source, sealing up for safekeeping 80. determine composition, comprise isotope value or the isotope value ratio of determining this element, whether more described definite value and benchmark isotope value or isotope value ratio and definite said composition contain the element of sealing up for safekeeping from fossil fuel source.

81. the method for claim 80, wherein this element is carbon, sulphur, nitrogen or boron.

82. the method for claim 80, wherein this element is a carbon, and this relatively is δ ¹³The C value.