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WO2017136288A1 - Échangeur de chaleur catalytique à matrice céramique - Google Patents

Échangeur de chaleur catalytique à matrice céramique Download PDF

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Publication number
WO2017136288A1
WO2017136288A1 PCT/US2017/015664 US2017015664W WO2017136288A1 WO 2017136288 A1 WO2017136288 A1 WO 2017136288A1 US 2017015664 W US2017015664 W US 2017015664W WO 2017136288 A1 WO2017136288 A1 WO 2017136288A1
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WO
WIPO (PCT)
Prior art keywords
fuel
catalytic
ceramic
oxidizer
heat exchanger
Prior art date
Application number
PCT/US2017/015664
Other languages
English (en)
Inventor
Robert G. Hockaday
Giampaolo Vacca
Jeff Poston
Pavlo Bagriy
Original Assignee
Ght Global Heating Technologies Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ght Global Heating Technologies Ag filed Critical Ght Global Heating Technologies Ag
Publication of WO2017136288A1 publication Critical patent/WO2017136288A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M27/00—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like
    • F02M27/02—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0861—Methods of heating the process for making hydrogen or synthesis gas by plasma
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D7/10—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically
    • F28D7/103—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically consisting of more than two coaxial conduits or modules of more than two coaxial conduits
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • F28D7/10—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically
    • F28D7/12—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically the surrounding tube being closed at one end, e.g. return type
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/04—Constructions of heat-exchange apparatus characterised by the selection of particular materials of ceramic; of concrete; of natural stone

Definitions

  • the present application relates to catalytic heaters that combust a fuel
  • oxidizer within a heater element to transfer heat to a working fluid, and more particularly to a catalytic heater that can efficiently combust the fuel in a plasma chamber.
  • high melting point materials are available that can withstand the tensions such as, carbon (3550°C), tungsten (3410°C), tantalum (2996°C), molybdenum (2617° C), chromium (1857°C), titanium (1660°C), iron (1535°C), nickel (1453°C), and their alloys but their oxidation temperatures in steam or air are all below 1000°C.
  • Ceramics with high melting points such as thorium dioxide (3050°C) zirconium oxide, (2700°C) aluminum oxide (Sapphire 2015°C) silicon dioxide (Quartz, 1610°C) Mullite (1840°C), Cordierite (1371°C maximum operational temperature) can withstand the oxidizing environment of combustion and can be fabricated into combustion system components, but are not suitable for tension applications. Ceramics in general have lower thermal expansion coefficients compared to the metals, high strength in compression but weak in tension. Some of these ceramic materials such as Cordierite and Mullite can withstand very high thermal gradients across their surfaces without stress failure due to their very low thermal expansion coefficients.
  • Mullite and Cordierite are used to form the tubular matrix monolith "honeycomb" porous catalyst supports in automobile catalytic converters. So there is a need for a method of delivering high temperature heat to engines and heat exchangers without oxidizing the pressurized components.
  • the present disclosure provides a catalytic heat exchanger
  • a heater element having a plurality of channels formed from a ceramic material and a ceramic envelope substantially enclosing the plurality of channels and defining a plasma chamber in a closed end.
  • At least one fuel nozzle and at least one oxidizer nozzle respectively dispense a fuel jet and an oxidizer jet that mix in the plasma chamber for combustion.
  • At least one of the fuel jet and oxidizer jet is directed through one or more channels toward the plasma chamber.
  • At least a portion of an exhaust flow from the plasma chamber is counter directed to contact at least one of the plurality of channels for catalytic combustion and to pre-heat the at least one of the fuel jet and the oxidizer jet.
  • the other of the fuel jet and oxidizer jet is pre-heated by the heater element.
  • Catalysts that promote catalytic combustion are positioned in contact with the mixed fuel and oxidizer jets and the exhaust flow.
  • the ceramic envelope that contains the plasma chamber heats a metal heat exchanger wall.
  • a space between the metal heat exchanger wall and the ceramic envelope contain an oxidization protective fluid.
  • FIG. 1 illustrates a cross-sectional view of heater with porous catalytic heat exchanger and enclosure, according to one or more embodiments.
  • FIG. 2 illustrates a cross-sectional view of switching catalytic heat exchanger with bayonet cylindrical geometry and fuel envelop, according to one or more embodiments
  • FIG 3A illustrates a cross-sectional view of switching catalytic heat exchanger with bayonet cylindrical geometry with fuel and oxidizer oscillatory nozzle array, according to one or more embodiments
  • FIG. 3B illustrates an isometric diagram of outbound jets of fuel and oxidizer that are loosely aligned with outlet holes in a honeycombed porous catalytic heat exchanger, according to one or more embodiments;
  • FIG. 3C illustrates an isometric diagram of inbound jets of fuel and outbound jets of oxidizer that are loosely aligned with outlet holes in a honeycombed porous catalytic heat exchanger, according to one or more embodiments;
  • FIG 4 illustrates a cross-sectional view of switching catalytic heat exchanger with planar radial geometry about a heat engine, according to one or more
  • FIG 5 illustrates a cross-sectional view of bore hole heater stacking arrangement, according to one or more embodiments
  • FIG 6A illustrates a cross-sectional view of central fuel and working gas tube heating catalytic heat exchange system, according to one or more embodiments
  • FIG. 6B illustrates a detail view of the central fuel and working gas tube heating catalytic heat exchange system of FIG. 6A, according to one or more embodiments;
  • FIG. 7 illustrates a cross-sectional view of borehole series heater stack in
  • hydrocarbon rich fractured geologic formation according to one or more
  • FIG. 8 illustrates an isometric view of a combination fuel and oxidizer manifold of an example heater, according to one or more embodiments
  • FIG. 9 illustrates a side cutaway diagram of a porous catalytic heat exchanger with water cooling, according to one or more embodiments.
  • FIG. 10 illustrates a side cutaway diagram of an underground oil stimulation system, according to one or more embodiments.
  • the present innovation provides catalytic heat exchanger and combustion heat system that uses jet flow ejected through low temperature components to impinge onto catalytic ceramic channeled matrix to do high temperature counter flow heat exchange to pre-heat reactant jets for plasma combustion within a cavity.
  • the combustion plasma in the cavity is converted to radiant emissions on contact with ceramic surfaces and the heat is transferred through an enclosing ceramic envelope.
  • Radiant heat is delivered through the enclosing ceramic envelope to components or materials separated from the combustion plasma and are radiantly heated through the ceramic envelope and can be protected from oxidation by an inert or reducing atmosphere.
  • Plasma combustion products are cooled with counter flow heat exchange with reactants catalytically oxidized in channels in the ceramic-channeled matrix adjacent to reactant inlet flow channels.
  • This system can heat engines, fuel cells, chemical processes, geologic oil deposits, water, and food. It is efficient, enduring, and non- polluting.
  • the present innovation utilizes tubular monoliths, such the catalytic honeycomb ceramic or metal monoliths used in automobile catalytic converters by using directed jet streams to control the flow of reactants into the tubular channels such that product flow will exchange heat and receive oxygen.
  • the encapsulating ceramic envelope forms a dead end cavity so the combustion products must flow back out through channels in the channel matrix that are not filled with inlet flows.
  • the tubular matrix forms a counter flow heat exchanger with the jet inlet side being cool and the plasma cavity side being hot.
  • the inlet jet flows of fuel and oxidizer being heated by exchanging heat with the outlet flowing combustion product gases and completing catalytic combustion in the porous catalytic channeled matrix.
  • the jet forming arrays and piping are kept cool and without a need for physical contact with the catalytic monolith so materials with high tensile strength such as metals can be used for form these components without oxidation.
  • the porous tubular catalytic monolith can be kept in an operational temperature range such that it can tolerate the thermal expansion stresses, oxidize, agglomerate, or melt.
  • This inventions temperature range and conditions is increased and enhanced by the physical features that catalytic ceramic monoliths utilized can withstand the high temperature reducing and oxidizing environments. Ceramics have very small thermal expansion coefficients and sufficient tensile and compressive strength to enable the temperature extremes as high as 1000°C across the monolith of 1 to 10 centimeters thick.
  • Channeled ceramic monoliths can withstand extreme thermal gradients because of their very low thermal expansion coefficients and sufficient tensile and compressive strength. Channeled ceramic monoliths have sufficient strength to withstand the small pressures exerted by the kinetic inlet jet streams and reverse outlet flows.
  • Our innovation includes using a protective gas technique to protect the metal components and to add a ceramic envelope that is not in high mechanical tension to contain the hydrogen rich atmosphere or inert gasses surrounding the metal surfaces of the heat exchangers. If the metal components can be protected from oxidation then it is possible to operate engines and heating systems far above the typical operational temperature ceiling of 1000°C. Heat engines made of molybdenum, tantalum, tungsten, and carbon, without internal cooling, are possible if they use inert or reducing working fluids such as argon or hydrogen gas. All of these materials have substantial structural strengths above 2000°C, but will oxidize typically in air above 800°C.
  • the reactants of fuel and oxidizers can be pre-heated in catalytic heat exchangers and heat exchangers removing heat from the exhaust gases.
  • Liquid fuels can be evaporated and some of these fuels can be also reformed in the hydrogen rich streams using the recovered heat from the exhaust.
  • the catalytic heat exchangers can be porous and transfer reactants such as oxygen from the incoming flow to gradually increase the oxygen content as the temperature declines in the heat exchanger tube flow to initially oxidize the carbon monoxide and then fully oxidize the nitrogen oxides.
  • the catalytic heat exchangers and non-catalytic heat exchangers are used to maximize the heating performance at the upper temperature of the combustion. For some of the fuels with low heating value without the pre-heating combustion will not occur so it is essential to pre-heat the reactants with the products.
  • a single side access can be designed to be insert-able and be a remove-able heater element. This feature of being able to remove heaters from a system without full disassembly can be a very useful. It reduces downtime and possibly enables the heater elements to be changed while the engine or system continues to operate. If the heater and engine interface has a low-pressure fuel gas or inert gas within a ceramic envelope it is possible to "hot swap" change out heater elements while the engine is at operating temperature.
  • the coefficient of thermal expansion differences between ceramic components and metal means that differential expansion must be accommodated.
  • Elastomeric and graphite seals can be used where components are cool and not exposed to hot reactive gasses. When temperatures are high components can be made with close fitting components that allow slippage and can contain protective gasses if they are low- pressure fluids. In this invention gaps in joints between the ceramic and metal components are arranged such that they are part of the fuel, oxidizer, or exhaust routes for the heater. This strategy permits much lower fit tolerances, and possibly sliding fits, to accommodate thermal expansion. To avoid seals in the high temperatures regions the components can be made long enough such that their metal ceramic interfaces can be elastomeric seals on the cooler ends.
  • Radiant heat transfer rates depend on facial area and absolute temperature to the fourth power if it is a black body.
  • the emission characteristics such as a narrow band- gap emissivity can modify the 4 th power emission rate somewhat.
  • This 4th power with temperature rate dependency as contrasted with conduction and convection heat transfer, creates an effect that catalytic heaters have a quick to equilibrate upper temperature set limit if the fueling rate is limited.
  • the heat exchangers arranged in this "dead end" loop with the combustion produced pre-heating reactant can as they run achieve very high temperatures to the point that they will melt the ceramic or reach heat loss equilibrium with the heat of combustion. Radiant heat losses will quickly rise with temperature such that an upper limit on the equilibrium point can be set.
  • the heaters operating temperature will be more constant than if the heat were removed by conduction or convention.
  • the plasma temperatures can be well above to where hydrocarbons will disassociate and combustion equilibrium can rapidly occur.
  • radiant emission can occur on the catalytic surfaces of the heat exchanger below roughly 800°C to enable the combustion to be completed and also not degrade the catalysts.
  • Emissivity surfaces in contact with the plasma such as thorium oxide
  • Heat to radiant energy emitters can be placed as coatings, nodules or fibers such that they make thermal contact with the plasma. Lining the ceramic envelope about the plasma and coating the aperture entrances to the catalytic matrix channels to make contact with the plasma. This cools the plasma exhaust, cools the ceramic substrates, and protects the catalysts within the catalytic heater exchanger from damaging temperatures.
  • the thorium oxide semiconductor produces a yellow light emission and is also a known catalyst.
  • Other semiconductors or materials can be chosen to emit in the longer wavelengths. Quartz or sapphire envelopes surrounding (containing) the plasma have a wide spectral emissivity. Infrared heating could be useful for shallow water heating. Short wavelength emission can be useful for lighting, deep water heating and photovoltaic conversion to electricity. Radiant heat delivery outside of the envelope can be selective by having reflective or absorbing surfaces.
  • the radiant surfaces and optical paths can be designed in a system such that heat can be delivered to specific areas with other areas being reflective. Uniform heating into a cavities or light pipes can be done with the design and placement of absorbing and reflective surfaces. This leads to an arrangement for uniform heating from a small radiant heater to have surfaces in close proximity having high albedo and distant surfaces having a low albedo
  • the ceramic envelopes containing the plasma combustion can be transparent to the radiant output of the plasma and catalytic combustion such as quartz and sapphire. These ceramics have light transmission windows from wavelengths of several microns to one-quarter micron and are able to transmit the high temperature radiant blackbody radiation. They also can withstand exposure to the combustion chemistry with a high oxygen content when they are kept bellow their melting points. [0039] Catalyst Protection
  • Catalytic heat exchangers can be used to pre-heat fuel and in some situations reform the fuels.
  • Low heating value fuels such as methanol and methane mixed with inert gases deliver less energy per unit mass than fuels such as kerosene.
  • air in combustion it roughly contains 80% inert gases, so a fraction of combustion energy is expended just to heat the inert gases and not delivering heat for the intended purpose, such as heating a boiler of a heat engine.
  • By transferring the heat from the exhaust to the incoming air the energy lost to heating the reactants up to the combustion temperature can be recovered. This heat transfer subsequently raises the combustion temperatures and the amount of delivered useful heat.
  • an endothermic reforming reaction in which the fuel is converted to hydrogen and carbon monoxide can be done on a catalyst while recovered heat from the exhaust. This can be used to increase total heat of combustion (Higher heating value) when the fuel is combusted.
  • the catalytic heat exchanger can be made of porous ceramics or metals that are impregnated with active catalytic particles. For mechanical integrity these can be monolithic honeycomb structures that have parallel channels of incoming and outgoing counter flows. These counter flows can be defined by using jets of gases flowing into the channels on the low temperature side of the heat exchanger and exhaust flows going out in remaining adjacent channels.
  • the jet manifolds can be made out of metals because they are not in thermal contact with the high temperature plasma, and they can perform additional lower temperature heat exchange of reactants and capturing heat and water from the exhaust flow.
  • Metal heat exchangers can be utilized bellow temperatures where the metal oxidizes in the working fluids.
  • the jet manifolds can be sealed and connected to pressurized sources of fuel and air.
  • the catalytic heat exchanger can exchange heat and diffuse reactants between the inflow and out flow. As the exhaust gases flow out of the heat exchanger they transfer heat and receive oxygen diffusing through the porous walls from the incoming airflow on the catalytic surfaces of the heat exchanger.
  • Pre-heating fuel and oxidizer gases in separate channels avoid a critical problem of pre-ignition. This separation of reactants prevents potential explosions and also protection of the metal from hot oxidizing gases.
  • the pre-heating of reactants; fuel and oxidizers in the counter flow catalytic heat exchangers enables the combustion temperatures and catalytic reactions to occur at higher temperatures than a single directional flow through a catalyst. By elevating temperatures, diffusion, combustion, and catalytic reactions happen faster.
  • pre-heating the reactants separately rather than as mixture it avoids the high temperature combustion in the ceramic matrix, that can be hot enough to melt the metals and ceramics and damage the catalysts in the channeled ceramic matrix, which can be unstable and possibly detonate damaging the heater system.
  • By mixing separated pre-heated reactants after the heat exchanger they combust as a hypergolic mixture that smoothly combusts when they make contact with each other into a cavity.
  • the catalytic heaters raises the surface temperatures of the catalyst surfaces more quickly, keeps catalytic surfaces above the dew point in the exhaust products, and can keep the inner hotter catalytic surfaces performing.
  • Condensed water can be pushed out through the small channels with the exhaust flow in the catalytic matrix. Condensed water can also be captured by wicking surfaces within the heat exchanger and catalytic surfaces and drawn away from the catalytic surfaces.
  • Upgrading is generally defined as any treatment of bitumen or heavy oil that increases its value. Therefore, the minimum objective is to reduce the viscosity of oil and the maximum objective is to obtain a crude oil substitute of higher quality.
  • Hydroprocessing reactions are thermal processes that take place in the presence of hydrogen. Such reactions can be both destructive and non-destructive.
  • Destructive hydrogenation hydrolysis and hydrocracking
  • Non-destructive hydrogenation or hydrotreating are simple hydrogenation reactions during which the quality of oil improves by removing certain contaminants of oil from its molecular structure such as sulfur (hydrodesulfurization (HDS)), nitrogen (hydrodenitrogenation (HDN)) and metals.
  • HDS hydrodesulfurization
  • HDN hydrodenitrogenation
  • reaction conditions vary in the different processes, however a typical
  • the temperature range is 300-345°C and the hydrogen partial pressure can be in the range of 500 to 1000 psi.
  • the catalyst used in hydrotreating reactions is normally cobalt-molybdenum with typically 10% molybdenum oxide and less than 1% cobalt oxide and the support is alumina.
  • a wide range of metals can be effective: cobalt, iron, nickel promoted copper and copper chromite.
  • the type of catalyst that is used in each process can change based on the immediate objective. For example, CoMo type formulae are generally used for HDS reactions, the NiMo type are employed for hydrogenation and HDN reaction and the NiW type are used for hydrogenation of very low sulfur cuts.
  • Hydrocracking is the reaction between hydrogen and oil fractions, mostly
  • hydrocracking can be divided into mild hydrocracking and conventional hydrocracking. Both of these two hydrocracking processes are similar with respect to the reactions, however, the products and their quality can vary because of the different reaction conditions. Mild hydrocracking normally takes place at some 50-80 bar (5-8 MPa) total pressure and temperature of 350-430°C, where conventional hydrocracking, the total pressure is about 100-200 bar (10-20 MPa) and the temperature is between 380-440°C.
  • the mechanism of hydrocracking is similar to that of catalytic cracking but includes concurrent hydrogenation.
  • the products of hydrocracking are either saturated or aromatic rings but not olefin.
  • hydrocracking reaction An important hydrocracking reaction is the partial hydrogenation of poly cyclic aromatics and the ultimate rupture of saturated rings to monocyclic aromatics.
  • hydrocracking is used for processes such as desulfurization and residue conversion to lower boiling distillates.
  • the reactions take place in the presence of dual -function catalysts.
  • Silica-alumina catalyst promotes cracking reactions where platinum, tungsten oxide, or nickel contributes to hydrogenation reactions.
  • the main advantages of down-hole upgrading include the reduction in refinery and upgrading costs, the reduction in size of surface upgrading facilities and the utilization of the pre-introduced heat from thermal processes.
  • a catalyst is introduced to the hydroprocessing zone where the catalyst may be a nano-particle catalyst that may be circulated within the hydroprocessing zone. Heat may be introduced to the one or more hydroprocessing zones (where different hydroprocessing reactions may occur) using the catalytic heat exchanger of the present invention.
  • the method of the invention controls the reaction
  • the catalytic heat exchanger can be used as a hydrocracker with hydrogen jets in channels and oxygen rich streams in other channels.
  • the arrangement of alternating and counter flowing channels with molecular exchange enables several solutions to the hydrocracking problem, in a small compact format.
  • Hydrocracking is generally accomplished by contacting the feedstock with a hydrocracking catalyst in a hydrocracking reaction vessel or zone at elevated temperature and pressure in the presence of hydrogen which results in a product containing a distribution of hydrocarbon products desired by the refiner.
  • the reactor operating conditions and the hydrocracking catalyst can be manipulated to influence the yield and composition of the hydrocracked products.
  • a typical heavy gas oil comprises about 50% or more hydrocarbon components boiling above about 371°C
  • a typical vacuum gas oil normally has a boiling point range roughly between 315 and 565°C (600 to about 1050°F).
  • the catalytic heater of the present invention is used to generate a gas
  • the pipe diameter is typically four (4) inches in diameter.
  • Heat transfer and hydrogen transfer into the oil or hydrocarbon is performed.
  • the jets of fuel and oxidizer can be periodically moved to an adjacent channel, switching the reducing or oxidizing environment of the channels. This enables coke deposits to be oxidized and the catalysts revitalized.
  • Hydrogen jets can surround the oxygen jet and the hydrogen rich diffusion into the hydrocarbons.
  • An aspect of embodiments of the present invention includes a device for
  • the device including an upper packer and a lower packer, which, when the device is placed within the borehole, together with the sides of the borehole, define a confined volume, a pump, communicable to the confined volume and configured and arranged to generate a pressure in the confined volume when the device is in use, and the catalytic heater of the present invention, configured and arranged to heat a fluid medium present in the confined volume when the device is in use.
  • the gas jets can be used to define the flow pattern of how fluids flows through ceramic and metal components and the combustion mixing.
  • the large difference in expansion coefficients between metals and ceramics results in the need for gaps between these components.
  • the gaps in the metal to ceramic interface can be used as the working nozzles and flow routes.
  • Gas jets can be defined as flowing into flow channels into ceramic monolith structures that due to their brittle nature cannot hold high internal pressures. Without physical seals between the metal jet nozzles and the ceramic catalytic tubular monolith it permits the nozzles to be moved in relation to the tubular monolith.
  • This periodic changing of the flow partem through the catalytic channels enables the catalytic chemistry to be periodically changed, which can swing between oxygen poor in the fuel jet to oxygen rich in the oxidizer jet, thereby oxidizing soot deposits and regenerating the catalyst.
  • One mechanism for the periodic movement can be to mount the nozzle arrays on bi-material spring mounts that causes the array to periodically rotate or displace a few mm with a thermal expansion- flow oscillation effect: Where the bi-material mounts are exposed to a change in temperature in the bi-material, that is causes by the changing of the manifold position, that causes a change in the flow pattern, which then causes a change in the bi-material temperature.
  • a second possible arrangement is to periodically restrict or open the jet nozzles with a rotating aperture plate inside the nozzle array manifold.
  • temperature heat exchanger can be made as a sealed pressurized metal envelope containing an inert or reducing working fluid.
  • the catalytic heat exchanger is used in one aspect to cover the exterior high temperature engine metal with a ceramic envelope that can contain an inert or reducing gas, about the high temperature portion of the engine to prevent oxidization.
  • the ceramic envelope can be sealed at the lower temperatures where elastic seals will survive.
  • the engine heat exchanger can be radiantly heated through the ceramic envelope or by inserting heaters into the engine ceramic envelope.
  • a power generation system with catalytic heat exchangers and heat recovery unit (HRU) and method.
  • a power generation system includes an array of one or more catalytic heat exchangers and an HRU.
  • the array of one or more catalytic heat exchangers operable to generate electrical power and heat from an catalytic reaction of the fuel and oxygen from an oxygen source.
  • the HRU is coupled to the array of catalytic heat exchangers and operable to generate electrical power from the heat.
  • the oxygen source may be preheated air and the fuel may be hydrogen, methane or methanol.
  • Heat generated by the catalytic heat exchangers includes radiant heat.
  • a power conditioning unit may be provided to receive and condition electrical power from the catalytic heat exchanger arrays and the HRU and to provide conditioned power to a load.
  • the HRU may be, for example, a thermoelectric HRU or a Stirling engine HRU.
  • the array of catalytic heat exchangers is operable to generate electrical power for a load from a thermoelectric source.
  • the array of catalytic heat exchangers may comprise 2, 4, 6, 8 or other suitable number of catalytic heat exchangers.
  • the present invention relates to a thermoelectric conversion generating device in which thermal energy is converted to electrical energy by imparting a temperature difference in a thermoelectric conversion module.
  • One aspect of the invention relates to a thermoelectric generator that generates electricity using heat energy of catalytic heat exchangers.
  • the catalytic heat exchangers has a combustion chamber into which the fuel source is placed for combustion.
  • thermoelectric generator mounted to the device (for example along a side) of the combustion chamber of the catalytic heat exchanger is a housing that encloses the thermoelectric generator, which generates an electrical output based on a difference in temperature on opposing sides (a "hot side” and a “cold side") of the thermoelectric device, wherein the larger the differential, the larger the electrical output.
  • Thermoelectric generators typically operate using the "Seebeck effect” (also referred to as the "thermoelectric effect”).
  • the temperature difference driving the thermoelectric generator may be provided between relatively hot radiant heat from the catalytic heat exchangers and relatively cold liquid fuel.
  • the thermoelectric generator may use the temperature difference between the relatively hot catalytic heat exchangers and the relatively cold fuel and/or air supply to produce electrical power.
  • the electrical power produced by the thermoelectric generator may be supplied to any electrical system including but not limited to an engine.
  • thermoelectric generator may be any suitable device configured to convert heat, in the form of a temperature difference, directly into electrical energy.
  • the thermoelectric generator may produce electrical power using the temperature difference between the catalytic heat exchangers (a high temperature source) and any suitable low temperature source.
  • thermoelectric generator includes a plurality of
  • thermoelectric modules e.g., cartridge type thermoelectric modules.
  • thermoelectric module has a circular cylindrical shape, for example.
  • thermoelectric module has an inner pipe through which coolant flows, an output pipe through which the inner pipe is inserted, and multiple thermoelectric conversion elements arranged between the inner pipe and the outer pipe. Also, the outer pipe (a heat receiving portion) is heated by the catalytic heat exchangers, and the inner pipe (a heat dissipating portion) is cooled by the coolant. As a result, a temperature difference is created between one side (the heat receiving portion side) and the other side (the heat dissipating portion side) of the thermoelectric conversion elements, and electricity is generated by the Seebeck effect in the thermoelectric conversion element.
  • the temperature control of the heaters can be controlled through control of the fuel, oxidizer and/or exhaust flow.
  • features of a switching catalytic heat exchanger can include:
  • Radiant heating receivers can be spatially separated and utilize varying absorbtivity and non-uniform heat delivery to remove deposits;
  • Radiant heating receivers can be spatially separated and utilize varying absorbtivity and non-uniform heat delivery to create hot spots, concentrate precipitate deposit points, and remove deposits;
  • Insertable combustors that can go into the heat exchangers can be made of ceramics, such as quartz, aluminum oxide, zirconium oxide, thorium oxide, and molybdenum disilicide;
  • (s) Working Fluid H, He, Ne, Ar, Kr, Xe, Rn, water, carbon dioxide, ammonia, methane, ethane, propane, methanol, chlorofluorocarbon fluids;
  • references within the specification to "one embodiment,” “an embodiment,” “embodiments”, or “one or more embodiments” are intended to indicate that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present disclosure.
  • the appearance of such phrases in various places within the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
  • various features are described which may be exhibited by some embodiments and not by others.
  • various requirements are described which may be requirements for some embodiments but not other embodiments.
  • FIG. 1 illustrates a heater system 100 that employs a catalytic heat exchanger
  • the heater element 104 includes a plurality of channels 106 formed from a ceramic material. For clarity, one fuel channel 106a and one oxidizer channel 106b are illustrated.
  • a ceramic envelope 108 substantially encloses the channels 106 and defines a plasma chamber 110 in a closed end 112. At least one fuel nozzle 114 and at least one oxidizer nozzle 116 respectively dispense a fuel jet 118 and an oxidizer jet 120 that mix in the plasma chamber 110 after passing through the channels 106a, 106b.
  • the heater element 104 is configured to utilize catalysts 122 formed of catalytic active materials supported by ceramic powders, beads, or fibers in the ceramic envelope 108 and heat exchanger.
  • a fuel manifold 124 formed by at least one stainless steel metal pipe 126 terminate in the fuel nozzle 114.
  • the fuel manifold 124 is supplied with pressurized fuel 128 such as hydrogen or methanol that is dispensed from as the fuel j et 118 into, or close proximity to, a proximal end 130 of one or more channels 106.
  • the channels 106 may be formed from quartz or alumina ceramic tubes that extend distally to a higher temperature perimeter of the plasma cavity 110.
  • the fuel jet 118 expands within the wider diameter of the channel 106 as compared to the fuel nozzle 114.
  • the fuel jet 118 flows forward with sufficient kinetic energy out of distal aperture 132 in the channel 106 to prevent back flow.
  • a gap between the ceramic channel 108 and the fuel manifold 124 is sufficient to accommodate the large differential thermal expansion of the metal pipe 126 yet not require a seal to prevent drawing in exhaust flow 128.
  • a temperature difference as high as 1000°C can occur between the ceramic channel 108 and the fuel manifold 124.
  • the metal fuel pipe 126 is cooled by the fast flowing expanding gas flow 128 as well as by liquid fuel vaporization at the fuel nozzle 114.
  • the ceramic channel 106 can be heated near the temperature of the exhaust flow 128.
  • An oxidizer manifold 134 can include at least one metal tube 136 is supplied with the pressurized gas oxidizer 138 such as air or oxygen.
  • the metal tube/s 136 inserted or placed in close proximity to the ceramic channel/s 106b with a larger flow area such that the oxidizer jet 120 flowing into the ceramic channel/s 106b is with sufficient kinetic energy that most of the air flows forward through the ceramic channel/s 106b.
  • the ceramic channel/s 106b contain the oxidizer jet 120 while heat is transferred into the oxidizer jet 120 and subsequently is released as hot gas into the plasma cavity 110.
  • the gap between the ceramic channel/s 106b and metal tubes 136 is sufficient to accommodate the large differential thermal expansion of the metal tube 136 and the ceramic channel/s 106b such as between stainless steel metal and quartz ceramic with a range of temperature that can be as high as 1000°C.
  • the metal tube 136 is cooled by the fast flowing and expanding oxidizer gas 138 while the ceramic channel/s 106b can be near the combustion exhaust flow temperature.
  • the plasma cavity 110 can be formed as a void in the catalysts 122.
  • catalytically active particles, fibers or beads can be molded into a porous ceramic envelope with a cavity using ceramic clays.
  • the ceramic envelope 108 can also be formed with a ceramic cage made of materials such as thorium oxide, quartz, mullite, alumina, and zirconium oxide surrounded by loose ceramic beads that are catalytic.
  • a radiant converter 140 as a coating or particles such as thorium oxide that can withstand contact with the combustion plasma, is placed on the walls of the plasma cavity 110 or ceramic channels 106.
  • the purpose of the radiation converters 140 is to convert heat from the low emissivity plasma, such as with hydrogen, methane and methanol, to light that can be transmitted through the porous ceramic envelope 108.
  • the radiant converters By converting heat energy in the plasma to radiant energy a large fraction of the heat energy can be removed from the plasma exhaust flow 134.
  • the radiant converters also spare catalysts 122 from the highest temperatures of the plasma since the catalyst 122 may not be able to withstand the temperatures of the plasma.
  • the radiant energy can move through the porous ceramic envelope 108 through the gaps or transmitted through the ceramic channels 106. Outside of the ceramic envelop 108 a metal enclosure 142 such as stainless steel or ceramic such as quartz enclosure (not shown) contains the heater element 104.
  • the porous ceramic envelope 108 forms a thermal barrier between the plasma and the metal envelope sufficient to keep the metal envelop from the corrosive hot oxidizing contact with the plasma 110.
  • This exterior metal enclosure 142 can be immersed into heat transfer working fluid 144 such as air or water to transfer heat.
  • the exterior metal envelope 142 could be placed as a part of vacuum chamber wall if only radiate heat is desired.
  • the exterior envelope catalysts 122 such a solution deposited platinum and palladium on powders, beads or fibers alumina ceramic substrates, can be loosely packed, or molded with (Castable Ceramics: Cotronics Corporation, 131 47 th Street, Brooklyn, NY 1 1232, and Kaowool moldable caulking: Sheffield Pottery 995 N. Main Street, Sheffield, MA 01257) into channels to allow exhaust flow routes from the plasma cavity 110.
  • the exit flow routes can be tortuous such as when the catalytic beads are packed about the ceramic tubes or can be an organized parallel flow channels or a network of branching channels.
  • catalytic porous flow channels function is to transfer heat via conduction, convection and radiation to incoming reactants and simultaneously catalytically on catalytic powders, beads or fibers in the heat exchanger 102 complete the combustion of hot plasma exhaust gas to the chemical equilibrium of a cool exhaust gas.
  • the exit flow routes can lead to the outside air or exhaust pipe.
  • pressurized cold fuel 128 and gas oxidizer 138 is delivered through the metal pipes 126, 136.
  • the exhaust flow 128 in contact with the metal pipes 126, 136 and catalysts 122 transfers heat to the fuel and oxidizer 128, 136. If the fuel 128 is liquid, sufficient heat needs to be transferred into the fuel 128 to vaporize the fuel 128 to a gas to enable gas-jetting into the ceramic channel/s 106.
  • the location of the transition between the ceramic and metal tubes is such that the combustion product temperatures are low enough, typically bellow 800°C, to not oxidize or melt the metal tubes 126,136, although high enough to vaporize the fuel 128.
  • the heater element 104 When the heater element 104 is at operational temperatures the pre-heat is sufficient to make the fuel 128 and oxidizer 138 become hyper gothic, and they ignite on contact with each other forming a plasma in the plasma chamber 110.
  • the fuel 128 and oxidizer 138 mix in the plasma chamber 110 without combustion and flow back through the catalytic exit flow routes where on contact with the catalysts 122 they catalytically combust the fuel 128 and oxidizer 138 releasing heat. This causes the catalysts 122 to rise in temperature and transfer heat into the incoming fuel 128 and oxidizer 138.
  • the ceramic channels/s 106 are kept within an operational temperature by imparting heat to the fuel 128 and oxidizer 138 and by a cooling effect as a pressurized flow expands upon gas-jetting, cooling the jets.
  • the plasma heats the radiant converters and the radiant output removes a fraction of energy content of the exhaust flow 134, 276. This reduces the enthalpy in the flow to the catalytic powders, beads and fibers 267. This removal of enthalpy by radiant heat transfer subsequently lowers of the operating temperature of the catalytic powders, beads or fibers 267, enabling the catalysts to maintain longer operational lifetimes.
  • the plasma exhaust flows further through the catalytic heat exchange routes 134, 268, 271 , 274, 276 heats is transferred from the heat capacity of the gas and the catalytic combustion on the catalytic particles 267 to the ceramic 106, 275 and metal tubes 126, 136.
  • FIG. 2 illustrates a switching catalytic heat exchanger 200 that heats a metal interior surface 202 of a heat exchanger wall 204 to transfer thermal energy to a working fluid 206 that is in contact with an exterior surface 208 of the heat exchanger wall 204.
  • the switching catalytic heat exchanger 200 is formed with a catalyst loaded ceramic tubular monolith 210 that is similar to those used in automobile catalytic converters.
  • the catalysts can be finely dispersed platinum, palladium and ruthenium on a refractory metal formed onto a Mullite or
  • Cordierite porous monolithic tubular substrate Cordierite porous monolithic tubular substrate.
  • the ceramic substrates can be formed by extrusion and firing to form channels 212 typically 1 mm in width.
  • the catalyst loaded ceramic tubular monolith 210 is formed to fit in a ceramic envelope 214, typically quartz.
  • the ceramic envelope 214 can be the shape of a test tube or beaker with a rounded or flat bottom. Cone-shaped fuel nozzles
  • Ceramic felts 220 can be inserted between the ceramic tubular monolith 210 and the ceramic envelope 214 to position and absorb vibrational energy.
  • Radiation converters 222 such thorium oxide can be distributed along walls 224 of a plasma cavity 226 formed by the closed end 218 of the ceramic envelope 214 and distal end 228 of the ceramic tubular monolith 210.
  • Radiation converters 222 such as thorium oxide mesh liners, nodules, fins, hairs, or speckled coatings can be used to have a low thermal capacity and allow equilibrium contact with plasma in the plasma cavity 226, while also allowing light to radiate out through the ceramic envelope 214.
  • Radiation converters 222 bonded or incorporated on to the face of the ceramic tubular monolith 210 can protect outer edges of the catalytic ceramic tubular monolith 210 from melting and convert exhaust heat of products of combustion in the plasma chamber 226 to light radiation as exhaust gas flows out of the plasma cavity 226 and over entrance edges of the channels 212 of the catalytic ceramic tubular monolith 210.
  • a radiant absorption layer 230 such as carbon black can be selectively coated on the metal interior surface 202 of the heat exchanger wall 204 outside of the ceramic envelop 214 to absorb the radiant energy where it is desired from a heater element 232 formed by the ceramic envelope 214 and ceramic tubular monolith 210.
  • the metal interior surface 202 of the heat exchanger wall 204 may be polished or coated with a reflector such as gold or silver to reflect light.
  • an oxidizer manifold 236 is formed with oxidizer fluid nozzles 238.
  • These oxidizer fluid nozzles 238 can be smaller in diameter then the widths of the channels 212 of the ceramic tubular monolith 210 such that oxidizer jets 240 from the oxidizer fluid nozzles 238 will flow in typically in one to two of the channels 212 in the ceramic tubular monolith 210.
  • the oxidizer manifold 236 is formed such that the oxidizer fluid nozzles 238 protrude out from the oxidizer manifold 236 and accommodate adjacent exhaust fluid flow 242 from adjacent ceramic monolith channels 212.
  • Fuel such as hydrogen, methane and or methanol is distally directed as fuel flow 244 into a space
  • the ceramic envelope 214 can be sealed to the metal interior surface 202 of the heat exchanger wall 204 by elastomeric seals (not shown) where the temperatures have been lowered due to the heat exchange between outgoing products of exhaust fluid flow 242 and incoming reactants of fluid flow 244.
  • liquid fuel such as methanol
  • the heat absorbed during evaporation of the liquid fuel can be used to keep a fuel manifold 248 and adjacent portions of the heat exchanger wall 204 and the ceramic envelope 214 below temperature limits of the elastomeric seals.
  • the fuel flow 244 in the space 246 is pressurized and will form a fuel jet 250 through each of the nozzles 216 in the ceramic envelope 214 into the plasma cavity 226.
  • the pressurized fuel flow 244 in the space 246 between the ceramic envelope 214 and the heat exchanger wall 204 can protect the metal interior surface 202 from oxidation.
  • Oxidizers such as air or pure oxygen can pressurize the oxidizer manifold 236 and can form the oxidizer jets 240 from the oxidizer fluid nozzles 238 that impinge into the channels 212 of the ceramic envelope 214.
  • oxidizers may be introduced respectively to the fuel and oxidizer manifolds 248, 236 since hydrogen can be catalytically reacted below -20°C. Diluted oxidizer mixtures with inert gasses such as nitrogen can be used to moderate the start-up and avoid explosions.
  • the oxidizer jets 240 and fuel jets 250 mix with each other in the plasma cavity 226 then contact the catalyst of the radiation converters 222 such as on the distal end 228 of the channels 212 and will spontaneously, catalytically combust in and around the outer channels 212. This combustion heats the ceramic tubular monolith 210 and enables conduction and radiant transfer of heat through the ceramic envelop 214.
  • the subsequent fuel flow 244 and oxidizer jets 240 will be pre-heated before entering the plasma cavity 226 until self-sustaining plasma combustion is achieved in the plasma cavity 226.
  • Sufficiently high carbon and low O2 contacting at a high temperature can be modulated to provide an optimum operation.
  • the small amount of O2 in the fuel decreases soot formation during combustion, avoiding a black smoky flame. The amount is kept below a level that can create a pop, explosion or a candle-like flame.
  • a fuel mixture that forms the fuel flow 244 can be changed as the plasma cavity temperature rises and is able to combust fuels at higher temperatures such as methane that has a catalytic reaction temperature of about 800°C.
  • the fuel could also be a mixture methane and a small fraction of hydrogen such that cold catalytic start-up will always occur, thereby avoiding complex fuel mixing controls.
  • a mixture of methanol and dimethyl ether is also a suitable fuel for catalytic combustion across the temperature range.
  • Methanol with water or hydrogen peroxide can be introduced as a liquid and as the heater heats the fuel manifold from exhaust flow, methanol vapor will flow though the space 246 between the ceramic envelope 214 and the metal interior surface 202 of the heat exchanger wall 204.
  • methanol in the fuel flow 244 decomposes to hydrogen and carbon monoxide above temperatures of approximately 200°C.
  • methane gas can thus be introduced and the switching catalytic heat exchanger 200 can run on methane fuel.
  • Mixtures of hydrogen, and hydrocarbons such as methane could be used to make the system more resilient to sudden shut downs and reduce the fueling cost depending on the cost of fuels. Care can be needed to avoid having a mixture that has a sufficiently high carbon and low oxygen content which can lead to coking of the fuel manifold 248 and the cone-shaped fuel nozzles 216.
  • the fuel and oxidizer are supplied as pressurized fluid of gas or liquid that can be flow regulated to produce a near stoichiometric mixture of fuel and oxidizer to achieve complete combustion.
  • the oxidizer jets 240 will flow along the vertical center axis of the plasma cavity 226 meeting the fuel jets 250 that are directed tangential to the axis of the cylindrical plasma cavity 226.
  • the resulting mixing flows in spiral and will spontaneously combust when temperatures in the flows are sufficiently high for ignition of this mixture of fuel and oxidizer.
  • the plasma will radiate heat energy and will heat the radiation converters 222 that line the walls 224 of a plasma cavity 226 and encounter a spiraling plasma flow 252.
  • the placement of the fuel jets from the device can be made to get a swirl or rotation of flow of gases in the combustion chamber.
  • the spiraling plasma flow 252 combusts and exits the plasma cavity 226 by displacement as exhaust flows 242 through the channels 212 not occupied by the oxidizer jets 240.
  • the exhaust flow 242 then cools, exchanging heat, combustion products, and oxidizer with the oxidizer flow.
  • the ceramic heat exchanger transfers heat to the reactants with counter-current flow.
  • Catalytic combustion of incomplete products such as carbon monoxide and nitrous oxides can occur on the surface of the porous catalytic tubular monolith 210.
  • the heated working fluid 206 outside of the exterior surface 208 of the heat exchanger wall 204 can be used for a variety of processes such as hydrocracking of oil, or heating the working fluid of a heat engine.
  • FIG. 3A illustrates a switching catalytic heat exchanger 300 that heats a metal interior surface 302 of a heat exchanger wall 304 to transfer thermal energy to a working fluid 206 that is in contact with an exterior surface 308 of the heat exchanger wall 304.
  • An absorption layer 330 on a portion of the metal interior surface 302 assists in transfer thermal energy from a distal end 313 of the ceramic envelope 314 through the heat exchanger wall 304.
  • the metal interior surface 302 is protected an oxidation protective gas 319 than can include an inert gas such as argon or a reducing gas such as hydrogen.
  • the switching catalytic heat exchanger 300 is formed with a catalyst loaded ceramic tubular monolith 310 having channels 312a - 312d that loosely fits within a ceramic envelope 308 having a rounded or flat test tube shape. For clarity, four channels 312a - 312d are depicted although embodiments according to the present innovation can have additional or fewer channels.
  • catalytic heaters consistent with aspects of the present innovation can incorporate a layer 318 of titanium dioxide (T1O2) as a photocatalyst that breaks down water, creating a protective layer of hydrogen ions.
  • T1O2 titanium dioxide
  • the T1O2 is super-hydrophilic so that oil will not stick to it and provides a surface attraction to more glass beads to serve as a catalyst surface.
  • Ti is made with glass beads painted on surfaces and then dried or baked on.
  • Ti is coated onto the quartz surface then heated to cause diffusion into the quartz .
  • the resulting T1O2 surface photocatalytically breaks down water with light from 322 light emitters or ambient light, leaves O2 surface, and organic compounds are eaten up on surface.
  • the T1O2 surface allows the system to become self-cleaning, avoiding oil to stick and foul the surface like an enamel coating.
  • the layer 318 can be exposed to gases, water, oil, oil and water, etc.
  • the layer 318 can be formed as or diffused into bumps on surface to increase surface area, enhancing the effect. Coating with T1O2 makes positive tertiary surface to push contaminants off. The shape of the surface changes surface tension and keeps precipitate such as salts from sticking to surface. Another compound that can be used for a similar effect is ZrC .
  • the present disclosure refers to "catalyst" as generally used herein refers to any chemical which enhances the rate and/or efficiency of molecular dissociation compared with the rate and/or efficiency of dissociation in the absence of the catalyst.
  • the energy of dissociation source includes a catalyst.
  • the catalyst enhances the rate of bond dissociation.
  • the catalyst can be any material of any physical configuration, which is compatible with the sample, and any other energy of dissociation sources.
  • Catalysts may be unifunctional, multifunctional, or a combination thereof. Catalysts can be used alone or in combination with other catalysts.
  • the catalyst is used to drive the reaction to 100% completion, i.e., dissociating generally every ammonia molecule into nitrogen and hydrogen.
  • the catalyst is applied to the target molecule or an interface between the energy source and the target molecule wherein the target molecule contacts the catalyst.
  • Catalyst is applied to a surface (such as a nanoparticle or tube), or dispersed into a surface.
  • the photocatalyst provides an effective means for converting light into chemical energy.
  • the catalyst or photocatalyst is semi-conductive material such as titanium oxides, platinized titania, amorphous manganese oxide, and copper-doped manganese oxide, titanium dioxide, strontium titanate, barium titanate, sodium titanate, cadmium sulfide, zirconium dioxide, and iron oxide.
  • Photocatalysts can also be semiconductors that support a metal, such as platinum, palladium, rhodium, and ruthenium, strontium titanate, amorphous silicon, hydrogenated amorphous silicon, nitrogenated amorphous silicon, poly crystalline silicon, and germanium, and combinations thereof.
  • Catalysts or photocatalysts can be carbon-based graphene or graphite, as well as carbon-doped semi-conductive or other magnetic material, for example, graphene doped AMO.
  • the ceramic envelope 308 lacks cone shaped fuel nozzles 216 (FIG. 2). Instead, a fuel manifold 348 proximate to a proximal end of the ceramic tubular monolith 310 has a fuel nozzle 316 that injects a fuel j et 350 into a fuel channel 312a.
  • the fuel can be pressurized hydrogen, vaporized methanol, or vaporized methane.
  • the heat received by the fuel manifold 348 vaporizes methanol or methane.
  • An oxidizer manifold has an oxidizer nozzle that injects an oxidizer jet into an oxidizer channel 312c.
  • the oxidizer is a pressurized oxidizer such as oxygen or air.
  • a first outer exhaust flow 342a moves proximally between the ceramic tubular monolith 310 and a portion of the ceramic envelope 314 proximate to the fuel nozzle 316.
  • a second outer exhaust flow 242c moves proximally between the ceramic tubular monolith 310 and a portion of the ceramic envelope 314 proximate to the oxidizer manifold 336.
  • An off-center exhaust flow 242d passes through an exhaust channel 212d proximate to the oxidizer manifold 336.
  • the mounting of the fuel and oxidizer manifolds 348, 336 within a cylindrical structure 356 of the switching catalytic heat exchanger 300 is radially spaced, bi- material leaf springs 358a - 358c that bend when heated and expand when cooled.
  • the mounting of the fuel and oxidizer manifolds 248, 236 are in close proximity to the catalytic tubular monolith 310 with the bi-material leaf springs 358a - 358c.
  • the arrangement of the exhaust flows 342a, 342d is made such that the switching catalytic heat exchanger 300 can latterly displace with respective the central axis of the cylindrical structure 356 at least the width of one channel 312a - 312d of the catalytic tubular monolith 310, which can be about 1 mm.
  • the channels 312a - 312d can change from injecting fuel or oxidizer to exhausting.
  • the off-center fuel and oxidizer manifolds 348, 336 will divert more of one outside exhaust flow 342a, 342d to the side that is lengthened (cooler), causing that bi-material leaf springs 358a - 358c to warm and bend, creating a restoring motion.
  • the bi-material leaf springs 358a - 358c can be made with sufficient thermal capacity and insulation so that there will be a time delay from the time the respective exhaust flow 342a, 342d impinges on the bi-material leaf springs 358a - 358c and the time the bi-material temperature rises and actuates. Similarly, a time delay can exist after the respective exhaust flow 342a, 342d is removed and the bi-material leaf springs 358a - 358c temperature continues to rise and then falls reversing its actuation. In operation, the respective exhaust flow 342a, 342d can oscillate over the bi-material leaf springs 358a - 358c.
  • the catalytic channels 312a - 312d can experience swings of chemical environments from the oxidizing environment to a reducing fuel environment.
  • This periodic swing of the chemical environment can clean and reactivate the catalysts in the porous ceramic and oxidize deposits such as coke that can form from the fuel decomposition when heated.
  • the pre- heated fuel and oxidizer jets 350, 340 exit the channels 312 of the ceramic catalytic tubular monolith 310 to enter a plasma cavity 326 where the jet 350, 340 mix, diffuse into each other and spontaneously combust as a plasma.
  • the combustion plasma in the plasma chamber 326 radiates light and is intensified when it comes in contact with radiant converters 322 such as ceramic fibers, nodules or coatings such as thorium oxide, that line the plasma cavity 326.
  • Radiant converters 322 on the distal end of the catalytic ceramic tubular monolith 310 cool the exhaust flows 342a - 342d by radiating energy back to the ceramic envelope 314 for externally transferring from the heater element 332 to protect the finely divided catalyst on the ceramic tubular monolith 310.
  • the exhaust products of the plasma flow through channels 312 in the catalytic tubular monolith 310 that are not occupied by the fuel or oxidizer jet flows 350, 340.
  • Full catalytic combustion of the cooling exhaust flows 242 occurs in catalytic channels by reacting carbon monoxide and nitrogen oxides (NOx) with oxygen and also receiving diffused oxidizer through the porous walls 360 of the tubular monolith 310 from the channels 212 that carry oxidizer. Heat from the catalytic combustion is transferred by conduction and radiation into the incoming oxidizer and fuel jets 340, 350.
  • NOx nitrogen oxides
  • Thorium dioxide/oxide operates as a light converter by getting hot and emitting light.
  • the light converter is 99% thorium and 1 % cerium oxide (or could be zirconium or yttrium).
  • Thorium is effective but is radioactive and can go through skin. Thorium is heavy, very dense, and does not aerosolize easily.
  • FIG. 3B illustrates inbound jets 370 of fuel (methane, methanol and water) and inbound jets 372 of oxidizer (oxygen or air) that are loosely aligned with outlet holes 374 in a honeycombed porous catalytic heat exchanger 376.
  • FIG. 3C illustrates outbound jets 378 of products (N 2 , H2O, CO2, exhaust) and inbound jets 372 of oxidizer (oxygen) that are loosely aligned with outlet holes 374 in a honeycombed porous catalytic heat exchanger 376, according to one or more embodiments.
  • Bimetallic actuations can induce (a) vibrations back and forth; (b) movements/rotation during use; and/or (c) turning off and on of jets. Changing the flow order bums off soot from catalyzation and change the oxidation environment.
  • the O2 can be a mix of
  • O2 and N 2 such as air, to be pre-heated.
  • Steam, carbon dioxide and nitrogen can be an output.
  • an O2 , N 2 , and fuel can be pre-heated with heat transferred from the output flow channels of steam and exhaust.
  • Exhaust streams find exit routes through any available port/tube not filled with an inbound jet.
  • FIG. 4 illustrates a heater system 400 that incorporates switching catalytic heat exchangers 200 to provide high temperature heating of a working fluid 406, such as an inert gas, of an external combustion heat engine 401.
  • a working fluid 406 such as an inert gas
  • the heat engine 401 could utilize one or more the switching catalytic heat exchangers 300 (FIG. 3).
  • a plurality of the switching catalytic heat exchangers 200 are radially aligned and spaced for rotation about an engine shaft 403.
  • the heat engine 401 has an enclosing metal enclosure 405 that seals inside an inert or reducing, pressurized working fluid 406 such as argon, hydrogen, or ammonia, inside.
  • the metal enclosure 405 that seals inside an inert or reducing, pressurized working fluid 406 such as argon, hydrogen, or ammonia, inside.
  • thermal insulation 409 surrounds a cylindrical portion 411 of each heat exchanger wall 204.
  • thermal insulation 409 include open cell foam glass or aerogels that fill the spaces between the annular high temperature core 407 and a lower temperature outer perimeter 413.
  • fluid seals such as graphite, Teflon or rubber 0-rings, can be used to seal, without damage, to a cool, proximal end of the ceramic envelopes 214 of the heater elements 232.
  • the fuel flow 244 that acts oxidation protection within the space 246 is sealed within the heat exchanger wall 204 of each switching catalytic heat exchangers 200.
  • the fuel is injected as tangential jets through fuel nozzle 216 in the ceramic envelope 214.
  • a ring oxidizer manifold 436 encircles the heat engine 401 and includes the oxidizer nozzles 438 that direct oxidizer jets into the catalytic ceramic tubular monoliths 210.
  • the operation of these heater elements 232 is described above with regard to FIG. 2.
  • Each heater element 232 can generate radiant light from the plasma combustion and radiant converters 222 can radiate the energy to the radiant absorption layers 230 on the metal interior surface 202 of a heat exchanger wall 204.
  • the heat in the heat exchanger walls 204 is transferred by conduction, convection and radiation into the working fluid 406 in the annular high temperature core 407.
  • the temperature of the working fluid 406 is increased by the heat transfer from the heat exchangers 200 and expands.
  • Downstream and upstream stator blades 415, 417 are radially attached to an upstream compressor annular ring 419 and a downstream turbine annular ring 420, respectively, that bracket the switching catalytic heat exchangers 200.
  • the downstream and upstream stator blades 415, 417 impede a convective flow 421 in the annular high temperature core 407 to compress the working fluid 406.
  • the upstream compressor annular ring 419 narrows in the direction of the convective flow 421 to cause compression of the working fluid 406.
  • the downstream turbine annular ring 420 widens in the direction of the convective flow 421 to cause decompression of the working fluid 406.
  • Upstream and downstream rotor blades 423, 425 interleaved respectively with the downstream and upstream stator blades 415, 417 and radially attached to the engine shaft 403 and respectively complete a compressor section 427 and a turbine section 429.
  • the maximum temperature that the working fluid 406 should be heated can be limited by the mechanical strength of the rotor blades 423, 425 in the working fluid 406 under stress. Being in a non-oxidizing environment and thus limited by internal cooling of 800°C, the mechanical strength temperature limits for these rotor blades 423, 425 can approach the melting temperatures of these materials such as, carbon 3550°C, tungsten 3410°C, tantalum 2996°C, molybdenum 2617° C, chromium 1857°C, titanium 1660°C, iron 1535°C, and nickel 1453°C. Further, the efficiency of the heat system 400 can be increased by raising the upper turbine temperature.
  • the temperature core 407 between the compressor annular ring 419 and a downstream turbine annular ring 420 causes the convective flow 421 to deliver more mechanical power to the downstream rotor blades 425 of the turbine section 429 than the compression to the working fluid 406 imparted by the upstream rotor blades 423 of the compressor section 427.
  • the extra mechanical energy can be delivered on the engine shaft 403 to an electric dynamo 431 having rotating magnets 433 and loops of wire 435. Front and rear bearings 437, 439 hold the engine shaft 403.
  • the electric dynamo 431 can be sealed in the metal enclosure 405 in the working fluid 406 to avoid having to make potentially leaky rotating shaft seals.
  • the working fluid 406 emerges from the turbine section 429 as a hot flow 441 and is directed to a counter flow heat exchanger 443 that cools the working fluid 406 down with chilled water 445 or other fluid.
  • the cooled working fluid 406 exits the counter flow heat exchanger 443 as a cooled flow 447 that returns to the compressor section 427 to complete a heat engine cycle.
  • Heated water 449 exits the counter flow heat exchanger 443 to go back to an evaporative cooler (not shown) to be chilled.
  • the heat engine cycle can generally be described as a Brayton cycle with adiabatic compression and decompression of an inert working fluid. Many other heat engine cycles such as Rankine, Ericsson, or Stirling cycles could be used with the switching catalytic heat exchangers 200 that can deliver radiant heat transfer to a heat exchanger.
  • FIG. 5 illustrates a catalytic heater system 500 that can heat geologic formations
  • Process heating such as hydro- cracking or food cooking, can be delivered faster and more uniformly by thermal radiation.
  • the radiant heating delivery rate is roughly proportional to the 4 th power of the absolute temperature and the emissivity of the source and absorptivity of the targets.
  • Metals used in piping, nozzles, and heat exchangers cannot resist oxidation in an oxygen rich plasma environment, but if the combustion mixture is oxygen poor the metal can resist oxidation but the combustion is incomplete and soot deposits can form eventually fouling the system. In all hydrocarbon combustion plasmas at and above 1000°C the combustion equilibrium is incomplete with a high fraction being carbon monoxide. Nitrogen oxides will be formed with high temperature air combustion.
  • a catalytic converter can be used to combust the incomplete products (CO and NOx) with oxygen added and heat is generated from the combustion. This heat energy from the catalytic converter is typically carried away by the exhaust products of water, carbon dioxide, and nitrogen, and represents wasted system energy.
  • the flow channels into a catalytic reactor can be reduced in proportion to the exposed surface area of the catalyst, to be efficient with catalytic material.
  • Combustion in catalytic beds will be constrained by the diffusion rates of reactants and products. Therefor diffusion-catalytic limited combustion systems will be relatively constant output over a wide range of pressures.
  • Flow through a catalytic reactor can be adjusted to have smaller diameter flow channels with respect to the catalytic body, or flow velocities of reactants and products could be slowed to compensate for increased reactant densities at higher pressure to maintain power outputs.
  • a technique of increasing the radiant emission from the combustion of non-carbon particle forming fuels is to insert a radiant emitter such as thorium oxide, carbon, or calcium oxide in contact with the combustion plasma.
  • a radiant emitter such as thorium oxide, carbon, or calcium oxide
  • Thorium oxide is a well-known candoluminescence emitter due to being a semiconductor that will emit light at 650nm and shorter wavelengths. This property has been used in gas light systems, but they typically had low efficiencies, and produced incomplete combustion products by exhausting their hot combustion gas to the atmosphere.
  • Catalytic heaters can combust fuels with oxidizers at low temperatures compares to flame combustion but at these low temperatures the products of the combustion can also condense at these temperatures. This leads to water blocking the surface of the catalysts.
  • the emission of the heater can be shifted to be closer to Black Body emission spectra by using a radiant emitter with large surface area and broad emission bands.
  • a radiant emitter with large surface area and broad emission bands An example is aluminum oxide fibers coated with fine particles of platinum and titanium dioxide. Emission in the longer wavelengths can be achieved by using a radiant emitter with its emission bands in the longer wavelengths such as smooth aluminum oxide coated with titanium dioxide.
  • Heat exchangers that utilize radiant heat transfer to convective heat transferring surfaces for fluid heat transfer can be designed differently compared to fluid-to-fluid heat transfer heat exchangers.
  • the radiant heat light rays need to have lines of sight toward the absorbers, and the convective heat transfer surfaces do not need to have high lateral thermal conductivity.
  • Selective heat transfer by coating the convective surfaces with light absorbing or reflective coatings can manage the spatial distribution of heat transfer into the convective heat transfer surfaces.
  • geologic deposits of high viscosity oils that can be extracted by reducing their viscosity.
  • a solution is to heat the geologic deposit, thereby reducing the viscosity, and push the oil out of the deposit with a pressure differential across and the deposit and water or other fluids displacing the oil.
  • High viscosity oil such as bitumen
  • Solvents are typically added to reduce this oils viscosity.
  • a possible solution, used in refineries, is to hydrocrack the oil by heating the oil 400°C to 850°C adding hydrogen, with a catalyst, at high pressure (typically at 3000 psi), for a short duration of microseconds.
  • the catalytic heater system 500 is configured to have heater elements 323 with the plasma cavities 326 head-to-head and the input fuel manifolds 548 and oxidizer manifolds 536 to be toe-to-toe.
  • These heater elements 323 can have duplicate parts.
  • the heater elements 323 can be used to heat viscous oil deposits or hydrocrack or retort pre-oil deposits.
  • the typical targeted temperatures rise needed in the geologic formation 502 ranges from 20°C to 400°C.
  • the heater element 323 is centered along the axis of the well casing 503. Pressurized fluid fuel 501 is delivered in fuel pipe/s 507 alongside the heater elements 323 in a bore pipe 509.
  • Fluid oxidizer 511 is delivered in oxidizer pipe/s 513 alongside the heater elements 323 within the bore pipe 509.
  • the reactant fuel and oxidizer pipes 507, 513 are attached and sealed to the fluid fuel and oxidizer manifolds 548, 536 and form the metal framework of the bore pipe 509 encaging the more brittle ceramic envelopes 314 of the heater elements 323.
  • the fluid fuel manifolds 548 and oxidizer manifolds 536 have internal channels for pressurized fuel 505 and oxidizer 511 that route to arrays of nozzles 515 - 518.
  • the nozzles 515 - 516 are designed and spaced such that the jets form alternate fuel jet flow 519, exhaust flow 520 and oxidizer jet flow 521.
  • the nozzles 515 - 518 are designed with diameters and lengths to impart velocity to the jets and sufficient pressure drop to create uniform flow rates from the nozzles in each manifold.
  • thermal actuated bi-material valves 523, 525 that when heated the thermal actuated bi-material valves 523, 525 block the flow of fuel 505 and oxidizer 511 respectively.
  • the thermal actuated bi-material valves 523, 525 are used to throttle back the heater elements 323 if they reach higher temperatures above a set limit. This local thermal limiting or throttling can useful particularly when stacks of heater elements 323 are in a pipe long enough such that the pressure drops down the supply fuel and oxidizer pipes 507, 513 is sufficient to create and higher pressures for the heater elements 323 close to the supply while the distant heater elements 323 operate at low pressures.
  • the heat transfer and temperatures of the geologic formation 502 may be different along the bore pipe 509 and well casing 503.
  • regulator mechanisms not shown may be needed within the reactant delivery piping and vent ports to avoid a range of uneven pressures or situations that could occur within a long heater strings and large geologic formations 502.
  • Electrical pressure sensors that measure stagnation and dynamic pressure of the flows can measure flow rates and could be installed in the reactant flow pipes.
  • Electrical temperature sensors such as thermocouples can be placed and protected in fuel flow pipes from oxidation to monitor heater performance. Both pressure/flow rates and temperature electrical sensor wiring and can similarly be protected from oxidation within the fuel supply lines. The data from these sensors can be used to control valves to control fuel and oxidizer supply flow rates.
  • FIGs. 6A - 6B illustrates a heater system 600 configured to heat working fluid
  • Oxidizer fluid jets 616 flow in channels 618 of a catalytic tubular monolith 620 by displacement forces of exhaust flow 622 through alternating channels, which are not shown for simplicity in the drawing.
  • the oxidizer jet 616 pre-heats with heat transferred by convection, conduction and radiation from the exhaust flows 622 and catalytic combustion of the outflowing exhaust flow 622.
  • the pre-heated oxidizer jet 616 such as air or oxygen, emerges into a toroid plasma cavity 624 bounded by the enclosing ceramic fuel envelope 612, an enclosing ceramic tube envelope 626 formed from a ceramic such as quartz, a catalytic tubular monolith 612, and ceramic insulation 628.
  • Fuel such as hydrogen, methane or methanol is flowed through a space 630 inside of the ceramic fuel tube 612 and outside of the metal pipe 604.
  • the fuel 614 is pre-heated radiantly as it flows through the ceramic fuel envelope 612 by the catalytic tubular monolith 620 and radiant heat from the combustion in the plasma cavity 624.
  • the fuel 614 protects the outer surface of the metal pipe 604 and delivers fuel to one or more fuel nozzles 632 in the ceramic tube. These fuel nozzles 632 direct fuel flow jets 634 to be tangential to the axis of the plasma chamber 624 and ceramic tube 626 to create a spiraling flow 636.
  • the spiraling pre-heated fuel 634 meets the oxidizer flow 638 along the axis of the plasma chamber and mix in the plasma cavity 624, spontaneously combusting on contact and spiraling 636 back along the walls of the cavity 626.
  • the plasma radiates through the ceramic fuel envelope 612 onto the metal pipe 604 and cools.
  • the plasma exits the cavity 624 it encounters the radiant converter ceramics 640 on the front surface of the catalytic tubular monolith 620 and it converts the heat to light.
  • This light radiates into the plasma cavity 624 and onto the metal pipe 604 enclosed by the ceramic fuel tube 612.
  • the ceramic envelope 626 has a high reflectivity such as fine-grained aluminum oxide ceramic that reflects light back onto the metal tube 604.
  • the exhaust flow 622 through the catalytic tubular monolith 620 follows channels 618 not occupied by oxidizer flow jets 616 and catalytically oxidizes as it cools, transferring heat into the incoming oxidizer flows 616.
  • Cool working fluid 602a is heated as is travels though the heater system 600 from radiant heating from the catalytic tubular monolith 620 and the combustion plasma 624 and then exits a hot working fluid 602b at a maximum hot temperature.
  • the working fluids 602 may be inert gases such as argon gas, reducing fluids such as hydrogen, methane, and sodium or reactive fluids such as oil, hydrocarbons, carbon dioxide, ammonia, oil, water, or salts.
  • the application of this heater system 600 could be placed in a borehole 501 and well casing 503 in a geologic formation 502 (FIG. 5).
  • FIG 7 illustrates the heater system 700 having a string of heater elements 701 to heat an oil bearing geologic formation 702 and simultaneously withdraw heated oil vapors and liquids 704 out through cracks 706 in the geologic formation 702.
  • oxidizer 708, fuel 710, exhaust 712, and hydrocarbon vapors 704 are channeled in concentric pipes 714, 718, 720 in a well bore casing 728.
  • a backflow stainless steel pipe 714 carrying the oil vapors and liquid 704 and exhaust 712 back to the earth's surface.
  • An oxidizer tube 716 formed by metal concentric stainless steel pipe surrounds the central pipe 714 forming an annulus 718 to carry oxidizer 708 such as 90% oxygen enriched air.
  • an inner ceramic envelope 720 such as a quartz tube, that forms an annular channel 722 for the fuel 710 and forms an inner wall of a plasma cavity 724.
  • An outer ceramic envelope 726 defines the outer wall of the plasma cavity 724; surround the central pipe 714, oxidizer tube 718, and inner quartz ceramic envelope tube 720.
  • stainless steel jet nozzle 730 and pipe interconnects 732 are shown that route flows of oxidizer 708 to the jet nozzle 730 arrays and allow oxidizer gas 734 to pass into catalytic ceramic tubular monolith channels 736. Only a few oxidizer and ceramic monolith channels 736 are shown for simplicity, while working devices the channels have typical channel dimensions of: wall thicknesses of 0.1 mm, 1mm channel widths, and 75 mm long in a tube array 50 to 100 mm in diameter.
  • the stainless steel nozzles 730 are typically 0.5 mm inside diameter or smaller.
  • the metal flow channel manifolds 732 also form the joints between heaters and use concentric pipe seal interconnections used in the drilling industry, but are not shown for drawing simplicity.
  • the inner ceramic tube 720 is held and sealed between the metal end jet manifolds 732 with graphite or elastomeric seals 738.
  • the outer ceramic envelope 726 has flow through channels 740 between the jet manifolds and does not need sealing but may use a ceramic alumina silicate fibrous felt 742 as an expansion joint between the ceramic envelop 726 and metal components 732, 714,716 and elastically holds the ceramic envelope 726 in place.
  • the fuel and oxidizer pipes 714, 716 deliver reactants from the earth's surface where they are pressurized and pumped to the heaters.
  • Suitable fuels 710 are methane mixed with hydrogen, dimethyl ether, propane, methanol, or town gas made from steam reforming of coal (predominately hydrogen and carbon monoxide). Hydrogen sulfide is removed from all fuel gases to prevent poisoning on the catalysts by reacting the coal reformates with high surface area iron sponge filters. Tangentially tilted nozzles 744 are formed in the inner ceramic tube 746 to form fuel jets 748 into the plasma cavity 724. The fuel jets 748 induce a spiral plasma flow 750 in the plasma cavity 724 when they met the oxidizer gas flowing along the center axis 752 of the plasma cavity.
  • the fuel is pre-heated with radiation and conductive heating from the plasma and radiant converters 754 by its flow through the annulus channel 756 between the oxidizer pipe 228 and the inner ceramic envelope 746.
  • Oxidizer gas jets flow 734 through the porous mullite ceramic tubular monolith 736 impregnated with platinum and palladium catalysts and pre-heats the oxidizer gas 734 using conduction and radiant heat exchange from the counter direction exhaust flow 712.
  • the pre-heated oxidizer 734, 752 and fuel jets 748 make contact and mix they spontaneously combust.
  • the resulting spiraling plasma 750 radiates heat within the annular plasma cavity between the outer ceramic envelop 726 and inner ceramic envelop 746 into the metal of the perforated well bore casing 728 and conducts heat into the oil bearing geologic formation 702 and into the fuel flow 710.
  • the radiant output of the plasma is increased when the plasma makes contact with the radiant converter coating 754 on the outer edge surfaces of the ceramic catalytic tubular monolith 736.
  • the plasma 712 cools and exchanges heat as it flows out through the ceramic catalytic tubular monolith 736.
  • This exhaust flow 712 catalytically combusts on contact with the catalytic tubular monolith 736 as it cools and receives diffused oxygen from the oxidizer flow 734, which adds additional heat to be exchanged with the incoming oxidizer gas flow 734.
  • the fully oxidized exhaust flows 712, 764 through the bi-material flap valve 762 and out with the vaporized and/or liquid oil 704 that flows though channels 740 in the outer quartz ceramic envelop 726 and through the jet manifold channels 732.
  • the combined exhaust flow and vaporized oil 704 flow back to the surface of the earth through the central pipe 714.
  • a fibrous ceramic plug 760 that forms a wall between the plasma cavities 724 to force the plasmas flows 750 back through the ceramic tubular monolith 736.
  • the ceramic plug 760 can be extended along the walls of the ceramic envelope 726 to hold the tubular monoliths in place 736.
  • Bi-material flap valves 762 are placed in outlet flow channels 764. These valves 762 shown schematically as two metals laminated together as a flap that when cold, such as when the heating system 700 is starting up, will restrict flow 764. The high thermal coefficient of expansion metal on one side will expand against the low thermal coefficient of expansion metal on the other side as the temperature rises curling the bi- material flap valve 762.
  • the flap valve 762 When the flap valve 762 is shown more open when the heater is running at the target temperature and the flap valve 231 is restricting flow when the heater temperature is over the target temperature. In all cases the flap valves 762 can act as a check valves to block back flow when the pressure in the geologic formation 702 is higher than the pressure of the flow 764, preventing back flow through the heater system and shutting the heater off. When pressure of the fuel 710 and oxidizer gas 708 is higher than the surroundings the flap valves 762 can open allowing flow of reactants and causing the catalytic combustion to resume.
  • the flap valves 762 with their temperature actuation restricting flow when above and below the target temperature can act as a temperature and flow equalizing mechanism in a multi-stack of heaters arrangement in a borehole.
  • the flap valves 762 will be able to partially compensate for these pressure and temperature environmental differences along the borehole as they occur by throttling the exhaust flow and heater outputs when the exhaust temperatures are close to a high temperature set point.
  • FIG. 7 illustrates thermal activated valves as an example as bi-material flap valves 762 as a cross-section of the curling bi-material made with metals within a channel, but a wide variety of arrangements and materials such as single or multiple valves, and/or bi-material rod and tube arrangements are suitable.
  • These valves can be formed such that they can also accomplish the objectives of check valves that open when reactant pressures are higher than the surroundings, but close and seal off the heater when the reactant pressures are lower than the surroundings. This enables the heaters to be immersed in liquid and contaminate rich borehole environments and avoid back flows that can clog and poison the catalytic heaters.
  • the flap valves can be set to have low temperature flow restriction for start-up and minimize losses in the event of a poisoned catalytic heater.
  • the flap valves 762 due to their bi-material actuation can open for maximum flow when the exhaust temperatures are at an optimum range for the heaters and can throttle and close off when upper temperatures in the exhaust flow occur.
  • FIG. 8 illustrates a combination fuel and oxidizer manifold 801 of an example heater 800, according to one or more embodiments. Most of the ports provide O2/N2 with few providing fuel. Manifold makes loose connections so moves and is not sealed, allowing ceramic and metal to work together across a huge temperature range.
  • FIG. 9 illustrates a porous catalytic heat exchanger 901 of a heater 900 with a water cooling system 903, according to one or more embodiments.
  • An oxidizing flow 904 and a fuel flow 906 in respective tubes 905 are preheated by the heater 900 to enhance combustion.
  • Tubes 905 of the porous catalytic heat exchanger 901 are made of a catalyst material and are somewhat porous in order to leak to a modest degree.
  • Pre-heating the fuel (Methane) 907 can create coke that would degrade performance.
  • migration of oxidizer (oxygen) 909 from an oxidizer supply 910 over to the tubes 905 containing fuel (methane) 907 prevent formation of coke.
  • the water cooling system 903 can be an active or passive device.
  • the former can implement a temperature sensor 911 that a temperature controller 913 responds to by actuating a controllable valve 915 to inject water 917 from a water supply 919 into a fuel (methane) supply 921 according to a temperature setting 923.
  • thermal energy from the heating element or heater 900 can cause a thermally-responsive heater actuator 925, which can include a manual temperature adjustment or setting 923, to modulate the controllable valve 915.
  • Use of methane (CH4) results in products of H2O and CO2.
  • water can be added to the oxidizer supply.
  • oxidizer can be added to the fuel.
  • steam treatment can be used to treat carbon or graphite buildup periodically.
  • FIG. 10 illustrates an underground oil stimulation system 1000 wherein a heating bore casing 1001 is within a heating bore 1002 that is drilled down and under a stratum 1004 that contains oil 1006 that is accessed from an oil bore 1008.
  • Catalytic heaters 1010 are positioned in a horizontal portion 1011 of the heating bore 1002 beneath the stratum 1004 and provided fuel 1012 through an inner fuel conduit 1014 and provide an oxidizer 1016 such as air through an outer oxidizer conduit 1018.
  • the fuel 1012 can be provided by a fuel supply 1020 that is moved by a fuel pump 1022.
  • the oxidizer 1016 can be provided by an air mover 1024.
  • the catalytic heaters 1010 release solid or viscous forms of oil 1006 from fissures 1025 in the stratum 1004 so that a pumping mechanism 1026 within an oil bore casing 1027 can retrieve the oil 1006 for capture in an oil tank 1028.
  • the pumping mechanism 1026 can include an upwardly and outwardly flared annular flapper seal 1028 attached for movement to a pump shaft 130.
  • the outwardly flared annular flapper seal 1028 is compressed toward the pump shaft 130 during a down stroke of the pump shaft 130 allowing oil 1006 to bypass the outwardly flared annular flapper seal 1028.
  • Above the outwardly flared annular flapper seal 1028 one or more inwardly and upwardly flared annular flapper seals 1032 are in sealing contact with pump shaft 130 when closed by pressure from oil 1006 above the inwardly and upwardly flared annular flapper seals 1032.
  • the outwardly flared annular flapper seal 1028 dynamically seals to the oil bore casing 1027 as bypassed oil 1006 is raised, forcing upward the inwardly and upwardly flared annular flapper seals 1032 out of sealing contact with the pump shaft 130, allowing bypassed oil 1006 to rise above the inwardly and upwardly flared annular flapper seals 1032.
  • the present innovation provides a
  • combustion heat delivery system comprised of: (1) one or more manifolds for fuel, oxidizer and exhaust fluids; (2) one or more ceramic enclosures largely impermeable to gas containing a catalytic tubular monolith with channels; (3) nozzles in manifolds form oxidizing fluid jet flow impinging on separate channels without seals into catalytic tubular monolith; (4) and/or nozzles in fuel jet fluid manifold flow impinge without seals into separate channels of catalytic tubular monolith; (4) and oxidizing fluid and or fuel fluid is heated by flow through catalytic tubular monolith emerging to mix and combust in cavity within largely impermeable ceramic enclosure, with products of combustion flowing through separate catalytic tubular monolith channels to transfer heat into oxidizing fluid and or fuel fluid in separate catalytic tubular monolith channels.
  • the present disclosure provides a combustion heat delivery system comprised of: (1) one or more manifolds for fuel, oxidizer and exhaust fluids; (2) one or more ceramic enclosures largely impermeable to gas, wherein the ceramic enclosure covers fuel or inert gas over oxidize able material, (3) wherein the ceramic envelope contains one or more ceramic catalytic tubular monolith with channels. Oxidizing fluid flows from manifold though ceramic catalytic tubular monolith in separate channels and or fuel fluid flows from manifolds into separate channels of ceramic catalytic tubular monolith.
  • Oxidizing fluid and or fuel fluid is heated by flow through catalytic tubular monolith emerging to mix and combust in cavity within largely impermeable ceramic enclosure transferring heat through ceramic enclosure to oxidize able material with products of combustion flowing through separate ceramic catalytic tubular monolith channels to catalytically oxidize and transfer heat into oxidizing fluid and or fuel fluid in separate ceramic catalytic tubular monolith channels.
  • the present disclosure provides a combustion heat
  • oxidizing fluid delivery system comprised of: one or more manifolds for fuel, oxidizer and exhaust fluids; one or more porous catalytic ceramic enclosures, wherein the porous catalytic ceramic enclosure contains at least one plasma cavity and prevents plasma contact with metal enclosure and metal fuel fluid and oxidizing fluid tubes, wherein the ceramic enclosure permits passage of two or more channels, wherein oxidizing fluid flows though channels into plasma cavity, wherein fuel flows through separate channel into plasma cavity, with fuel and oxidizer mixing and partially combusting in plasma cavity, wherein oxidizing fluid and fuel fluid is heated by flow through ceramic channels and metal tubes with exchange of heat with plasma exhaust being cooled catalytic combustion occurring within ceramic channels as exhaust flow of plasma departs through porous catalytic enclosure, wherein metal tubes flow fuel into ceramic channels and metal tubes flow oxidizer into ceramic channels without seals between ceramic channels and metal tubes.
  • the catalytic tubular monolith can be a porous ceramic that supports finely dispersed catalyst particles or coatings.
  • catalysts can contain platinum, palladium, rubidium, iridium, ruthenium, thorium oxide.
  • the porous ceramic can contain aluminum oxide, cerium oxide, zirconium oxide, silicon dioxide, calcium silicate, Mullite or Cordierite.
  • the catalytic tubular monolith channels can be parallel. At least one ceramic enclosure covers fuel or inert gas over oxidizable material.
  • the catalytic tubular monolith channels can be porous and can transfer heat and reactants to flowing streams in separate channels.
  • catalytic tubular monolith channels can be porous and can transfer heat and reactants to counter flowing streams in separate channels.
  • Metal components can be protected by a fuel or inert gas outside of largely impermeable envelope and metal components.
  • heat is delivered into fluid or wall of heat engine.
  • the plasma combustion can rotate with the ceramic envelope to interact with catalysts.
  • the catalytic enclosure can contain catalyst coated ceramic beads, fibers, or powders.
  • the plasma combustion rotation can be induced by reactant jet flow impingement on plasma.
  • the ceramic envelope can be penetrated by holes to flow fuel or oxidizer fluid into the plasma cavity.
  • radiant heat transfers through ceramic envelope.
  • radiation converters in the plasma cavity can convert thermal energy from the plasma combustion to radiant energy that transmits through the ceramic envelope.
  • the radiant converters such as a ceramic that converts heat to light can be next to apertures of the catalytic tubular monolith that encounter combustion products from the plasma cavity.
  • the ceramic envelope can be impermeable and can be insertable or immersible into fluid or material.
  • the ceramic envelope can be part of enclosure for fuel.
  • the catalytic tubular monolith can heat exchange to reform fuel.
  • the combustion heat delivery system can be used immersed in fluid to heat fluid, can be used within holes bored in the ground, and can be used for chemical reforming.
  • the heat output can be used to heat through metal walls of a well bore, fluids of oil, hydrocarbons, water, carbon dioxide, salts, and/or, solids of minerals, soil, sand, rocks, concrete, metals, and or salts.
  • the combustion heat delivery system can receive reactant or product flows that are controlled by temperature activated valves.
  • the combustion heat delivery system can receive reactant or product flows that are regulated by pressure activated valves.
  • the reactant flows are controlled by valves actuated with electrical power and controlled though electrical sensors of temperature and/or pressures.
  • the ceramic envelope is transparent to thermal radiation.
  • receivers of radiant energy such as radiant absorption layers through ceramic envelope can be spatially patterned.
  • receivers of radiant energy through ceramic envelope can be spatially patterned to produce spatially separated temperature differences.
  • receivers of radiant energy through ceramic envelope are light to electricity converters.
  • the catalytic tubular monolith channel walls are permeable and diffuse oxygen through channel wall with oxygen bearing fluid through channel wall and catalytically oxidize combustion product fluid flowing in adjacent channels. Separate fuel and/or oxidizer flow jet or jets impingement placement on tubular monolith channels is oscillated in time.
  • the ceramic envelope of heater is insertable into a form-fitting receptacle for receiving heat energy.
  • the combustion heat delivery system can utilize fuel containing one of more of hydrogen, methane, methanol, dimethyl ether, ethanol, propanol, ethane, butane, propane, or ammonia.
  • Metal surfaces, electronics and/or wires of the combustion heat delivery system can be protected from oxidation by an inert gas that contains one or more of helium, neon, argon, krypton, xenon, radon or
  • the combustion heat delivery system can be used to heat using radiant energy through the ceramic envelope a fluid of oil, water, carbon dioxide, ammonia, hydrogen, methane, methanol, dimethyl ether, ethanol, propanol, ethane, butane, or propane.
  • Embodiments consistent with aspects of the present innovation can use an
  • Embodiments of the present innovation can include a domed heater device used in borehole drilling/fracking. Embodiments of the present innovation can be used for cooktops for a heating element. Embodiments of the present innovation can be used for engines that perform thermal heating (e.g., a steam engine). Embodiments of the present innovation can provide a water heater to power a steam generator.
  • catalytic heaters consistent with aspects of the present disclosure can be used for food cooking such as in barbeque grills, oil frying equipment, and stoves. Catalytic heaters consistent with aspects of the present disclosure can be used for institutional and residential ambient air heating and water heating.
  • the present disclosure relates to radiant cooking devices and, more particularly, to cooking devices that employ infrared radiant energy to cook food.
  • the embodiments disclosed herein provide a cooking assembly that uses infrared radiant energy from catalytic heaters consistent with aspects of the present disclosure to cook food.
  • the cooking assembly includes a cooker that may include a heating element configured to conductively heat a cooking vessel placed within the cooker.
  • the catalytic heat exchangers utilize radiant heat transfer to convectively heat surfaces.
  • the cooking vessel may be made of a generally transmissive material, as opposed to opaque materials, such that a larger percentage of the infrared radiant energy can be transmitted through the cooking vessel.
  • the infrared radiant energy transmitted into the cooking vessel is then able to be emitted toward and absorbed by the food placed within the cooking vessel.
  • Suitable transmissive materials that may be used for the cooking vessel include, but are not limited to, glasses, glass- ceramics, stovetop ceramics, and vitro-ceramics.
  • a catalytic heater according aspects disclosed
  • a heater having an AI2O3 window can allow radiant light to enter to heat and can tolerate high pressures.

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Abstract

L'invention concerne un système de chaleur de combustion, lequel système utilise un écoulement de jet éjecté par l'intermédiaire d'éléments à basse température pour frapper une matrice à canaux catalytique pour effectuer un échange de chaleur à contre-courant à haute température pour préchauffer des jets réactifs pour une combustion à plasma à l'intérieur d'une cavité. Le plasma de combustion dans la cavité est converti en émissions de rayonnement lors du contact avec des surfaces et la chaleur est transférée par l'intermédiaire d'une enveloppe en céramique de confinement. La chaleur rayonnante est fournie par l'intermédiaire de l'enveloppe en céramique de confinement à des éléments ou à des matériaux séparés du plasma de combustion, ces derniers étant chauffés par rayonnement par l'intermédiaire de l'enveloppe en céramique et pouvant être protégés de l'oxydation par une atmosphère inerte ou réductrice. Les produits de plasma de combustion sont refroidis et oxydés de façon catalytique dans des canaux lors de leur écoulement de sortie dans les canaux de matrice catalytique adjacents à des canaux d'écoulement d'entrée.
PCT/US2017/015664 2016-02-01 2017-01-30 Échangeur de chaleur catalytique à matrice céramique WO2017136288A1 (fr)

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CN108757247A (zh) * 2018-08-07 2018-11-06 天津开发区天盈企业有限公司 一种燃油催化节能油箱
CN113324247A (zh) * 2021-05-26 2021-08-31 华中科技大学 一种高效预热的小型非预混燃烧器高温热源
CN113513764A (zh) * 2021-07-16 2021-10-19 陕西正涛能源科技有限公司 一种氩回收的分离设备及分离方法
CN116963326A (zh) * 2023-08-02 2023-10-27 南通通杰照明有限公司 陶瓷加热器和电热塞
WO2024074504A1 (fr) * 2022-10-03 2024-04-11 First Graphene (UK) Limited Perfectionnements se rapportant à des matériaux carbonés

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CN108757247A (zh) * 2018-08-07 2018-11-06 天津开发区天盈企业有限公司 一种燃油催化节能油箱
CN113324247A (zh) * 2021-05-26 2021-08-31 华中科技大学 一种高效预热的小型非预混燃烧器高温热源
CN113513764A (zh) * 2021-07-16 2021-10-19 陕西正涛能源科技有限公司 一种氩回收的分离设备及分离方法
CN113513764B (zh) * 2021-07-16 2023-11-03 上海联风气体有限公司 一种氩回收的分离设备及分离方法
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CN116963326A (zh) * 2023-08-02 2023-10-27 南通通杰照明有限公司 陶瓷加热器和电热塞

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