WO2005001977A1 - Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions - Google Patents

Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions Download PDF

Info

Publication number
WO2005001977A1
WO2005001977A1 PCT/US2004/019379 US2004019379W WO2005001977A1 WO 2005001977 A1 WO2005001977 A1 WO 2005001977A1 US 2004019379 W US2004019379 W US 2004019379W WO 2005001977 A1 WO2005001977 A1 WO 2005001977A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbonaceous
gas
waste
cell
exit
Prior art date
Application number
PCT/US2004/019379
Other languages
French (fr)
Inventor
Terry Galloway
Original Assignee
Intellergy Corporation
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
Priority claimed from US10/602,536 external-priority patent/US7132183B2/en
Application filed by Intellergy Corporation filed Critical Intellergy Corporation
Priority to EP04755504A priority Critical patent/EP1652256A4/en
Priority to CA2530496A priority patent/CA2530496C/en
Publication of WO2005001977A1 publication Critical patent/WO2005001977A1/en

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/005Rotary drum or kiln gasifiers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02Fixed-bed gasification of lump fuel
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0643Gasification of solid fuel
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0668Removal of carbon monoxide or carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0969Carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0973Water
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/16Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656Conversion of synthesis gas to chemicals
    • C10J2300/1659Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/18Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807Recycle loops, e.g. gas, solids, heating medium, water
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/18Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807Recycle loops, e.g. gas, solids, heating medium, water
    • C10J2300/1823Recycle loops, e.g. gas, solids, heating medium, water for synthesis gas
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H01M8/04156Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
    • H01M8/04164Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal by condensers, gas-liquid separators or filters
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
    • H01M8/0631Reactor construction specially adapted for combination reactor/fuel cell
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00Combustion technologies with mitigation potential
    • Y02E20/16Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/30Fuel from waste, e.g. synthetic alcohol or diesel
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry

Definitions

  • This application is not a continuation-in-part of the latter application, U.S. Serial No. 09/186,766, as stated in the parent application, U.S. Serial No. 10/184,264.
  • This invention relates to non-greenhouse gas emitting processes and systems which accomplish the conversion of a carbonaceous gas stream and a greenhouse gas into a synthesis gas comprising hydrogen and carbon monoxide without the need for expensive catalysts and or high pressure operations.
  • BACKGROUND OF THE INVENTION The burning of fossil fuels in boilers to raise high temperature, high- pressure steam that can be used to power turbo-electric generators produces a problem source of carbon dioxide and other greenhouse gases, e.g. methane, ozone and fluorocarbons.
  • the process and system of the invention converts carbonaceous feedstock from fossil fuels and other combustible materials into energy without the production of unwanted greenhouse emissions.
  • the present process comprises the following steps: (a) converting a carbonaceous feedstock and a greenhouse gas stream in a gasification unit to synthesis gas comprising mainly carbon monoxide and hydrogen, where the gasification unit is a non-catalytic high temperature, gas-phase reactor operating at conditions to achieve a gas exit temperature of from at least 700° to about 1600°C (1300-2900°F); (b) electrochemically oxidizing at least a portion of the synthesis gas from the gasification unit in a first half-cell of a fuel cell to produce a first half-cell exit gas comprising carbon dioxide and water; (c) recovering the carbon dioxide from the first half-cell exit gas to serve as a greenhouse gas stream in step (a); and (d) electrochemically reducing an oxygen-containing gas in a second half-cell of the fuel cell completing the circuit and resulting in the
  • the invention disclosed and claimed in the '465 patent preferably used a gasification unit containing a catalyst that operates at a temperature in the range of about 400° to about 700°C (750-1300°F) and still more preferably, a gasification unit using a fluidized catalytic bed.
  • a catalytic bed requires expensive catalysts and/or high- pressure operations.
  • the catalysts e.g., nickel or copper-based ceramic supported catalyst typically used in steam reforming of methane or shift converters are easily poisoned by halogens or heavy metals found in waste streams that are a desirable candidate for waste-to-energy-systems.
  • the present system comprises the following: (a) the gasification unit that is a non-catalytic high temperature, gas-phase reactor operating at conditions to achieve a gas exit temperature of from at least 700° to about 1600°C (1300 to 2900°F), for converting a carbonaceous and a greenhouse gas stream feedstock into the synthesis gas; (b) the fuel cell for the production of electrical energy comprising the first half-cell having an inlet in fluid communication with the synthesis gas and a first means or anode for electrochemically oxidizing synthesis gas into the first half-cell exit gas, a second half-cell having a second means or cathode for electrochemically reducing the oxygen-containing gas, and a membrane separating the first and second half cells that will not allow passage of the gaseous components from the respective half-cells; and
  • the non-catalytic, gas-phase reactor is a kiln having an inlet means, a gas outlet means, and a solids outlet between the inlet means and the gas outlet means and operating at a temperature gradient along the length of the kiln of about 200° to about 1600°C (400-2900°F).
  • the present process avoids the difficult path of attempting to strip and capture the carbon dioxide from stack gases and without attempting to carry out separate chemical reactions of carbon dioxide to attempt to produce useful products.
  • the process and system of the present invention uses unique gasification technology combined with fuel cells to generate electricity at high efficiency. This is accomplished by taking advantage of a very unique property of fuel cells - namely, the two anodic and cathodic reactions are separated by an electronically conducting membrane that keeps the product gases separate.
  • a combustible feed gas can be fully oxidized in the first half-cell of the fuel cell without being commingled with the final products of the air reduction in the second half-cell electrode, i.e., N 2 .
  • synthesis gas is formed consisting predominantly of hydrogen and carbon monoxide.
  • This synthesis gas is fed into the first half-cell, i.e., the anode or negative terminal side, of the fuel cell, such as the solid oxide or molten carbonate types, where it is oxidized to water and carbon dioxide.
  • These gases are not diluted by the typical nitrogen remaining after oxygen reduction in the second or remaining half-cell, i.e., the cathode side or positive terminal, of the fuel side.
  • Nitrogen and combustion gases are commingled when combustion air is used in boilers or furnaces.
  • the synthesis gas syngas
  • the fuel cell-produced water and carbon dioxide are simply separated from each other by condensing the liquid water and allowing the carbon dioxide to return to the gasifier.
  • the carbon dioxide being injected into the high temperature gasifier undergoes a reaction with the high temperature carbonaceous feed to form more carbon monoxide, repeating the cycle.
  • the carbon dioxide in the fuel cell is easily kept separate from the air side and any nitrogen. This carbon dioxide can be recycled back to the gasifier in nearly pure form.
  • steam in pure form can be recycled as well in different amounts under gasifier control system requirements to maintain the ideal hydrogen to carbon monoxide ratio in the range of about 1.75 to about 2.5.
  • This helps maintain a high hydrogen content in the gasifier so that a portion of the gasif ⁇ er-produced syngas can be used downstream in a chemical reactor such as a Fischer-Tropsch reaction system for the production of a variety of useful chemicals ranging from methanol to paraffin waxes.
  • useful chemicals such as naphtha, gas oil, and kerosine, or agricultural chemicals or carbide abrasives. The latter are not ever burned in their lifecycle, and they sequester the carbon forever.
  • the carbon monoxide is used to produce useful chemicals instead of discarding the valuable carbon source in the carbon dioxide.
  • the carbon balance of the plant is maintained such that the mass of carbon input in the waste feed is equal to the carbon mass leaving the plant as valuable hydrocarbon products; not carbon dioxide.
  • What has been achieved is a chemical plant merged with a power plant that produces useful hydrocarbon products, high efficiency electric power without any carbon dioxide or other greenhouse gas emissions.
  • most importantly gasification is much more flexible than a refinery or a coal boiler, since a wide variety of waste streams can be used as the feed material. Thus, this solves two serious problems.
  • the process of the present invention is designed for use in a waste-to- energy plant using carbonaceous feedstocks such as coal; hydrocarbon oil; natural gas; petroleum coke; oil shale; carbonaceous-containing waste oil; carbonaceous- containing medical waste; carbonaceous-containing military waste including explosives, spent armaments, chemical and biological weapons agents, and unexploded ordinance; carbonaceous-containing industrial waste including hazardous waste, insecticides, pesticides, fumicides, algaecides, and the like; carbonaceous- containing sewage sludge and municipal solid waste (MSW); carbonaceous- containing agricultural waste; carbonaceous-containing biomass, biological and biochemical waste; and mixtures thereof.
  • carbonaceous feedstocks such as coal; hydrocarbon oil; natural gas; petroleum coke; oil shale; carbonaceous-containing waste oil; carbonaceous- containing medical waste; carbonaceous-containing military waste including explosives, spent armaments, chemical and biological weapons agents, and unexploded ordinance; carbonaceous-containing industrial waste including hazardous waste, insect
  • FIG. 1 is a schematic process flow diagram of a preferred embodiment of the process and system of the present invention
  • FIG. 2 is a plot of the commercial steam reforming of methane to make syngas consisting of hydrogen and carbon monoxide
  • FIG. 3 shows a plot of the steam reforming of a mixture methane and fuel cell produced carbon dioxide at about 20% in the feed
  • FIG.4 shows a plot of the steam reforming of a mixture methane and fuel cell produced carbon dioxide at 25% in the feed
  • FIG. 5 shows a plot of the steam reforming methane and fuel cell produced carbon dioxide at 30% in the feed
  • FIG. 1 is a schematic process flow diagram of a preferred embodiment of the process and system of the present invention
  • FIG. 2 is a plot of the commercial steam reforming of methane to make syngas consisting of hydrogen and carbon monoxide
  • FIG. 3 shows a plot of the steam reforming of a mixture methane and fuel cell produced carbon dioxide at about 20% in the feed
  • FIG.4 shows a plot of the steam reforming
  • FIG. 6 shows a plot of the steam reforming methane and fuel cell produced carbon dioxide at 27.6% in the feed with elevated steam at 36.7%
  • FIG. 7 shows a plot of the steam reforming of a mixture of a typical industrial waste, but without fuel cell produced carbon dioxide added in the feed, with stoichiometric steam at 49.45%
  • FIG. 8 shows a plot of the steam reforming of a mixture of a typical industrial waste, but without fuel cell produced carbon dioxide added in the feed, with super-stoichiometric steam at 66%
  • FIG. 9-10 show plots of the steam reforming of a mixture of a typical industrial waste and fuel cell produced carbon dioxide at least about 20% added in the feed with super-sub steam at 46-51% achieving high hydrogen and the cleanest syngas in accordance with the preferred embodiment of the present invention
  • FIG. 11 show a cross-sectional view of a superheater
  • FIG. 12 is a schematic diagram of a preferred gasifier as shown in FIG.
  • FIG.l illustrates a specific embodiment of the process and system of the present invention in which a carbonaceous waste feed material is passed via inlet line 10 to a non-catalytic high temperature, gas-phase reactor 12 and is converted into synthesis gas at high temperature in the range of about 700° to about 1600°C (1300- 2900°F).
  • a rotary kiln is used as gasifier 12 having outlet 14 to remove the buildup of solids.
  • the syngas produced in gasifier 12 that leaves through outlet line 18 is then split downstream into two flow lines 20 and 22.
  • the syngas in flow line 20 enters fuel cell 26 at port 28.
  • the second syngas stream is passed via flow line 22 to Fischer-Tropsch catalytic reactor 30.
  • gasifier 12 is a slightly inclined horizontal rotary kiln that is heated externally and is called an "indirectly heated rotary kiln.” The slight inclination encourages the feedstock to move axially along the rotary kiln away from the inlet as it is rotated slowly.
  • the carbonaceous feedstock or waste at or near room temperature is introduced into one end of the kiln where the temperature is at about 200°C and it is subjected to increasing temperatures as it moves along the length of the kiln toward the gas exit end.
  • the temperature of the gas leaving the exit end is in the range of about 1100° to 1600°C (1650-2900°F).
  • this can be done by pulling the exit gases through a superheater of the type shown in FIG. 11 , which can be located in the region adjacent the exit end of the kiln shown in FIG. 12.
  • a superheater of the type shown in FIG. 11 , which can be located in the region adjacent the exit end of the kiln shown in FIG. 12.
  • the higher temperatures and added steam are needed to accomplish the high levels of destruction required by U.S. EPA law should there be hazardous waste contaminant in a waste feedstock.
  • these solids are removed from the kiln before they are melted.
  • these solids are removed from the rotary kiln at solids exit 14, which is at an appropriate along the length of kiln where it is estimated that waste feed has reached a temperature of about 400°C (750°) and before the solids have melted.
  • Examples of indirectly heated rotary kilns that are suitable for the present invention are manufactured by: Von Roll, Inc., 302 Research Drive, Suite 130, Norcross, GA 30092; Surface Combustion, Inc., 1700 Indian Wood, Cir., Maunee, OH 43537; and Bethlehem Steel of International Steel Group, Inc., 3250 Interstate Drive - 2nd Floor, Richfield, OH 44286.
  • the syngas feed passes upward through the electrolyte
  • Membrane 44 is ionically conducting, but will not allow any of the gases or hydrocarbon species on either side of fuel cell 26 to pass through.
  • fuel cells that can accept syngas and are suitable for fuel cell 26 of the present invention include the Solid Oxide Fuel Cell manufactured by Westinghouse, Monroeville, Pennsylvania or by Technical Management, Inc., Cleveland, Ohio and the Molten Carbonate Fuel Cell manufactured by FuelCell Energy Corp., Danbury, Connecticut. The pertinent portion of the following references are incorporated by reference into this Detailed Description of the Invention: C. M. Caruana, "Fuel Cells Poised to Provide Power," Chem. Eng. Progr., pp.
  • the oxidized syngas consisting essentially of hydrogen and carbon monoxide, leaves anode 42 of fuel cell 26 mostly as water vapor and carbon dioxide.
  • This stream of oxidized syngas passes via line 48 into air-cooled condenser 50, where the water vapor is condensed into liquid water and is removed from the condenser bottoms via line 52 for reuse. Wastewater recovered from a municipal sewage system can be used in gasifier 12.
  • This standard air electrode allows the entering oxygen-containing gas in line 64, typically air, to pass upward through the air electrolyte 66 around and through electrode 60.
  • the inert components of the air stream consisting mostly of nitrogen, pass through the cathode half-cell and are removed via exit stream 68.
  • the cathode half-cell can also use pure oxygen instead of air to achieve higher efficiencies and more heat production.
  • the fuel cell produces substantial electrical power ranging from 4 to 9 kilowatts per standard cubic foot per minute of hydrogen feed.
  • the syngas in line 22 is reacted over a catalyst 70 to form higher boiling hydrocarbons, such as waxes or other useful hydrocarbon products recovered in line 76.
  • waxes for example, can form a feedstock to a Shell Middle Distillates Synthesis Process where they are reacted to form naphtha, fuel gas, and kerosine, which are all valuable chemical products; see J. Eilers, S. A. Posthuma, and S. T. Sie, "The Shell Middle Distillate Synthesis Process (SMDS),” Catalysis Letter, 7, pp. 253-270 (1990).
  • SMDS Shell Middle Distillate Synthesis Process
  • the pertinent portions of this paper are incorporated by reference into this Detailed Description of the Invention.
  • the carbon mass entering the feed via line 10 leaves as carbon mass in the form of useful hydrocarbon products, which are recovered, via line 76, thus avoiding the release of carbon dioxide when a hydrocarbon feedstock is gasified.
  • FIG. 2 is a plot of the commercial steam reforming of methane that is a well known commercial process and is the principal process for manufacturing hydrogen gas in refineries for use in petroleum hydro-cracking and hydro-reforming process steps as well as manufacturing hydrogen gas as a commodity sold in the marketplace. Standard nickel catalysts are used for this conversion in order to lower the reactor tube temperatures so that less expensive alloys can be used and their process lifetime extended.
  • the plots shown in FIGS. 2-10 are based on calculations performed by the method of the Gibbs Free Energy Minimization to yield gas compositions at thermodynamic equilibrium from the lowest temperature of 200°C up to 2000°C.
  • the chemistry is started by placing methane (CH 4 ) and steam (H 2 O) at one atmosphere in the gaseous (subscript, g) in a vessel at 200°C. After waiting a sufficient amount of time, the compounds react slightly and form a small quantity of hydrogen (H 2 ) and carbon dioxide (CO 2 ) as shown in Fig. 2.
  • This composition of the gas mixture is that which occurs if the chemical kinetics were fast enough to allow the reaction to reach completion in the time allotted.
  • the following two reactions are occurring simultaneously: CH 4 + 2 H 2 O ⁇ 4 H 2 + CO 2 (1) H 2 + CO 2 ⁇ H 2 O + CO (2) As soon as the H 2 + CO 2 are formed in reaction (1), the "Water gas shift reaction" forms H 2 O and CO by reaction (2).
  • the gas compositions shown in FIG. 2 can be achieved at temperatures above about 600°C without the use of catalysts since the approach to thermodynamic equilibrium can be achieved in reasonable residence times.
  • the commercial embodiment carries out the gas-phase chemistry inside of catalyst-coated tubes or tubes filled with catalyst-coated ceramic beads. These tubes are heated externally by means of very hot flue gas from a gas-fired furnace, sometimes using oxygen- enriched combustion air. As the molecular complexity of the feed hydrocarbons increase, the temperatures have to be increased to levels well above 600°C in order to approach their chemical thermodynamic equilibrium composition without the enhancing and accelerating effect of catalysts.
  • the '465 patent discloses a preferred embodiment involving the use of a catalytic bed for gasifier 12 operating at temperatures in the range of about 400° to about 700°C.
  • the wastes must be carefully selected so the catalysts are not easily poisoned when wastes are used as feedstock and have halogen and heavy metal contaminates.
  • FIG. 3 shows the steam reforming of a mixture of methane and fuel cell-produced carbon dioxide added into the feed at about 20%.
  • the gasifier preferably uses a catalytic bed to form syngas. It has been found at high temperatures over 700°C, the syngas compositions shown are achieved without the need for catalysts. Comparing FIG. 2 and FIG.
  • Reaction (3) stoichiometry is the rough optimum, maximizing hydrogen content. Varying the stoichiometric quantities of the reactants produces less than optimum hydrogen. It is noteworthy that the addition of CO 2 to the feed reduces the requirements for steam below stoichiometric requirements. In fact, there is an optimum combination of using both CO 2 and steam.
  • a generalized chemical reaction can be written for any carbonaceous feedstock, as expressed by the generalized empirical formula C a H b O c : 5 C a H b Oc + D CO 2 + (5a-5c-D) H 2 O ⁇ (5a+D) CO + [5(a+0.5b-c)-D] H 2 (4)
  • the H 2 /CO ratio can be optimized by the right combination of CO 2 and H 2 O for a given waste feed mixture characterized by the empirical formula, C a H b O c .
  • H _ 5(a + 0.5b - c) -D CO 5a + D
  • H _ 5(a + 0.5b - c) -D CO 5a + D
  • FIG. 7 shows a plot of the steam reforming of a mixture of a typical industrial solvent waste (acetone, formaldehyde, methanol, dimethylbenzene, butanol, trichlor, and perchlor), without fuel cell produced carbon dioxide added in the feed, but with steam at 49.45%.
  • a typical industrial solvent waste acetone, formaldehyde, methanol, dimethylbenzene, butanol, trichlor, and perchlor
  • the syngas product composition starts at the highest with hydrogen, at 48.9%; then carbon monoxide at 35.5%; methane at 6.3%; acetylene (C 2 H 2 ) at 2%; hydrogen chloride gas at 0.9%; benzene (C ⁇ H ⁇ ) at 0.5%; ethylene (C 2 H 4 ) at 0.4%; naphthalene at 0.28%; propylene- 1 (C 6 H 4 ) at 85 ppm; propylene-2 (C 3 H ) at 50 ppm; ethane (C 2 H 6 ) at 25 ppm; methyl radical (CH 3 ) at 25 ppm; hydrogen radical at 9 ppm; water at 7 ppm; carbon dioxide at 2 ppm; with all other compounds at levels below 0.01 ppm.
  • FIG. 8 shows a plot of the steam reforming of the same mixture of industrial solvent waste as in the composition for FIG. 7, without fuel cell produced carbon dioxide added in the feed, but with steam at 66%. It is noted that the hydrogen product remains high and steady at 48.9% at 1000°C and beyond. The syngas is quite clean, with undesirable compounds at the 10 "5 mole percent level (i.e. 0.1 ppm). This syngas ratio H 2 /CO of about 1.2 is excellent for Fischer Tropsch synthesis as well as molten carbonate or solid oxide fuel cells, after the hydrogen chloride (and any other acid gases) are removed. Referring to FIG.
  • the syngas product composition starts at the highest with hydrogen, at 63%; then carbon monoxide at 40%; hydrogen chloride gas at 0.6% ppm; water at 0.5%; carbon dioxide at 0.1%; methane at 100 ppm; hydrogen radical at 10 ppm; acetylene at 4 ppm; ethylene at 1 ppm; with all other compounds at levels below 0.09 ppb. It is noted that this is only about 10,000 times cleaner in minor contaminants where the goal of the present invention is a million times cleaner. Even further improvements can be made, unexpectedly, as are shown in FIG. 9, by increasing the CO 2 / H 2 O ratio from the 1.3 in FIG. 7 up to 2.8 in FIG. 9.
  • FIG. 10 by slightly increasing the recycle H 2 O from the 46.3% in FIG. 9 up to 50.9% in FIG. 10. This CO 2 from the fuel cell was 23% of the waste feed.
  • FIG. 10 is actually cleaner. Referring to FIG. 10 at 1200°C, the syngas product composition starts at the highest with hydrogen at 48.9%, then carbon monoxide at 40.0%; water at
  • a superheater 100 is shown in which a mixture of air and natural gas or other suitable fuel is fed through inlet 110 in gas feed tube 111 after fuel-air supply valve 112 is in the open position to supply matrix burner 114.
  • a suitable matrix burner is described in U.S. Patent No. 6,065,963, the description of which is incorporated herein by reference.
  • Matrix or conical surface burners of the type suitable for use in the superheater of the present invention are manufactured by N.V. Acotech S.A and Hauck Manufacturing Company.
  • the flue gases from matrix burner 114 are removed from superheater 100 via flue 114 in tube 116.
  • Process gases from gasifier 12 enter through a plurality of process gas inlets 120 supplied by an annular manifold (not shown) around the circumference of the walls 122 of superheater 100 and pass into flow annulus 124.
  • steam is introduced through line 150 (see FIG. 12) operably connected to a plurality of steam inlets 126 supplied by an annular manifold into annulus 124.
  • the heated exit gases pass through exit gas outlet 18.
  • gasifier 12 comprising rotary kiln 130 and superheater 100 positioned partially within the exit region 138 of kiln 130
  • superheater 100 can also be operably positioned entirely outside of kiln 130 in order to superheat the intermediate gas stream from the kiln that enter the process gas inlet 120 (see FIG. 11) of superheater 100 to temperatures in the range at least 700° to about 1600°C (1300-2900°F) before the exit gas stream passes through exit gas outlet 18.
  • a standard expansion bellows 139, a rotary seal assembly 140, and a plurality of pneumatic struts 142 are operably mounted around the outside circumference of kiln 130 to allow for approximately one foot of expansion of kiln 130 during its operation.

Abstract

The process and system of the invention converts carbonaceous feedstock such as coal, hydrocarbon oil, natural gas, petroleum coke, oil shale, carbonaceous-containing waste oil, carbonaceous-containing medical waste, carbonaceous-containing military waste, carbonaceous-containing industrial waste, carbonaceous-containing medical waste, carbonaceous-containing sewage sludge and municipal solid waste, and mixtures thereof into electrical energy without the production of unwanted greenhouse emissions. The process and system uses a combination of a gasifier (12), such as a kiln, operating in the exit range of at least 700° to about 1600°C (1300-2900°F) to convert the carbonaceous feedstock and a greenhouse gas stream into a synthesis gas comprising mostly carbon monoxide and hydrogen without the need for expensive catalysts and or high pressure operations. One portion of the synthesis gas from the gasifier becomes electrochemically oxidized in an electricity-producing fuel cell (26), into an exit gas comprising carbon dioxide and water. The latter is recycled back to the gasifier after a portion of water is condensed out. The second portion of the synthesis gas from the gasifier is converted into useful hydrocarbon products.

Description

PROCESS AND SYSTEM FOR CONVERTING CARBONACEOUS FEEDSTOCKS INTO ENERGY WITHOUT GREENHOUSE GAS EMISSIONS This application is a continuation-in-part of application U.S. Serial No. 10/602,536 filed June 23, 2003 and U.S. Serial No. 10/184,264 filed June 27, 2002 (published as Publication No. 2003/0022035 on January 30, 2003). This application is related to and contains common subject matter with U.S. Serial No. 09/186,766 filed November 5, 1998; now U.S. Patent No. 6,187,465 issued February 13, 2001 (the '465 patent), which claims the benefit of U.S. provisional application Serial No. 60/064,692 filed November 7, 1997. This application is not a continuation-in-part of the latter application, U.S. Serial No. 09/186,766, as stated in the parent application, U.S. Serial No. 10/184,264. This invention relates to non-greenhouse gas emitting processes and systems which accomplish the conversion of a carbonaceous gas stream and a greenhouse gas into a synthesis gas comprising hydrogen and carbon monoxide without the need for expensive catalysts and or high pressure operations. BACKGROUND OF THE INVENTION The burning of fossil fuels in boilers to raise high temperature, high- pressure steam that can be used to power turbo-electric generators produces a problem source of carbon dioxide and other greenhouse gases, e.g. methane, ozone and fluorocarbons. This fossil fuel combustion, especially of coal, needs a technological fix to avoid the emission of carbon dioxide and other greenhouse gases with their attendant undesirable release to the earth's atmosphere resulting in the absorption of solar radiation known as the greenhouse effect. Much of the world depends on coal for power. There have been significant efforts to develop clean coal technologies to greatly reduce the release of acid gases, such as sulfur oxides and nitrogen oxides. However, to date none of these clean coal programs aim to eliminate the emissions of carbon dioxide and other greenhouse gases. Efforts to use pure oxygen in power plants and gasification systems to avoid the diluting effects of nitrogen and to achieve higher efficiency suffers from the unacceptable cost of requiring an air separation plant and the problems of excessive temperatures in oxygen-fed combustion turbogenerators. There is also widespread effort to increase the efficiency of power plants by utilizing advanced thermodynamic combined cycles, more efficient turbogenerators, improved condensers and cooling towers, and similar systems. A small portion of this effort involves the use of fossil fuel gasification processes, which are highly efficient because they avoid combustion and large combustion product emissions. Finally there is an effort by Westinghouse (Corporate literature,
"SureCell®" 1996 ) and others to combine the use of advanced high temperature turbo-generators and fuel cells to accomplish conversion to electricity at about 70% instead of current conventional combined cycle power plants of about 47%. Today there is worldwide concern that the atmospheric buildup of carbon dioxide and other greenhouse gases will start to have serious environmental consequences for the earth's tropospheric temperature, global rainfall distribution, water balance, severe weather storms, and similar consequences. Technological solutions are being demanded throughout the world. The worldwide research establishment, encouraged by government funding from various agencies, continues to be focused on identifying commercially attractive gas separation technologies to remove carbon dioxide from stack gases and also attractive chemistry that will utilize this carbon dioxide as a raw material to manufacture useful products. This has, indeed, been a very large challenge with poor successes as summarized by the review papers; see Michele Aresta, and Eugenio Quaranta, "Carbon Dioxide: A Substitute for Phosgene," Chem.Tech. pp. 32-40, March 1997. and Bette Hileman, "Industry Considers CO2 Reduction Methods", Chem & Engr. News, pg. 30, June 30, 1997. Trying to scrub the CO2 from stack gases and trying to chemically react the recovered CO2 clearly is not the right path of research because of the technical difficulty and the process expense of reacting carbon dioxide. SUMMARY OF THE INVENTION The process and system of the invention converts carbonaceous feedstock from fossil fuels and other combustible materials into energy without the production of unwanted greenhouse emissions. The present process comprises the following steps: (a) converting a carbonaceous feedstock and a greenhouse gas stream in a gasification unit to synthesis gas comprising mainly carbon monoxide and hydrogen, where the gasification unit is a non-catalytic high temperature, gas-phase reactor operating at conditions to achieve a gas exit temperature of from at least 700° to about 1600°C (1300-2900°F); (b) electrochemically oxidizing at least a portion of the synthesis gas from the gasification unit in a first half-cell of a fuel cell to produce a first half-cell exit gas comprising carbon dioxide and water; (c) recovering the carbon dioxide from the first half-cell exit gas to serve as a greenhouse gas stream in step (a); and (d) electrochemically reducing an oxygen-containing gas in a second half-cell of the fuel cell completing the circuit and resulting in the production of electrical energy. In contrast to the present invention, the invention disclosed and claimed in the '465 patent preferably used a gasification unit containing a catalyst that operates at a temperature in the range of about 400° to about 700°C (750-1300°F) and still more preferably, a gasification unit using a fluidized catalytic bed. The requirement for the use of a catalytic bed requires expensive catalysts and/or high- pressure operations. The catalysts, e.g., nickel or copper-based ceramic supported catalyst typically used in steam reforming of methane or shift converters are easily poisoned by halogens or heavy metals found in waste streams that are a desirable candidate for waste-to-energy-systems. Although catalysts allow for significant reductions in the gas-phase temperature to carry out the synthesis gas formation chemistry, these catalysts only function as long as they remain active and not poisoned by low level contaminates found in the waste feedstocks. The present system comprises the following: (a) the gasification unit that is a non-catalytic high temperature, gas-phase reactor operating at conditions to achieve a gas exit temperature of from at least 700° to about 1600°C (1300 to 2900°F), for converting a carbonaceous and a greenhouse gas stream feedstock into the synthesis gas; (b) the fuel cell for the production of electrical energy comprising the first half-cell having an inlet in fluid communication with the synthesis gas and a first means or anode for electrochemically oxidizing synthesis gas into the first half-cell exit gas, a second half-cell having a second means or cathode for electrochemically reducing the oxygen-containing gas, and a membrane separating the first and second half cells that will not allow passage of the gaseous components from the respective half-cells; and (c) passage means for passing the carbon dioxide from the first half- cell to serve as a greenhouse gas stream for the gasification unit. Preferably the non-catalytic, gas-phase reactor is a kiln having an inlet means, a gas outlet means, and a solids outlet between the inlet means and the gas outlet means and operating at a temperature gradient along the length of the kiln of about 200° to about 1600°C (400-2900°F). The present process avoids the difficult path of attempting to strip and capture the carbon dioxide from stack gases and without attempting to carry out separate chemical reactions of carbon dioxide to attempt to produce useful products. The process and system of the present invention uses unique gasification technology combined with fuel cells to generate electricity at high efficiency. This is accomplished by taking advantage of a very unique property of fuel cells - namely, the two anodic and cathodic reactions are separated by an electronically conducting membrane that keeps the product gases separate. In this way, a combustible feed gas can be fully oxidized in the first half-cell of the fuel cell without being commingled with the final products of the air reduction in the second half-cell electrode, i.e., N2. For example, in coal gasification, synthesis gas is formed consisting predominantly of hydrogen and carbon monoxide. This synthesis gas is fed into the first half-cell, i.e., the anode or negative terminal side, of the fuel cell, such as the solid oxide or molten carbonate types, where it is oxidized to water and carbon dioxide. These gases are not diluted by the typical nitrogen remaining after oxygen reduction in the second or remaining half-cell, i.e., the cathode side or positive terminal, of the fuel side. Nitrogen and combustion gases are commingled when combustion air is used in boilers or furnaces. Thus, in the fuel cell, the synthesis gas (syngas) is oxidized without being combusted with air and without being diluted by other gases. The fuel cell-produced water and carbon dioxide are simply separated from each other by condensing the liquid water and allowing the carbon dioxide to return to the gasifier. The carbon dioxide being injected into the high temperature gasifier undergoes a reaction with the high temperature carbonaceous feed to form more carbon monoxide, repeating the cycle. By means of the present process and system, the carbon dioxide in the fuel cell is easily kept separate from the air side and any nitrogen. This carbon dioxide can be recycled back to the gasifier in nearly pure form. Likewise steam in pure form can be recycled as well in different amounts under gasifier control system requirements to maintain the ideal hydrogen to carbon monoxide ratio in the range of about 1.75 to about 2.5. This helps maintain a high hydrogen content in the gasifier so that a portion of the gasifϊer-produced syngas can be used downstream in a chemical reactor such as a Fischer-Tropsch reaction system for the production of a variety of useful chemicals ranging from methanol to paraffin waxes. These in turn are used to make useful chemicals such as naphtha, gas oil, and kerosine, or agricultural chemicals or carbide abrasives. The latter are not ever burned in their lifecycle, and they sequester the carbon forever. Thus, the carbon monoxide is used to produce useful chemicals instead of discarding the valuable carbon source in the carbon dioxide. The carbon balance of the plant is maintained such that the mass of carbon input in the waste feed is equal to the carbon mass leaving the plant as valuable hydrocarbon products; not carbon dioxide. What has been achieved is a chemical plant merged with a power plant that produces useful hydrocarbon products, high efficiency electric power without any carbon dioxide or other greenhouse gas emissions. And, most importantly gasification is much more flexible than a refinery or a coal boiler, since a wide variety of waste streams can be used as the feed material. Thus, this solves two serious problems. The process of the present invention is designed for use in a waste-to- energy plant using carbonaceous feedstocks such as coal; hydrocarbon oil; natural gas; petroleum coke; oil shale; carbonaceous-containing waste oil; carbonaceous- containing medical waste; carbonaceous-containing military waste including explosives, spent armaments, chemical and biological weapons agents, and unexploded ordinance; carbonaceous-containing industrial waste including hazardous waste, insecticides, pesticides, fumicides, algaecides, and the like; carbonaceous- containing sewage sludge and municipal solid waste (MSW); carbonaceous- containing agricultural waste; carbonaceous-containing biomass, biological and biochemical waste; and mixtures thereof. BRIEF DESCRIPTION OF THE DRAWINGS Advantages of the present invention will become apparent to those skilled in the art from the following description and accompanying drawings in which: FIG. 1 is a schematic process flow diagram of a preferred embodiment of the process and system of the present invention; FIG. 2 is a plot of the commercial steam reforming of methane to make syngas consisting of hydrogen and carbon monoxide; FIG. 3 shows a plot of the steam reforming of a mixture methane and fuel cell produced carbon dioxide at about 20% in the feed; FIG.4 shows a plot of the steam reforming of a mixture methane and fuel cell produced carbon dioxide at 25% in the feed; FIG. 5 shows a plot of the steam reforming methane and fuel cell produced carbon dioxide at 30% in the feed; FIG. 6 shows a plot of the steam reforming methane and fuel cell produced carbon dioxide at 27.6% in the feed with elevated steam at 36.7%; FIG. 7 shows a plot of the steam reforming of a mixture of a typical industrial waste, but without fuel cell produced carbon dioxide added in the feed, with stoichiometric steam at 49.45%; FIG. 8 shows a plot of the steam reforming of a mixture of a typical industrial waste, but without fuel cell produced carbon dioxide added in the feed, with super-stoichiometric steam at 66%; FIGS. 9-10 show plots of the steam reforming of a mixture of a typical industrial waste and fuel cell produced carbon dioxide at least about 20% added in the feed with super-sub steam at 46-51% achieving high hydrogen and the cleanest syngas in accordance with the preferred embodiment of the present invention; FIG. 11 show a cross-sectional view of a superheater; and FIG. 12 is a schematic diagram of a preferred gasifier as shown in FIG.
1 in which a rotary kiln is combined with a superheater shown in FIG. 11 so that the superheater is positioned within the exit region of the kiln in order to elevate the gas temperature and enrich the syngas exiting the kiln. DETAILED DESCRIPTION OF THE INVENTION Preferred Embodiment of Process for Hydrogen Fuel Cell Energy
Without Production of Unwanted Greenhouse Gases Using a Kiln. FIG.l illustrates a specific embodiment of the process and system of the present invention in which a carbonaceous waste feed material is passed via inlet line 10 to a non-catalytic high temperature, gas-phase reactor 12 and is converted into synthesis gas at high temperature in the range of about 700° to about 1600°C (1300- 2900°F). Preferably, a rotary kiln is used as gasifier 12 having outlet 14 to remove the buildup of solids. The syngas produced in gasifier 12 that leaves through outlet line 18 is then split downstream into two flow lines 20 and 22. The syngas in flow line 20 enters fuel cell 26 at port 28. The second syngas stream is passed via flow line 22 to Fischer-Tropsch catalytic reactor 30. Preferably gasifier 12 is a slightly inclined horizontal rotary kiln that is heated externally and is called an "indirectly heated rotary kiln." The slight inclination encourages the feedstock to move axially along the rotary kiln away from the inlet as it is rotated slowly. The carbonaceous feedstock or waste at or near room temperature is introduced into one end of the kiln where the temperature is at about 200°C and it is subjected to increasing temperatures as it moves along the length of the kiln toward the gas exit end. Preferably the temperature of the gas leaving the exit end is in the range of about 1100° to 1600°C (1650-2900°F). Preferably this can be done by pulling the exit gases through a superheater of the type shown in FIG. 11 , which can be located in the region adjacent the exit end of the kiln shown in FIG. 12. The higher temperatures and added steam are needed to accomplish the high levels of destruction required by U.S. EPA law should there be hazardous waste contaminant in a waste feedstock. For recovery of metals and glass for possible recycling, these solids are removed from the kiln before they are melted. Preferably, these solids are removed from the rotary kiln at solids exit 14, which is at an appropriate along the length of kiln where it is estimated that waste feed has reached a temperature of about 400°C (750°) and before the solids have melted. Examples of indirectly heated rotary kilns that are suitable for the present invention are manufactured by: Von Roll, Inc., 302 Research Drive, Suite 130, Norcross, GA 30092; Surface Combustion, Inc., 1700 Indian Wood, Cir., Maunee, OH 43537; and Bethlehem Steel of International Steel Group, Inc., 3250 Interstate Drive - 2nd Floor, Richfield, OH 44286. In fuel cell 26, the syngas feed passes upward through the electrolyte
40 around and through the porous catalytic anode electrode 42 wherein the gases are oxidized electrochemically. Membrane 44 is ionically conducting, but will not allow any of the gases or hydrocarbon species on either side of fuel cell 26 to pass through. Examples of fuel cells that can accept syngas and are suitable for fuel cell 26 of the present invention include the Solid Oxide Fuel Cell manufactured by Westinghouse, Monroeville, Pennsylvania or by Technical Management, Inc., Cleveland, Ohio and the Molten Carbonate Fuel Cell manufactured by FuelCell Energy Corp., Danbury, Connecticut. The pertinent portion of the following references are incorporated by reference into this Detailed Description of the Invention: C. M. Caruana, "Fuel Cells Poised to Provide Power," Chem. Eng. Progr., pp. 11-21, September, 1996 and S.C. Singhal, "Advanced in Tubular Solid Oxide Fuel Cell Technology," Proceedings of the 4th International Symposium on Solid Oxide Fuel Cells, Pennington, N.J., Vol. 95-1, pp. 195-207 (1995). The oxidized syngas, consisting essentially of hydrogen and carbon monoxide, leaves anode 42 of fuel cell 26 mostly as water vapor and carbon dioxide. This stream of oxidized syngas passes via line 48 into air-cooled condenser 50, where the water vapor is condensed into liquid water and is removed from the condenser bottoms via line 52 for reuse. Wastewater recovered from a municipal sewage system can be used in gasifier 12. However, all or a portion of the relatively pure water in line 52 can be sold or recycled and combined with the wastewater passing into gasifier 12 via line 38. The carbon dioxide gas is not condensed in condenser 50 and passes through into the condenser overhead as carbon dioxide gas to be fed back to the gasifier 12 via line 36. The carbon dioxide in high temperature gasifier 12 reacts therein with the carbonaceous feed material to form more syngas to further assist in the overall reaction. CO2 or other greenhouse gases can be passed into gasifier 12 via line 56 to maintain the desired H/C ratio of the feedstock. To complete the description of FIG. 1, it is noted that the other half- cell of fuel cell 26 involves air reduction on cathode 60. This standard air electrode allows the entering oxygen-containing gas in line 64, typically air, to pass upward through the air electrolyte 66 around and through electrode 60. The inert components of the air stream, consisting mostly of nitrogen, pass through the cathode half-cell and are removed via exit stream 68. Although more expensive, the cathode half-cell can also use pure oxygen instead of air to achieve higher efficiencies and more heat production. The fuel cell produces substantial electrical power ranging from 4 to 9 kilowatts per standard cubic foot per minute of hydrogen feed. In the Fischer-Tropsch catalytic reactor 30, the syngas in line 22 is reacted over a catalyst 70 to form higher boiling hydrocarbons, such as waxes or other useful hydrocarbon products recovered in line 76. These waxes, for example, can form a feedstock to a Shell Middle Distillates Synthesis Process where they are reacted to form naphtha, fuel gas, and kerosine, which are all valuable chemical products; see J. Eilers, S. A. Posthuma, and S. T. Sie, "The Shell Middle Distillate Synthesis Process (SMDS)," Catalysis Letter, 7, pp. 253-270 (1990). The pertinent portions of this paper are incorporated by reference into this Detailed Description of the Invention. Thus, overall the carbon mass entering the feed via line 10 leaves as carbon mass in the form of useful hydrocarbon products, which are recovered, via line 76, thus avoiding the release of carbon dioxide when a hydrocarbon feedstock is gasified. There is no expensive and troublesome alkali stripper to recover carbon dioxide from stack gases, as would be the case in a normal combustion/steam-turbine power plant configuration. FIG. 2 is a plot of the commercial steam reforming of methane that is a well known commercial process and is the principal process for manufacturing hydrogen gas in refineries for use in petroleum hydro-cracking and hydro-reforming process steps as well as manufacturing hydrogen gas as a commodity sold in the marketplace. Standard nickel catalysts are used for this conversion in order to lower the reactor tube temperatures so that less expensive alloys can be used and their process lifetime extended. The plots shown in FIGS. 2-10 are based on calculations performed by the method of the Gibbs Free Energy Minimization to yield gas compositions at thermodynamic equilibrium from the lowest temperature of 200°C up to 2000°C. The chemistry is started by placing methane (CH4) and steam (H2O) at one atmosphere in the gaseous (subscript, g) in a vessel at 200°C. After waiting a sufficient amount of time, the compounds react slightly and form a small quantity of hydrogen (H2) and carbon dioxide (CO2) as shown in Fig. 2. This composition of the gas mixture is that which occurs if the chemical kinetics were fast enough to allow the reaction to reach completion in the time allotted. The following two reactions are occurring simultaneously: CH4 + 2 H2O → 4 H2 + CO2 (1) H2 + CO2 <→ H2O + CO (2) As soon as the H2 + CO2 are formed in reaction (1), the "Water gas shift reaction" forms H2O and CO by reaction (2). In this way, reactions (1) and (2) interact according to each of their free energy driving forces to arrive at an equilibrium balance, and the final compositions are shown in the FIG. 2 As the temperature is raised, the equilibrium shifts to forming H O and CO. Practically speaking; however, commercially one cannot wait long periods of time for the slow chemical kinetics at 200°C to reach the equilibrium composition. The gas composition curves are achieved more quickly with less residence time when active surface catalysts are used to impart extra energy into the gases to encourage them to react more quickly. As the temperature is increased, the kinetic velocities and energies are increased by the increased kinetic activities of the gases carrying more energy in their collisions and forming other compounds more quickly. Eventually, as the temperature is increased significantly to say 600°C, the kinetics become so fast that no active surface catalyst is needed. Thus, the gas compositions shown in FIG. 2 can be achieved at temperatures above about 600°C without the use of catalysts since the approach to thermodynamic equilibrium can be achieved in reasonable residence times. To make commercial H2, the commercial embodiment carries out the gas-phase chemistry inside of catalyst-coated tubes or tubes filled with catalyst-coated ceramic beads. These tubes are heated externally by means of very hot flue gas from a gas-fired furnace, sometimes using oxygen- enriched combustion air. As the molecular complexity of the feed hydrocarbons increase, the temperatures have to be increased to levels well above 600°C in order to approach their chemical thermodynamic equilibrium composition without the enhancing and accelerating effect of catalysts. In fact, it has been found based on experimental testing and the simulations performed pursuant to the present invention that above 700°C is practically where catalysts are no longer needed when dealing with organic wastes. Commercial gasification processes for coal, coke, petroleum, organic waste and similar feedstock also use catalytic fixed or preferably fluidized catalytic beds, such as the Texaco gasifier or the Shell gasification process as discussed in the '465 patent. These catalysts allow low enough temperatures that more cost-effective alloys can be used at high pressures for these commercial gasification vessels. Wastes, such as those contemplated as feedstocks for the process of the present invention, contain contaminates that are catalyst poisons. Therefore, extreme care must be taken in the acceptance of such a broad classes of wastes. The '465 patent discloses a preferred embodiment involving the use of a catalytic bed for gasifier 12 operating at temperatures in the range of about 400° to about 700°C. The wastes must be carefully selected so the catalysts are not easily poisoned when wastes are used as feedstock and have halogen and heavy metal contaminates. Now introducing fuel cells into the process, FIG. 3 shows the steam reforming of a mixture of methane and fuel cell-produced carbon dioxide added into the feed at about 20%. In accordance to the teaching of the '465 patent, the gasifier preferably uses a catalytic bed to form syngas. It has been found at high temperatures over 700°C, the syngas compositions shown are achieved without the need for catalysts. Comparing FIG. 2 and FIG. 3 beyond 800°C, it is noted that the hydrogen content is slightly lowered by the presence of increased carbon monoxide and water that is formed and by the residual carbon dioxide, since all three act as significant diluents in the formed syngas product, diluting the hydrogen. In fact, the carbon dioxide has no positive effect in the reaction, other than that it is consumed so that it is not released to the environment. These effects are even more exaggerated as shown in FIGS.4-5 at carbon dioxide concentrations of 25% and 30%, respectively. In the latter case shown in FIG. 5, the hydrogen concentration is dropped down to 46.5% from the higher hydrogen of 58% with carbon dioxide increased to 30% in the feed. But most importantly, in all these cases with increased carbon dioxide, the hydrogen is found to drop gradually with increasing temperatures over 800°C where the thermodynamic equilibrium is achieved without the use of a catalyst. Increasing the fraction of steam in the feed, as shown in FIG. 6, does not correct this problem, as one of ordinary skill in the art would have thought. This situation, under conventional wisdom, dictated that with the use of lower temperature aided by the use of catalysts, the catalysts were strongly preferred to maximize the hydrogen product concentration desired. This was the dilemma faced by the inventor of the '465 patent. Unexpectedly, a much-preferred solution has now been discovered to optimize this fuel cell link that has been overlooked and not exploited previously. It involves using elevated steam feed and CO2 simultaneously with complex waste streams that have higher carbon/hydrogen ratios than simpler compounds such as methane. This approach appears to be contrary to conventional wisdom and practice, which suggests that to achieve higher hydrogen concentrations at high temperature, the worst option is to increase the carbon content of the feed. However, this simplistic logic has been found to be very wrong. The very simplified chemical reaction with the waste stream is fairly characterized entirely by carbon as in the following reaction: 3.8 C + 0.6 CO2 + 3 H2O → 4.4 CO + 3 H2 (3) Reaction (3) is already 68% by volume hydrogen (i.e. mole percent), which is far better than the hydrogen levels in FIGS. 3-6. Therein, one would have expected about 46% by volume H . Reaction (3) stoichiometry is the rough optimum, maximizing hydrogen content. Varying the stoichiometric quantities of the reactants produces less than optimum hydrogen. It is noteworthy that the addition of CO2 to the feed reduces the requirements for steam below stoichiometric requirements. In fact, there is an optimum combination of using both CO2 and steam. A generalized chemical reaction can be written for any carbonaceous feedstock, as expressed by the generalized empirical formula CaHbOc: 5 CaHbOc + D CO2 + (5a-5c-D) H2O → (5a+D) CO + [5(a+0.5b-c)-D] H2 (4) The H2/CO ratio can be optimized by the right combination of CO2 and H2O for a given waste feed mixture characterized by the empirical formula, CaHbOc. It is noted that the amount of H2O needed is reduced below its stoichiometric requirements (5a-5c) for conventional steam reforming by the "D" amount of CO2 used, since the stoichiometric coefficient on H2O is (5a-5c-D). Also, to help to adjust the H2/CO ratio needed for Fischer-Tropsch synthesis of useful chemical co-products to sequester the carbon and avoid greenhouse gas emissions, examining this H2/CO ratio is helpful, since it is expressed as: H _ = 5(a + 0.5b - c) -D CO 5a + D One notes for a given carbonaceous feedstock with the empirical formula, CaHbOc, one can adjust the amount of CO2 , "D", to satisfy the Fischer- Tropsch synthesis requirements. To achieve higher hydrogen concentrations at high temperature to drive the fuel cells, increased feedstock hydrogen content together with an excess steam below stoichiometric levels, (5a-5c-D), is allowed and is combined with the recycled fuel cell carbon dioxide, D. As shown in Fig. 7-10, this provides the chemistry at thermodynamic equilibrium that achieves a higher hydrogen-rich syngas that remains high and steady in hydrogen over a broad high temperature range up to and beyond 1300°C without catalysts. FIG. 7 shows a plot of the steam reforming of a mixture of a typical industrial solvent waste (acetone, formaldehyde, methanol, dimethylbenzene, butanol, trichlor, and perchlor), without fuel cell produced carbon dioxide added in the feed, but with steam at 49.45%. As before, there are no kinetic limitations in compositions above 700°C and the gas compositions are very accurate, and this fact has been confirmed by on-line gas chromatography and mass spectrometry. The H2/CO was about 1.4. One notes that the hydrogen product remains high and steady at 48.9% at 700°C and beyond. However, the syngas is quite dirty; with many undesirable compounds at the 0.5 mole percent level (i.e. carcinogenic benzene). This syngas is not acceptable for molten carbonate or solid oxide fuel cells even after the hydrogen chloride (and any other acid gases) are removed. Referring to FIG. 7 at 1200°C, the syngas product composition starts at the highest with hydrogen, at 48.9%; then carbon monoxide at 35.5%; methane at 6.3%; acetylene (C2H2) at 2%; hydrogen chloride gas at 0.9%; benzene (CβHβ) at 0.5%; ethylene (C2H4) at 0.4%; naphthalene at 0.28%; propylene- 1 (C6H4) at 85 ppm; propylene-2 (C3H ) at 50 ppm; ethane (C2H6) at 25 ppm; methyl radical (CH3) at 25 ppm; hydrogen radical at 9 ppm; water at 7 ppm; carbon dioxide at 2 ppm; with all other compounds at levels below 0.01 ppm. FIG. 8 shows a plot of the steam reforming of the same mixture of industrial solvent waste as in the composition for FIG. 7, without fuel cell produced carbon dioxide added in the feed, but with steam at 66%. It is noted that the hydrogen product remains high and steady at 48.9% at 1000°C and beyond. The syngas is quite clean, with undesirable compounds at the 10"5 mole percent level (i.e. 0.1 ppm). This syngas ratio H2/CO of about 1.2 is excellent for Fischer Tropsch synthesis as well as molten carbonate or solid oxide fuel cells, after the hydrogen chloride (and any other acid gases) are removed. Referring to FIG. 8 at 1200°C, the syngas product composition starts at the highest with hydrogen, at 63%; then carbon monoxide at 40%; hydrogen chloride gas at 0.6% ppm; water at 0.5%; carbon dioxide at 0.1%; methane at 100 ppm; hydrogen radical at 10 ppm; acetylene at 4 ppm; ethylene at 1 ppm; with all other compounds at levels below 0.09 ppb. It is noted that this is only about 10,000 times cleaner in minor contaminants where the goal of the present invention is a million times cleaner. Even further improvements can be made, unexpectedly, as are shown in FIG. 9, by increasing the CO2/ H2O ratio from the 1.3 in FIG. 7 up to 2.8 in FIG. 9.
This added CO2 from the fuel cell is 25% of the waste feed. The steam used in FIG. 8 is actually a decrease to 60% in the amount of steam consumption in the process, with the advantage of the steam-reforming reactor being able to accept more CO2, contrary to conventional thinking. Referring to FIG. 9 at 1200°C, the syngas product composition starts at the highest with hydrogen, at 49.9%; then carbon monoxide at 42.4%; water at 5.4%;
CO2 at 1.73%; hydrogen chloride gas at 0.6% ppm; hydrogen radical at 13 ppm; methane at 1.6 ppm; acetylene at 0.2 ppb; ethylene at 0.03 ppb; with all other compounds at levels below 0.1 ppb. It is noted that this is about 10 million times cleaner or lower in minor contaminants. Even further optimizing improvements can be made as are shown in
FIG. 10 by slightly increasing the recycle H2O from the 46.3% in FIG. 9 up to 50.9% in FIG. 10. This CO2 from the fuel cell was 23% of the waste feed. The syngas in
FIG. 10 is actually cleaner. Referring to FIG. 10 at 1200°C, the syngas product composition starts at the highest with hydrogen at 48.9%, then carbon monoxide at 40.0%; water at
8.1%; CO2 at 2.5%; hydrogen chloride gas at 0.6% ppm; hydrogen radical at 13 ppm; methane at 2.5 ppm; acetylene at 0.1 ppb; ethylene at 0.01 ppb; with all other compounds at levels below 0.04 ppb. It is noted that this is about 20 million times cleaner or lower in minor contaminants. Both of these improvements shown in FIGS. 9 and 10 are economically attractive commercially. This yields a H2/CO about 1.2 that is a syngas composition more amenable to making more valuable chemical co-products than methanol (selling only @ 50 /lb), for example, that requires a H2/CO of 2.0 for its synthesis. Thus, the addition of shift reactors to adjust the H2/CO upward or downward are not required - a further economic advantage of this process of the present invention. Referring to FIG. 11, a superheater 100 is shown in which a mixture of air and natural gas or other suitable fuel is fed through inlet 110 in gas feed tube 111 after fuel-air supply valve 112 is in the open position to supply matrix burner 114. A suitable matrix burner is described in U.S. Patent No. 6,065,963, the description of which is incorporated herein by reference. Matrix or conical surface burners of the type suitable for use in the superheater of the present invention are manufactured by N.V. Acotech S.A and Hauck Manufacturing Company. The flue gases from matrix burner 114 are removed from superheater 100 via flue 114 in tube 116. Process gases from gasifier 12 enter through a plurality of process gas inlets 120 supplied by an annular manifold (not shown) around the circumference of the walls 122 of superheater 100 and pass into flow annulus 124. Similarly, steam is introduced through line 150 (see FIG. 12) operably connected to a plurality of steam inlets 126 supplied by an annular manifold into annulus 124. The heated exit gases pass through exit gas outlet 18. Although FIG. 12 shows gasifier 12 comprising rotary kiln 130 and superheater 100 positioned partially within the exit region 138 of kiln 130, superheater 100 can also be operably positioned entirely outside of kiln 130 in order to superheat the intermediate gas stream from the kiln that enter the process gas inlet 120 (see FIG. 11) of superheater 100 to temperatures in the range at least 700° to about 1600°C (1300-2900°F) before the exit gas stream passes through exit gas outlet 18. A standard expansion bellows 139, a rotary seal assembly 140, and a plurality of pneumatic struts 142 are operably mounted around the outside circumference of kiln 130 to allow for approximately one foot of expansion of kiln 130 during its operation. Further, without departing from the spirit and scope of this invention, one of ordinary skill in the art can make various other embodiments and aspects of the process and system of the present invention to adapt it to specific usages and conditions. As such, these changes and modifications are properly, equitably, and intended to be, within the full range of equivalents of the following claims.

Claims

WHAT IS CLAIMED IS: 1. A process for converting carbonaceous feedstocks into energy without the production of unwanted greenhouse gas emissions comprising: (a) converting a carbonaceous feedstock selected from the group consisting of coal, hydrocarbon oil, natural gas, petroleum coke, oil shale, carbonaceous-containing waste oil, carbonaceous-containing medical waste, carbonaceous-containing military waste, carbonaceous-containing industrial waste, carbonaceous-containing medical waste, carbonaceous-containing sewage sludge and municipal solid waste, carbonaceous-containing agricultural waste, carbonaceous- containing biomass, biological and biochemical waste, and mixtures thereof, and a greenhouse gas stream in a gasification unit to synthesis gas comprising carbon monoxide and hydrogen, said gasification unit is a non-catalytic high temperature, gas-phase reactor operating at conditions to achieve a gas exit temperature of from at least 700° to about 1600°C (1300-2900°F); (b) electrochemically oxidizing at least a portion of said synthesis gas from said gasification unit in a first half-cell of a fuel cell (anode) to a first half-cell exit gas comprising carbon dioxide and water; (c) recovering the carbon dioxide from said first half-cell exit gas to serve as at least 20 % of said greenhouse gas stream in step (a); and (d) electrochemically reducing an oxygen-containing gas in a second half-cell of said fuel cell (cathode) completing the circuit and resulting in the production of electrical energy.
2. The process of Claim 1 wherein said greenhouse gas stream is carbon dioxide.
3. The process of Claim 1 is used as in a waste-to-energy fossil fuel plant.
4. The process of Claim 1 is used in a petroleum refinery.
5. The process of Claim 1 is used in a petrochemical plant.
6. The process of Claim 1 wherein said gasification unit contains a rotary kiln.
7. The process of Claim 1 wherein a portion of said synthesis gas from said gasification unit is converted in a chemical reactor into useful hydrocarbon products.
8. The process of Claim 7 wherein said chemical reactor is a Fischer-Tropsch reactor.
9. The process of Claim 1 wherein a major portion of the water is condensed from said first half-cell exit gas using a condenser.
10. The process of Claim 9 wherein CO2 and at least a portion of the condensed water is passed to said gasification unit in an amount to adjust the hydrogen to carbon ratio of the combined carbonaceous feedstock and greenhouse gas stream is sufficient to result in a synthesis gas having an optimum ratio for the Fischer-Tropsch reactor.
11. The process of Claim 10 wherein said synthesis gas has a hydrogen to carbon ratio in the range of about 1.75 to about 2.5.
12. The process of Claim 1 wherein the amount of greenhouse gas stream is adjusted in step (a) so that the combined carbonaceous feedstock and greenhouse gas stream to said gasification unit has a hydrogen to carbon monoxide ratio in the range of about 1.75 to about 2.5.
13. The process of Claim 1 wherein the oxygen-containing gas in step (d) is air and the nitrogen portion as a result of the electrical reduction is exited into the atmosphere.
14. The process of Claim 1 wherein said first half-cell of said fuel cell contains an electrolyte surrounding a porous catalytic anode electrode.
15. The process of Claim 14 wherein said second half-cell of said fuel cell contains an electronically conducting electrolyte surrounding a catalytic cathode electrode.
16. The process of Claim 15 wherein said first and second half- cells of said fuel cell are separated by an ionically conducting membrane that will not allow passage of components from the respective half-cells.
17. A system for converting carbonaceous feedstocks into energy without the production of unwanted greenhouse gas emissions which comprises: (a) a gasification unit containing a non-catalytic high temperature, gas-phase reactor and having inlet means for a carbonaceous feedstock selected from the group consisting of coal, hydrocarbon oil, natural gas, petroleum coke, oil shale, carbonaceous-containing waste oil, carbonaceous-containing medical waste, carbonaceous-containing military waste, carbonaceous-containing industrial waste, carbonaceous-containing medical waste, carbonaceous-containing sewage sludge and municipal solid waste, carbonaceous-containing agricultural waste, carbonaceous- containing biomass, biological and biochemical waste, and mixtures thereof, and a greenhouse gas stream operating at conditions to achieve a gas exit temperature of from at least 700° to about 1600°C ( 1300-2900°F) for converting a combined feedstock into synthesis gas comprising carbon monoxide and hydrogen and an outlet for the synthesis gas; (b) a fuel cell for the production of electrical energy comprising a first half-cell having an inlet in fluid communication with the synthesis gas and first means for electrochemically oxidizing synthesis gas into a first half-cell exit gas of carbon dioxide and water, a second half-cell having second means for electrochemically reducing an oxygen-containing gas, and a membrane separating said first and second half cells that will not allow passage of components from the respective half-cells; and (c) passage means for passing the carbon dioxide from said first half- cell to serve as a greenhouse gas stream for said gasification unit.
18. The system of Claim 17 wherein the greenhouse gas stream is carbon dioxide.
19. The system of Claim 17 wherein said gasification unit contains a rotary kiln.
20. The system of Claim 17 further comprising a chemical reactor in fluid communication with said gasification unit to convert a portion of said synthesis gas from said gasification unit into useful hydrocarbon products.
21. The system of Claim 20 wherein said chemical reactor is a Fischer-Tropsch reactor.
22. The system of Claim 21 wherein a condenser is used to condense a major portion of the water from said first half-cell exit gas.
23. The system of Claim 22 wherein the CO2 and at least a portion of the condensed water is passed to said gasification unit in an amount to adjust the hydrogen to carbon ratio of the combined carbonaceous feedstock and greenhouse gas stream sufficiently to result in a synthesis gas having an optimum ratio for the Fischer-Tropsch reactor.
24. The system of Claim 23 wherein said synthesis gas has a hydrogen to carbon ratio in the range of about 1.75 to about 2.5.
25. The system of Claim 21 wherein the amount of greenhouse gas stream is adjusted in step (a) so that exit gas stream of said gasification unit has a hydrogen to carbon monoxide ratio in the range of about 1.75 to about 2.5.
26. The system of Claim 17 wherein the oxygen-containing gas is air and the nitrogen formed as a result of the ionic reduction is exited into the atmosphere.
27. The system of Claim 17 wherein said first half-cell of said fuel cell contains an electrolyte surrounding a porous catalytic anode electrode.
28. The system of Claim 27 wherein said second half-cell of said fuel cell contains an electronically conducting electrolyte surrounding a catalytic cathode electrode.
29. A system for converting carbonaceous feedstocks into energy without the production of unwanted greenhouse gas emissions which comprises: (a) a gasification unit containing an indirectly heated rotary kiln and having inlet means for a carbonaceous feedstock selected from the group consisting of coal, hydrocarbon oil, natural gas, petroleum coke, oil shale, carbonaceous-containing waste oil, carbonaceous-containing medical waste, carbonaceous-containing military waste, carbonaceous-containing industrial waste, carbonaceous-containing medical waste, carbonaceous-containing sewage sludge and municipal solid waste, carbonaceous-containing agricultural waste, carbonaceous-containing biomass, biological and biochemical waste, and mixtures thereof, and a greenhouse gas stream, a gas exit means, and a solids exit means between the inlet means and the exit means operating at conditions to achieve a gas exit temperature of from at least 700° to about 1600°C (1300-2900°F) for converting a converting the combined feedstock into synthesis gas comprising carbon monoxide and hydrogen and an outlet for the synthesis gas; (b) a fuel cell for the production of electrical energy comprising a first half-cell having an inlet in fluid communication with the synthesis gas and first means for electrochemically oxidizing synthesis gas into a first half-cell exit gas of carbon dioxide and water, a second half-cell having second means for electrochemically reducing an oxygen-containing gas, and a membrane separating said first and second half cells that will not allow passage of components from the respective half-cells; and (c) passage means for passing the carbon dioxide from said first half- cell to serve as a greenhouse gas stream for said gasification unit.
30. The system of Claim 29 wherein said gasification unit further comprising a superheater means for superheating the exit gas to a temperature in the range from at least 700° to about 1600°C (1300-2900°F).
31. The system of Claim 30 wherein said gasification unit comprises said indirectly heated rotary kiln having said inlet means for said carbonaceous feedstock, said gas exit means, and said solids exit means, and having said superheater operably positioned at least partially within said kiln in the region adjacent to the gas exit means.
PCT/US2004/019379 2003-06-23 2004-06-16 Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions WO2005001977A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP04755504A EP1652256A4 (en) 2003-06-23 2004-06-16 Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
CA2530496A CA2530496C (en) 2003-06-23 2004-06-16 Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US10/602,536 US7132183B2 (en) 2002-06-27 2003-06-23 Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
US10/602,536 2003-06-23
US10/719,504 2003-11-21
US10/719,504 US7220502B2 (en) 2002-06-27 2003-11-21 Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions

Publications (1)

Publication Number Publication Date
WO2005001977A1 true WO2005001977A1 (en) 2005-01-06

Family

ID=33555805

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2004/019379 WO2005001977A1 (en) 2003-06-23 2004-06-16 Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions

Country Status (4)

Country Link
US (1) US7220502B2 (en)
EP (1) EP1652256A4 (en)
CA (1) CA2530496C (en)
WO (1) WO2005001977A1 (en)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008057467A2 (en) * 2006-11-02 2008-05-15 Terry Galloway Appliance for converting household waste into energy
EP2014744A1 (en) * 2006-05-02 2009-01-14 Institut Problem Khimicheskoi Fiziki Rossiiskoi AK Method for processing condensed fuel by gasification and a device for carrying out said method
WO2010062879A2 (en) * 2008-11-26 2010-06-03 Good Earth Power Corporation Enhanced product gas and power evolution from carbonaceous materials via gasification
EP2217554A1 (en) * 2007-12-13 2010-08-18 Gyco, Inc. Method and apparatus for reducing co2 in a stream by conversion to a syngas for production of energy
WO2014151216A1 (en) * 2013-03-15 2014-09-25 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in fischer-tropsch synthesis
US9077008B2 (en) 2013-03-15 2015-07-07 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using fuel cells
US9212059B2 (en) 2007-12-13 2015-12-15 Gyco, Inc. Method and apparatus for improving the efficiency of an SMR process for producing syngas while reducing the CO2 in a gaseous stream
US9556753B2 (en) 2013-09-30 2017-01-31 Exxonmobil Research And Engineering Company Power generation and CO2 capture with turbines in series
WO2017096467A1 (en) * 2015-12-07 2017-06-15 1304342 Alberta Ltd. Upgrading oil using supercritical fluids
US9755258B2 (en) 2013-09-30 2017-09-05 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using solid oxide fuel cells
US9774053B2 (en) 2013-03-15 2017-09-26 Exxonmobil Research And Engineering Company Integrated power generation and carbon capture using fuel cells
US10787891B2 (en) 2015-10-08 2020-09-29 1304338 Alberta Ltd. Method of producing heavy oil using a fuel cell
US10968725B2 (en) 2016-02-11 2021-04-06 1304338 Alberta Ltd. Method of extracting coal bed methane using carbon dioxide
US11211621B2 (en) 2018-11-30 2021-12-28 Exxonmobil Research And Engineering Company Regeneration of molten carbonate fuel cells for deep CO2 capture
US11335937B2 (en) 2019-11-26 2022-05-17 Exxonmobil Research And Engineering Company Operation of molten carbonate fuel cells with high electrolyte fill level
US11424469B2 (en) 2018-11-30 2022-08-23 ExxonMobil Technology and Engineering Company Elevated pressure operation of molten carbonate fuel cells with enhanced CO2 utilization
US11476486B2 (en) 2018-11-30 2022-10-18 ExxonMobil Technology and Engineering Company Fuel cell staging for molten carbonate fuel cells
US11649550B1 (en) 2022-07-26 2023-05-16 Nant Holdings Ip, Llc Methods and systems for producing carbon-neutral fuels from aragonite
US11664519B2 (en) 2019-11-26 2023-05-30 Exxonmobil Research And Engineering Company Fuel cell module assembly and systems using same
US11695122B2 (en) 2018-11-30 2023-07-04 ExxonMobil Technology and Engineering Company Layered cathode for molten carbonate fuel cell
US11742508B2 (en) 2018-11-30 2023-08-29 ExxonMobil Technology and Engineering Company Reforming catalyst pattern for fuel cell operated with enhanced CO2 utilization
US11866395B2 (en) 2018-03-07 2024-01-09 1304338 Alberta Ltd. Production of petrochemical feedstocks and products using a fuel cell
US11888187B2 (en) 2018-11-30 2024-01-30 ExxonMobil Technology and Engineering Company Operation of molten carbonate fuel cells with enhanced CO2 utilization

Families Citing this family (87)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7396603B2 (en) 2004-06-03 2008-07-08 Fuelcell Energy, Inc. Integrated high efficiency fossil fuel power plant/fuel cell system with CO2 emissions abatement
KR20130102646A (en) * 2005-01-18 2013-09-17 엔퀘스트 파워 코포레이션 Method for steam reforming carbonaceous material
MY142221A (en) * 2005-04-06 2010-11-15 Cabot Corp Method to produce hydrogen or synthesis gas
US8114176B2 (en) * 2005-10-12 2012-02-14 Great Point Energy, Inc. Catalytic steam gasification of petroleum coke to methane
WO2007106819A2 (en) * 2006-03-13 2007-09-20 Patrick Herda Method preventing toxic runoff in conjunction with plasma gasification
US7922782B2 (en) * 2006-06-01 2011-04-12 Greatpoint Energy, Inc. Catalytic steam gasification process with recovery and recycle of alkali metal compounds
US20090049748A1 (en) * 2007-01-04 2009-02-26 Eric Day Method and system for converting waste into energy
US8163047B2 (en) * 2007-01-10 2012-04-24 General Electric Company Methods and apparatus for cooling syngas in a gasifier
US8163048B2 (en) * 2007-08-02 2012-04-24 Greatpoint Energy, Inc. Catalyst-loaded coal compositions, methods of making and use
US8641991B2 (en) * 2007-08-30 2014-02-04 Chevron U.S.A. Inc. Hybrid refinery for co-processing biomass with conventional refinery streams
US20090056225A1 (en) * 2007-08-30 2009-03-05 Chevron U.S.A. Inc. Process for Introducing Biomass Into a Conventional Refinery
WO2009048723A2 (en) * 2007-10-09 2009-04-16 Greatpoint Energy, Inc. Compositions for catalytic gasification of a petroleum coke and process for conversion thereof to methane
WO2009086363A1 (en) * 2007-12-28 2009-07-09 Greatpoint Energy, Inc. Coal compositions for catalytic gasification and process for its preparation
WO2009086407A2 (en) 2007-12-28 2009-07-09 Greatpoint Energy, Inc. Steam generating slurry gasifier for the catalytic gasification of a carbonaceous feedstock
WO2009086370A2 (en) * 2007-12-28 2009-07-09 Greatpoint Energy, Inc. Processes for making syngas-derived products
US20090165383A1 (en) * 2007-12-28 2009-07-02 Greatpoint Energy, Inc. Catalytic Gasification Process with Recovery of Alkali Metal from Char
CN101910370B (en) * 2007-12-28 2013-09-25 格雷特波因特能源公司 Catalytic gasification process with recovery of alkali metal from char
US7901644B2 (en) * 2007-12-28 2011-03-08 Greatpoint Energy, Inc. Catalytic gasification process with recovery of alkali metal from char
US9698439B2 (en) 2008-02-19 2017-07-04 Proton Power, Inc. Cellulosic biomass processing for hydrogen extraction
US8303676B1 (en) 2008-02-19 2012-11-06 Proton Power, Inc. Conversion of C-O-H compounds into hydrogen for power or heat generation
CA2716135C (en) 2008-02-29 2013-05-28 Greatpoint Energy, Inc. Particulate composition for gasification, preparation and continuous conversion thereof
US8286901B2 (en) * 2008-02-29 2012-10-16 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
WO2009111332A2 (en) * 2008-02-29 2009-09-11 Greatpoint Energy, Inc. Reduced carbon footprint steam generation processes
US20090217582A1 (en) * 2008-02-29 2009-09-03 Greatpoint Energy, Inc. Processes for Making Adsorbents and Processes for Removing Contaminants from Fluids Using Them
US7926750B2 (en) * 2008-02-29 2011-04-19 Greatpoint Energy, Inc. Compactor feeder
US8366795B2 (en) 2008-02-29 2013-02-05 Greatpoint Energy, Inc. Catalytic gasification particulate compositions
US8297542B2 (en) 2008-02-29 2012-10-30 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
US20090260287A1 (en) * 2008-02-29 2009-10-22 Greatpoint Energy, Inc. Process and Apparatus for the Separation of Methane from a Gas Stream
US8114177B2 (en) 2008-02-29 2012-02-14 Greatpoint Energy, Inc. Co-feed of biomass as source of makeup catalysts for catalytic coal gasification
US20090220406A1 (en) * 2008-02-29 2009-09-03 Greatpoint Energy, Inc. Selective Removal and Recovery of Acid Gases from Gasification Products
US20090217575A1 (en) 2008-02-29 2009-09-03 Greatpoint Energy, Inc. Biomass Char Compositions for Catalytic Gasification
US8709113B2 (en) 2008-02-29 2014-04-29 Greatpoint Energy, Inc. Steam generation processes utilizing biomass feedstocks
US20090249685A1 (en) * 2008-03-28 2009-10-08 Flowers Troy D Closed loop biomass energy system
CA2718295C (en) 2008-04-01 2013-06-18 Greatpoint Energy, Inc. Processes for the separation of methane from a gas stream
US8192716B2 (en) 2008-04-01 2012-06-05 Greatpoint Energy, Inc. Sour shift process for the removal of carbon monoxide from a gas stream
US7819932B2 (en) * 2008-04-10 2010-10-26 Carbon Blue-Energy, LLC Method and system for generating hydrogen-enriched fuel gas for emissions reduction and carbon dioxide for sequestration
US20090307974A1 (en) * 2008-06-14 2009-12-17 Dighe Shyam V System and process for reduction of greenhouse gas and conversion of biomass
US8647402B2 (en) * 2008-09-19 2014-02-11 Greatpoint Energy, Inc. Processes for gasification of a carbonaceous feedstock
WO2010033846A2 (en) 2008-09-19 2010-03-25 Greatpoint Energy, Inc. Char methanation catalyst and its use in gasification processes
JP5384649B2 (en) * 2008-09-19 2014-01-08 グレイトポイント・エナジー・インコーポレイテッド Method for gasification of carbonaceous feedstock
US8858900B2 (en) * 2008-10-14 2014-10-14 Intellergy, Inc. Process and system for converting waste to energy without burning
US8202913B2 (en) * 2008-10-23 2012-06-19 Greatpoint Energy, Inc. Processes for gasification of a carbonaceous feedstock
WO2010065137A1 (en) * 2008-12-05 2010-06-10 Global Energies, Llc Recycling of greenhouse gasses in large scale plasma processes
WO2010078297A1 (en) 2008-12-30 2010-07-08 Greatpoint Energy, Inc. Processes for preparing a catalyzed carbonaceous particulate
US8734548B2 (en) 2008-12-30 2014-05-27 Greatpoint Energy, Inc. Processes for preparing a catalyzed coal particulate
US8500868B2 (en) * 2009-05-01 2013-08-06 Massachusetts Institute Of Technology Systems and methods for the separation of carbon dioxide and water
KR101468768B1 (en) * 2009-05-13 2014-12-04 그레이트포인트 에너지, 인크. Processes for hydromethanation of a carbonaceous feedstock
US8268899B2 (en) * 2009-05-13 2012-09-18 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
WO2010132551A2 (en) 2009-05-13 2010-11-18 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
US8690977B2 (en) 2009-06-25 2014-04-08 Sustainable Waste Power Systems, Inc. Garbage in power out (GIPO) thermal conversion process
WO2011034889A1 (en) * 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Integrated hydromethanation combined cycle process
WO2011034888A1 (en) * 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Processes for hydromethanation of a carbonaceous feedstock
WO2011034891A1 (en) * 2009-09-16 2011-03-24 Greatpoint Energy, Inc. Two-mode process for hydrogen production
WO2011049861A2 (en) 2009-10-19 2011-04-28 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
AU2010310846B2 (en) 2009-10-19 2013-05-30 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
AU2010339952B8 (en) * 2009-12-17 2013-12-19 Greatpoint Energy, Inc. Integrated enhanced oil recovery process
CN102754266B (en) 2010-02-23 2015-09-02 格雷特波因特能源公司 integrated hydrogenation methanation fuel cell power generation
US8652696B2 (en) 2010-03-08 2014-02-18 Greatpoint Energy, Inc. Integrated hydromethanation fuel cell power generation
KR101440710B1 (en) 2010-04-26 2014-09-17 그레이트포인트 에너지, 인크. Hydromethanation of a carbonaceous feedstock with vanadium recovery
CN102906230B (en) 2010-05-28 2015-09-02 格雷特波因特能源公司 Liquid heavy hydrocarbon feedstocks is to the conversion of gaseous product
WO2012024369A1 (en) 2010-08-18 2012-02-23 Greatpoint Energy, Inc. Hydromethanation of carbonaceous feedstock
JP6124795B2 (en) 2010-11-01 2017-05-10 グレイトポイント・エナジー・インコーポレイテッド Hydrogenation methanation of carbonaceous feedstock.
CN103391989B (en) 2011-02-23 2015-03-25 格雷特波因特能源公司 Hydromethanation of a carbonaceous feedstock with nickel recovery
CN103582693A (en) 2011-06-03 2014-02-12 格雷特波因特能源公司 Hydromethanation of a carbonaceous feedstock
WO2013052553A1 (en) 2011-10-06 2013-04-11 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
CN102354744A (en) * 2011-10-08 2012-02-15 中国电子科技集团公司第十八研究所 Method for improving stability in batch production of lithium iron phosphate
WO2013112619A1 (en) 2012-01-23 2013-08-01 Battelle Memorial Institute Separation and/or sequestration apparatus and methods
US9023243B2 (en) 2012-08-27 2015-05-05 Proton Power, Inc. Methods, systems, and devices for synthesis gas recapture
US10005961B2 (en) 2012-08-28 2018-06-26 Proton Power, Inc. Methods, systems, and devices for continuous liquid fuel production from biomass
CN104704204B (en) 2012-10-01 2017-03-08 格雷特波因特能源公司 Method for producing steam from original low rank coal raw material
CN104685038B (en) 2012-10-01 2016-06-22 格雷特波因特能源公司 Graininess low rank coal raw material of agglomeration and application thereof
CN104685039B (en) 2012-10-01 2016-09-07 格雷特波因特能源公司 Graininess low rank coal raw material of agglomeration and application thereof
WO2014055351A1 (en) 2012-10-01 2014-04-10 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
CN104004548B (en) * 2013-02-22 2015-09-23 石家庄新华能源环保科技股份有限公司 A kind of gasification production equipment
US10563128B2 (en) 2014-01-10 2020-02-18 Proton Power, Inc. Methods for aerosol capture
US20150307784A1 (en) 2014-03-05 2015-10-29 Proton Power, Inc. Continuous liquid fuel production methods, systems, and devices
US11268038B2 (en) 2014-09-05 2022-03-08 Raven Sr, Inc. Process for duplex rotary reformer
US9896339B2 (en) 2014-10-17 2018-02-20 Sabic Global Technologies B.V. Carbon monoxide production from carbon dioxide reduction by elemental sulfur
US9890332B2 (en) 2015-03-08 2018-02-13 Proton Power, Inc. Biochar products and production
US11390521B2 (en) * 2016-06-18 2022-07-19 Think Tank 42 Pty Ltd Method and system for carbon capture and recycling
KR20230011393A (en) 2018-03-16 2023-01-20 퓨얼셀 에너지, 인크 System and method for producing hydrogen using high temperature fuel cells
US10464872B1 (en) 2018-07-31 2019-11-05 Greatpoint Energy, Inc. Catalytic gasification to produce methanol
US10797332B2 (en) * 2018-08-31 2020-10-06 Fuelcell Energy, Inc. Low pressure carbon dioxide removal from the anode exhaust of a fuel cell
US10344231B1 (en) 2018-10-26 2019-07-09 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization
US10435637B1 (en) 2018-12-18 2019-10-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization and power generation
US10618818B1 (en) 2019-03-22 2020-04-14 Sure Champion Investment Limited Catalytic gasification to produce ammonia and urea
RU2723865C1 (en) * 2019-08-12 2020-06-17 Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный технологический университет" (ФГБОУ ВО "КубГТУ") Method for synthesis gas production from plant biomass

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4473622A (en) * 1982-12-27 1984-09-25 Chludzinski Paul J Rapid starting methanol reactor system
US4874587A (en) * 1986-09-03 1989-10-17 Thermolytic Decomposer Hazardous waste reactor system
US5068159A (en) * 1988-12-24 1991-11-26 Ishikawajima-Harima Heavy Industries Co., Ltd. Electric power producing system using molten carbonate type fuel cell
US5616430A (en) * 1994-08-30 1997-04-01 Toyota Jidosha Kabushiki Kaisha Reformer and fuel cell system using the same
US6065963A (en) 1997-01-10 2000-05-23 N.V. Bekaert S.A. Conical surface burner
US6187465B1 (en) * 1997-11-07 2001-02-13 Terry R. Galloway Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
US20030175561A1 (en) * 2002-03-18 2003-09-18 Lightner Gene E. Production of electricity from fuel cells achieved by biomass gasification

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60177571A (en) 1984-02-22 1985-09-11 Ishikawajima Harima Heavy Ind Co Ltd Coke oven gas energy recovery power-generating method
US5248566A (en) 1991-11-25 1993-09-28 The United States Of America As Represented By The United States Department Of Energy Fuel cell system for transportation applications
US5423891A (en) * 1993-05-06 1995-06-13 Taylor; Robert A. Method for direct gasification of solid waste materials
JP3053362B2 (en) 1995-08-01 2000-06-19 株式会社東芝 Separation method of carbon dioxide gas Foam carbon dioxide gas absorbent and carbon dioxide gas separation device
US5662052A (en) * 1995-11-13 1997-09-02 United States Department Of Energy Method and system including a double rotary kiln pyrolysis or gasification of waste material
US6086722A (en) * 1996-07-17 2000-07-11 Texaco Inc. Minimizing evaporator scaling and recovery of salts during gasification
US20030022035A1 (en) * 1997-11-07 2003-01-30 Galloway Terry R. Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
US5985474A (en) 1998-08-26 1999-11-16 Plug Power, L.L.C. Integrated full processor, furnace, and fuel cell system for providing heat and electrical power to a building

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4473622A (en) * 1982-12-27 1984-09-25 Chludzinski Paul J Rapid starting methanol reactor system
US4874587A (en) * 1986-09-03 1989-10-17 Thermolytic Decomposer Hazardous waste reactor system
US5068159A (en) * 1988-12-24 1991-11-26 Ishikawajima-Harima Heavy Industries Co., Ltd. Electric power producing system using molten carbonate type fuel cell
US5616430A (en) * 1994-08-30 1997-04-01 Toyota Jidosha Kabushiki Kaisha Reformer and fuel cell system using the same
US6065963A (en) 1997-01-10 2000-05-23 N.V. Bekaert S.A. Conical surface burner
US6187465B1 (en) * 1997-11-07 2001-02-13 Terry R. Galloway Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
US20030175561A1 (en) * 2002-03-18 2003-09-18 Lightner Gene E. Production of electricity from fuel cells achieved by biomass gasification

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BETTE HILEMAN: "Industry Considers C02 Reduction Methods", CHEM & ENGR. NEWS, 30 June 1997 (1997-06-30), pages 30
MICHELE ARESTA, EUGENIO QUARANTA: "Carbon Dioxide : A Substitute for Phosgene", CHEM.TECH., March 1997 (1997-03-01), pages 32 - 40
See also references of EP1652256A4

Cited By (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2014744A1 (en) * 2006-05-02 2009-01-14 Institut Problem Khimicheskoi Fiziki Rossiiskoi AK Method for processing condensed fuel by gasification and a device for carrying out said method
EP2014744A4 (en) * 2006-05-02 2012-04-11 Inst Khim Fiz Rossiiskoi Ak Method for processing condensed fuel by gasification and a device for carrying out said method
WO2008057467A3 (en) * 2006-11-02 2009-03-05 Terry Galloway Appliance for converting household waste into energy
WO2008057467A2 (en) * 2006-11-02 2008-05-15 Terry Galloway Appliance for converting household waste into energy
US8916617B2 (en) 2007-12-13 2014-12-23 Gyco, Inc. Method and apparatus for reducing CO2 in a stream by conversion to a syngas for production of energy
EP2217554A1 (en) * 2007-12-13 2010-08-18 Gyco, Inc. Method and apparatus for reducing co2 in a stream by conversion to a syngas for production of energy
EP2217554A4 (en) * 2007-12-13 2012-05-30 Gyco Inc Method and apparatus for reducing co2 in a stream by conversion to a syngas for production of energy
US8507567B2 (en) 2007-12-13 2013-08-13 Gyco, Inc. Method and apparatus for reducing CO2 in a stream by conversion to a Syngas for production of energy
US9212059B2 (en) 2007-12-13 2015-12-15 Gyco, Inc. Method and apparatus for improving the efficiency of an SMR process for producing syngas while reducing the CO2 in a gaseous stream
WO2010062879A2 (en) * 2008-11-26 2010-06-03 Good Earth Power Corporation Enhanced product gas and power evolution from carbonaceous materials via gasification
WO2010062879A3 (en) * 2008-11-26 2010-10-28 Good Earth Power Corporation Enhanced product gas and power evolution from carbonaceous materials via gasification
US9650246B2 (en) 2013-03-15 2017-05-16 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in fischer-tropsch synthesis
US9786939B2 (en) 2013-03-15 2017-10-10 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using fuel cells
US9077008B2 (en) 2013-03-15 2015-07-07 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using fuel cells
US9077006B2 (en) 2013-03-15 2015-07-07 Exxonmobil Research And Engineering Company Integrated power generation and carbon capture using fuel cells
US9077007B2 (en) 2013-03-15 2015-07-07 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using fuel cells
US9178234B2 (en) 2013-03-15 2015-11-03 Exxonmobil Research And Engineering Company Integrated power generation using molten carbonate fuel cells
WO2014151214A1 (en) * 2013-03-15 2014-09-25 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in fischer-tropsch synthesis
US9257711B2 (en) 2013-03-15 2016-02-09 Exxonmobil Research And Engineering Company Integrated carbon capture and chemical production using fuel cells
US9263755B2 (en) 2013-03-15 2016-02-16 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in iron and steel processing
US9343764B2 (en) 2013-03-15 2016-05-17 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in methanol synthesis
US9343763B2 (en) 2013-03-15 2016-05-17 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells for synthesis of nitrogen compounds
US9362580B2 (en) 2013-03-15 2016-06-07 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in a refinery setting
US9419295B2 (en) 2013-03-15 2016-08-16 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using fuel cells at a reduced electrical efficiency
US9455463B2 (en) 2013-03-15 2016-09-27 Exxonmobil Research And Engineering Company Integrated electrical power and chemical production using fuel cells
US9520607B2 (en) 2013-03-15 2016-12-13 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells with fermentation processes
US9553321B2 (en) 2013-03-15 2017-01-24 Exxonmobile Research And Engineering Company Integrated power generation and carbon capture using fuel cells
US10676799B2 (en) 2013-03-15 2020-06-09 Exxonmobil Research And Engineering Company Integrated electrical power and chemical production using fuel cells
US9647284B2 (en) 2013-03-15 2017-05-09 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in Fischer-Tropsch synthesis
WO2014151216A1 (en) * 2013-03-15 2014-09-25 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in fischer-tropsch synthesis
US10093997B2 (en) 2013-03-15 2018-10-09 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in iron and steel processing
US9735440B2 (en) 2013-03-15 2017-08-15 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in fischer-tropsch synthesis
US9941534B2 (en) 2013-03-15 2018-04-10 Exxonmobil Research And Engineering Company Integrated power generation and carbon capture using fuel cells
US9774053B2 (en) 2013-03-15 2017-09-26 Exxonmobil Research And Engineering Company Integrated power generation and carbon capture using fuel cells
US9077005B2 (en) 2013-03-15 2015-07-07 Exxonmobil Research And Engineering Company Integration of molten carbonate fuel cells in Fischer-Tropsch synthesis
US9923219B2 (en) 2013-03-15 2018-03-20 Exxonmobile Research And Engineering Company Integrated operation of molten carbonate fuel cells
US9755258B2 (en) 2013-09-30 2017-09-05 Exxonmobil Research And Engineering Company Integrated power generation and chemical production using solid oxide fuel cells
US9556753B2 (en) 2013-09-30 2017-01-31 Exxonmobil Research And Engineering Company Power generation and CO2 capture with turbines in series
US11149531B2 (en) 2015-10-08 2021-10-19 1304342 Alberta Ltd. Producing pressurized and heated fluids using a fuel cell
US10787891B2 (en) 2015-10-08 2020-09-29 1304338 Alberta Ltd. Method of producing heavy oil using a fuel cell
US11473021B2 (en) 2015-12-07 2022-10-18 1304338 Alberta Ltd. Upgrading oil using supercritical fluids
WO2017096467A1 (en) * 2015-12-07 2017-06-15 1304342 Alberta Ltd. Upgrading oil using supercritical fluids
US10968725B2 (en) 2016-02-11 2021-04-06 1304338 Alberta Ltd. Method of extracting coal bed methane using carbon dioxide
US11866395B2 (en) 2018-03-07 2024-01-09 1304338 Alberta Ltd. Production of petrochemical feedstocks and products using a fuel cell
US11843150B2 (en) 2018-11-30 2023-12-12 ExxonMobil Technology and Engineering Company Fuel cell staging for molten carbonate fuel cells
US11476486B2 (en) 2018-11-30 2022-10-18 ExxonMobil Technology and Engineering Company Fuel cell staging for molten carbonate fuel cells
US11424469B2 (en) 2018-11-30 2022-08-23 ExxonMobil Technology and Engineering Company Elevated pressure operation of molten carbonate fuel cells with enhanced CO2 utilization
US11616248B2 (en) 2018-11-30 2023-03-28 ExxonMobil Technology and Engineering Company Elevated pressure operation of molten carbonate fuel cells with enhanced CO2 utilization
US11695122B2 (en) 2018-11-30 2023-07-04 ExxonMobil Technology and Engineering Company Layered cathode for molten carbonate fuel cell
US11742508B2 (en) 2018-11-30 2023-08-29 ExxonMobil Technology and Engineering Company Reforming catalyst pattern for fuel cell operated with enhanced CO2 utilization
US11211621B2 (en) 2018-11-30 2021-12-28 Exxonmobil Research And Engineering Company Regeneration of molten carbonate fuel cells for deep CO2 capture
US11888187B2 (en) 2018-11-30 2024-01-30 ExxonMobil Technology and Engineering Company Operation of molten carbonate fuel cells with enhanced CO2 utilization
US11664519B2 (en) 2019-11-26 2023-05-30 Exxonmobil Research And Engineering Company Fuel cell module assembly and systems using same
US11335937B2 (en) 2019-11-26 2022-05-17 Exxonmobil Research And Engineering Company Operation of molten carbonate fuel cells with high electrolyte fill level
US11888199B2 (en) 2019-11-26 2024-01-30 ExxonMobil Technology and Engineering Company Operation of molten carbonate fuel cells with high electrolyte fill level
US11649550B1 (en) 2022-07-26 2023-05-16 Nant Holdings Ip, Llc Methods and systems for producing carbon-neutral fuels from aragonite
US11761098B1 (en) 2022-07-26 2023-09-19 Nant Holdings Ip, Llc Methods and systems for producing carbon-neutral fuels from aragonite

Also Published As

Publication number Publication date
EP1652256A1 (en) 2006-05-03
US7220502B2 (en) 2007-05-22
CA2530496A1 (en) 2005-01-06
CA2530496C (en) 2013-03-19
US20040115492A1 (en) 2004-06-17
EP1652256A4 (en) 2010-08-11

Similar Documents

Publication Publication Date Title
US7220502B2 (en) Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
US7132183B2 (en) Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
US20030022035A1 (en) Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
US6187465B1 (en) Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
US6548197B1 (en) System integration of a steam reformer and fuel cell
Guandalini et al. Comparative assessment and safety issues in state-of-the-art hydrogen production technologies
Steinberg et al. Modern and prospective technologies for hydrogen production from fossil fuels
EP2969927B1 (en) Integrated power generation and chemical production using fuel cells
US7753973B2 (en) Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions
CA2439773C (en) Apparatus and process for the production of hydrogen
US20140272734A1 (en) Electrochemical device for syngas and liquid fuels production
KR20160114632A (en) Reformer-electrolyzer-purifier(rep) assembly for hydrogen production, systems incorporating same and method of producing hydrogen
WO2008137815A1 (en) Reduced-emission gasification and oxidation of hydrocarbon materials for liquid fuel production
AU2014235198B2 (en) Integrated power generation and chemical production using fuel cells
US20230264955A1 (en) Process for producing a gas stream comprising carbon monoxide
NO176339B (en) Procedure for converting fuel to electricity
US20220017826A1 (en) Production of hydrogen and ft products by steam/co2 reforming
Slimane et al. Production of hydrogen by superadiabatic decomposition of hydrogen sulfide
CN113711401B (en) Fuel cell classification for molten carbonate fuel cells
CN113228361B (en) With increased CO 2 High pressure operation of a high utilization molten carbonate fuel cell
Iaquaniello et al. 1 An overview of today’s industrial processes to make hydrogen and future developments’ trend
TW202319334A (en) Method for hydrogen production coupled with co2capture
Galloway HAWAII’S FUTURE WITH INTEGRATED GASIFICATION FUEL CELL COMBINED CYCLE

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2530496

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2004755504

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2004755504

Country of ref document: EP