WO1999046032A2 - Process gas purification and fuel cell system - Google Patents
Process gas purification and fuel cell system Download PDFInfo
- Publication number
- WO1999046032A2 WO1999046032A2 PCT/US1999/005238 US9905238W WO9946032A2 WO 1999046032 A2 WO1999046032 A2 WO 1999046032A2 US 9905238 W US9905238 W US 9905238W WO 9946032 A2 WO9946032 A2 WO 9946032A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen
- module
- purge
- membrane
- product
- Prior art date
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 158
- 238000000746 purification Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 38
- 239000007789 gas Substances 0.000 claims abstract description 306
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 165
- 239000001257 hydrogen Substances 0.000 claims abstract description 164
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 164
- 239000012528 membrane Substances 0.000 claims abstract description 134
- 238000010926 purge Methods 0.000 claims abstract description 108
- 238000003860 storage Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 161
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 69
- 238000000926 separation method Methods 0.000 claims description 61
- 229910001868 water Inorganic materials 0.000 claims description 39
- 239000001301 oxygen Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 238000011084 recovery Methods 0.000 claims description 21
- -1 oxygen ion Chemical class 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012466 permeate Substances 0.000 claims description 4
- 239000003507 refrigerant Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000003487 electrochemical reaction Methods 0.000 claims 4
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000004020 conductor Substances 0.000 claims 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims 2
- 239000003574 free electron Substances 0.000 claims 2
- 230000001737 promoting effect Effects 0.000 claims 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 claims 1
- 239000008236 heating water Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000003570 air Substances 0.000 description 28
- 238000002485 combustion reaction Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000008901 benefit Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001172 regenerating effect Effects 0.000 description 5
- 238000013459 approach Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
- B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/08—Flat membrane modules
- B01D63/087—Single membrane modules
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0251—Physical processing only by making use of membranes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/22—Cooling or heating elements
- B01D2313/221—Heat exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/42—Catalysts within the flow path
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04014—Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
- H01M8/04022—Heating by combustion
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
- H01M8/04156—Arrangements 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
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Definitions
- This invention relates to a system of process gas purification including an apparatus and method for the separation of a gas from a mixed gas stream, whereby the separated and purified gas can be used in industrial and commercial processes.
- This invention also relates to a system whereby the separated gas, for use by a fuel cell, can be stored in the system for further and later use by the fuel cell.
- the invention relates to the purification of a mixed stream by separating therefrom a product which forms part of the mixed stream.
- purification processes have major industrial significance, and are also important to small-scale operations.
- the purification process may involve the separation of any one of a number of gasses, but more typically pertain to the separation of hydrogen or oxygen. These are the two major product gases of interest. However, other gases, for example, nitrogen, argon, carbon dioxide, ammonia, methane and others may be separated by the purification process and separation apparatus of the present invention.
- the pressure of the pure product gas stream must be less than the partial pressure of the product gas in the mixed gas stream to ensure a positive driving force toward purification. Because the pressure of the pure product gas stream cannot exceed the partial pressure of the product gas in the mixed gas stream, the pressure of the pure product gas stream must be less than the pressure of the mixed gas stream. Failure of seals or pins holes in the membrane will compromise the purity of the pure product gas stream due to bulk flow of mixed gas into the pure product stream.
- Product gas recovery factors such as the ratio of pure product gas and product gas in the inlet mixed gas stream and the total membrane surface area required may be considered as measures of the effectiveness of the separation process.
- the inlet pressure of the mixed gas stream is elevated to several atmospheres, and this helps to minimize the surface area of the membrane in the system, maximize recovery factors and increase the pressure of the pure product gas .
- the partial pressure of the product gas in the mixed gas stream exit must be greater than three atmospheres. Assuming the mixed gas stream has an inlet product gas concentration of 50%, and a 75% recovery factor was required, the product gas in the outlet of the mixed gas stream would represent one fifth of the gas stream.
- the inlet gas consists of 8 parts, 4 of which are product gas and 4 of which are other gases.
- Recovery of 75% of the product gas implies that 3 of the 4 product gas parts are removed, and therefore, the remaining mixed gas stream consists of 4 parts other gases and 1 part product gas .
- the product gas partial pressure at the exit of the mixed gas stream side is 1/5 or 20% of the total mixed gas pressure. Since the desired pure product gas is 3 atmospheres, the pressure of the mixed gas stream is 3 atmospheres/20% or equal to 15 atmospheres. Therefore, the mixed gas stream feed pressure would need to be greater than or equal to 15 atmospheres, assuming there was no process flow pressure drop.
- the partial pressure driving force across the membrane is 4.5 atmospheres at the inlet (15 atmospheres * 20%-3 atmospheres) , and approximately zero at the outlet.
- the average driving force is thus 2.25 atmospheres.
- most of the surface area of the membrane is used to achieve the recovery factor, because the driving force approaches zero at the outlet of the mixed gas stream.
- the cost and volume of the membrane would be extremely large.
- the membrane and its seals would have to be constructed so as to maintain cross- pressures of up to 12 atmospheres without leakage in order to maintain the product gas purity.
- the present invention is for a gas purification system, wherein a product gas, contained within a mixed gas stream, is removed from the mixed gas stream across a membrane into a purge gas stream flowing counter current to the mixed gas stream on the opposite side of the membrane.
- the pressures of the mixed gas stream and the purge gas stream respectively are controlled, as is the partial pressure of the product gas on each side of the membrane, to facilitate flow of the product gas through the membrane.
- the invention also facilitates the use of a system where high precision seals of the membrane and other components, and the total absence of pinholes, is not essential to the purity of the product gas separated from the mixed gas stream.
- the mixed gas stream and purge gas stream flow counter-current to each other in a separation module.
- the mixed gas stream contains a product gas which is typically hydrogen or oxygen, but the principles of the system can be used to good effect with other product gases, including but not limited to, nitrogen, argon, carbon dioxide, ammonia and methane.
- the purge gas is an easily separated process gas, and may typically comprise water vapor or a refrigerant, but is not limited to these examples .
- the present invention is a method and apparatus for the purification of hydrogen gas from a mixed gas stream exiting from a reformer or an under-oxidized burner.
- the mixed gas and purge gas streams are separated by an appropriate membrane which must be permeable or effectively permeable to the product gas being separated from the mixed gas stream.
- the membranes will be selected and incorporated into the separation module according to the nature of the product gas being separated from the mixed gas stream.
- "palladium type" metal membranes have demonstrated effectiveness as hydrogen separation membranes, because the hydrogen gas absorbs into the lattice structure of the metal in direct proportion to the partial pressure of the hydrogen gas.
- the partial pressure difference between the hydrogen gas on opposing sides of the membrane is typically used as the driving force to move the hydrogen gas from the mixed gas stream to the purge/product gas stream on the other side of the membrane.
- these separation membranes operate at elevated temperatures in order to maximize the rate of transfer of the product gas, in this particular embodiment hydrogen gas is transferred through the membrane.
- the product gas transferred is hydrogen.
- Ceramic membranes especially at elevated temperatures, absorb oxygen ions into the lattice structure thereof, and these membranes have therefore been used as oxygen separation membranes.
- An example of a ceramic membrane is zirconia and yttria stabilized zirconia.
- Purely ionic conducting membranes are used in electrochemical reactors, where electric power is the primary driving force for separation.
- mixed ionic and electric conducting membranes have been used, where, as with palladium type membranes, only the partial pressure driving force is used to separate oxygen from a mixed gas stream and to purify the oxygen gas.
- the present invention therefore uses, according to one aspect thereof, an innovative approach to the gas membrane separation process, at the same time reducing or eliminating the problem of ensuring high precision seals and significant pressure differentials which tend to more readily expose any weaknesses in the membrane seals.
- a separation module permits the flow of two streams through it and separates the streams by an appropriate membrane.
- a mixed gas stream flows from an inlet to an outlet across the membrane, while on the other side of the membrane, high pressure water vapor is purged in a counter flow direction to that of the mixed gas stream.
- a mixed gas stream is fed into the separation module at 15 atmospheres, the mixed gas stream having a 50% concentration of the product gas.
- the product gas is that component that is to be separated out from the mixed gas stream, and which permeates across the membrane into the purge/product gas stream.
- a water vapor stream is the purge gas and flows on the opposite side of the membrane to that of the mixed gas stream, and in a counter-flow direction to the mixed gas stream.
- the volumetric flow rate of the purge gas stream is twice that of the mixed gas stream, and the pressure thereof slightly greater than that of 15 atmospheres.
- the recovery factor may well approach 100%. Since the partial pressure of the product gas in the purge/product gas is zero at the inlet, the partial pressure of the product gas in the mixed gas stream at the outlet can also approach zero. The partial pressure at the inlet of the purge/product gas stream is in fact zero since the amount of product gas at the inlet of the purge gas stream is zero and, the purge gas at the inlet is pure water vapor.
- the purge/product gas stream exiting the module contains four parts product gas and sixteen parts of water vapor. Since the inlet purge gas stream and therefore the purge/product gas stream is at 15 atmospheres, the product gas partial pressure at the exit of the purge/product gas stream exit is approximately 3 atmospheres. The driving force at the inlet of the mixed gas stream is 4.5 atmospheres and zero at the outlet of the mixed gas stream. This translates to an average driving force of 2.25 atmospheres which is the same as the above example and therefore a similar amount of surface area would be needed.
- the inventive system provides near 100% recovery of the product gas from a mixed gas stream, using similar hardware as conventional systems that achieve only 75% recovery.
- the absolute pressure of purge/product gas stream is higher than the absolute pressure of the mixed gas stream on the other side of the membrane. Any pinholes in the membrane, or poor seals with respect to the membrane or other components of the system, will only allow leakage of purge/product gas into the mixed gas stream, and therefore, the purity of the product gas will not be affected as a result of such leakage.
- the absolute pressures are selected such that any leakage which may occur will only flow in the direction that does not compromise the purity of the separated product gas, also minimizing the need for critical membrane quality, and tightness of the seals within the system.
- the cross-pressure, or absolute pressure differential is very small, representing only a fraction of the absolute pressure.
- the membrane thickness can be decreased since it will not have to support the additional forces resulting from any substantial pressure differentials.
- the ability to decrease the thickness of the membrane not only enhances the system performance, but also reduces the costs thereof.
- the invention also relates to the treatment of the purge/product gas stream so that product gas can be delivered to a customer, or downstream equipment, as the situation requires.
- the purge/product gas stream exits the separation module at 15 atmospheres, and can thus be delivered downstream, at near 15 atmospheres.
- this delivery may be achieved by including a regenerative steam generator and water vapor condenser downstream of the separation module.
- the regenerative steam generator the water vapor is condensed out of the purge/product gas stream, leaving only pure product gas at the stream pressure of near 15 atmospheres.
- the regenerative steam generator is used to recycle as much of the thermal energy as possible to minimize energy needs.
- the thermal energy produced by the condensation of the water vapor stream is used in the system to heat and evaporate water introduced into the separation module at the inlet of the purge gas stream.
- this inventive example illustrates that the pure product gas is at near 15 atmospheres or five times the product gas pressure in the conventional example .
- the separation system and process can be designed so as to require less surface area, assuming more limited or lower recovery factor objectives are acceptable. If, for example, only
- the partial pressure of the product gas at the outlet of the mixed gas stream will be 3 atmospheres, as defined in the original example provided above.
- the driving force at the mixed gas stream exit is now 3 atmospheres, and therefore the average driving force has increased to 3.75 atmospheres across the entire surface area of the membrane separating the mixed gas stream and the purge gas stream.
- the surface area of the membrane needed for the separation is substantially less than when the near 100% recovery was desired.
- the cost -and volume of the separation module would also be significantly less since the average driving force is increased and less surface area is required. Nevertheless, even where the recovery requirements are less than near 100%, the overall benefits of the system remain. These include enhanced recovery factors, higher pressure pure product gas exiting from the system, as well as the minimized seal criticality.
- Figure 1 is a schematic representation of a first embodiment of the present invention illustrating a single membrane component and its inlet and outlet stream;
- Figure 2 is a schematic representation of a second embodiment of the present invention illustrating a single electrochemical membrane component, and its inlet and outlet streams;
- Figure 3 is a schematic representation of the overall process including a single membrane component and related structures, including a flow circuit of the purge gas stream;
- Figure 4(a) is a schematic flow representation showing a conventional fuel cell power system
- Figure 4(b) is a graph showing power loads on the system illustrated in Figure 4(a).
- Figure 5 is a schematic flow representation showing a fuel cell power system of the invention.
- FIG. 1 With reference to the attached drawings, there is shown a single membrane separation module, both of the ionic and electric power type, as well as a separation module in association with other components. These are shown in Figures 1 to 3 of the drawings.
- Figures 4 to 5 represent a conventional fuel cell system, and a fuel cell system of the invention, respectively, highlighting the differences and inventive aspects of the fuel cell system as described in this invention.
- FIG. 1 illustrates a separation membrane module, generally designated by reference numeral 10, comprising a gas separation membrane 12 and flow chambers 14 and 16 on each side of the membrane 12.
- the flow chamber 14 is for receiving and conveying a mixed gas stream 18, while the flow chamber 16 is for receiving and conveying a purge gas stream 20.
- the mixed gas stream flow chamber 14 has an inlet port 22 at one end and an outlet port 24 at the opposite end.
- the 16 has an inlet port 26 at one end and an outlet port 28 at its other end. It will be noted that the inlet port 22 for the mixed gas stream 18 is on the opposite side of the module 10 to the inlet port 26 for the purge gas stream 20, and that the mixed gas stream 18 and purge gas stream 20 therefore flow in opposite directions, or counter current to each other.
- the gas separation membrane 12 has a membrane surface 30 which is exposed to the mixed gas stream 18, and a membrane surface 32 which is exposed to the purge gas stream 20.
- the mixed gas stream 18 at its point of entry into the flow chamber 14 near the inlet port 22 is designated by the reference numeral 34 while the mixed gas stream exiting the mixed flow chamber 14 near the outlet port 12 is designated by the reference numeral 36.
- the reference numeral 38 represents this stream near the inlet port 26 as it enters the flow chamber 16
- the reference numeral 40 represents the stream 20, including the product, as will be described more fully below, as it exits the flow chamber 16 near the outlet port 28.
- the membrane 12 is preferably a palladium silver type membrane for hydrogen (H 2 ) gas separation.
- the membrane 12 may comprise a mixed ionic/electronic conducting ceramic membrane.
- any conventional or other type membrane that is selectively permeable to the desired product gas or liquid, whether hydrogen, oxygen, carbon dioxide, ammonia, methane or other product gas being separated from a mixed gas flow stream, would be appropriate and suitable in the circumstances.
- the membrane will, of course, be in contact with the respective streams, with the surface 30 of the membrane being in contact with the mixed gas stream, and the surface 32 of the membrane being in contact with the purge gas stream.
- Mixed gas stream 34 enters the flow chamber 14 at the inlet port 22. After passing through the flow chamber 14 it then exits as the mixed gas stream 36 through the outlet port 12.
- This mixed gas stream consists of a stream comprised of the product gas (for example hydrogen, oxygen, or other gas or liquid to be separated from the mixed gas stream) and other gases which are separated from the product gas.
- a purge gas stream 38 enters through the inlet port 26, travels through the flow chamber 16 and exits as the purge/product gas 40 at the outlet port 28.
- the purge gas stream can be water vapor or any other gas that can be easily separated from the product gas, as described below, downstream of the separation module 10. Discussed below is a particular embodiment for separating hydrogen or oxygen, as the product gas. Although these gases are discussed in this particular embodiment, other gases or liquids may also be separated from a mixed gas stream within the parameters of the present invention.
- Hydrogen is a product gas contained within the mixed gas stream 18 flowing through the flow chamber 14 of the separation module 10.
- the hydrogen reacts on the surface 30 of the membrane and is absorbed into the lattice of the membrane 12.
- the extent of the hydrogen gas in the surface is proportional to the partial pressure of hydrogen in the mixed gas stream above the membrane surface 30.
- the purge gas stream 20 flows through the flow chamber 16 such that the hydrogen partial pressure at the surface 32 of the membrane is maintained at a partial pressure less than that of the hydrogen at the surface 30 on the other side of the membrane 12. Therefore, hydrogen in the lattice near the surface 30 of the separation membrane 12 migrates through the membrane 12 to the surface 32.
- the hydrogen exits the lattice structure of the membrane 12 and enters the purge gas stream (essentially converting the purge gas stream to a purge/product gas stream) and exits as the stream 40 through the outlet port 28.
- the pressure of the purge gas stream 38 near the inlet port 26 and the purge/product gas stream 40 near the outlet port 28, as well as the flow therebetween, is maintained at a pressure greater than the pressure of the mixed gas stream 18. Furthermore, the flow rate of the purge gas stream 20 is maintained sufficiently high to effect a positive hydrogen partial pressure driving force along the entire surface of the gas separation membrane 12.
- the effect of maintaining the hydrogen partial pressure higher in the mixed gas stream 18 while maintaining the pressure of the purge gas stream 38 higher in the flow chamber 16 effectively ensures that hydrogen gas can migrate across the separation membrane 12 from the chamber 14 to the chamber 16, but other components of the mixed gas flow stream within the chamber 14 will be prevented from migrating across the separation membrane 12 even if membrane 12 has pinholes or poor seals.
- FIG. 1 have been used for corresponding elements in this Figure 2.
- the separation module shown in Figure 2 differs from that in Figure 1 by the presence of an electrode 42 between the flow chamber 16 and the separation membrane 12, and an electrode 44 between the separation membrane 12 and the flow chamber 14.
- the gas separation membrane 12 illustrated in Figure 2 is an ionic conductive membrane, such as zirconia, but other types of conductive membranes can be used as appropriate.
- the separation membrane 12 is coated with the electrodes 42 and 44, which are in contact with the purge gas stream 20 and the mixed gas stream 18 respectively.
- the electrodes 42 and 44 which are in contact with the purge gas stream 20 and the mixed gas stream 18 respectively.
- an oxygen-ion conductive membrane there is used an oxygen-ion conductive membrane, but other suitable membranes which employ negatively charged ions, or even positively charged ions, are feasible and fall within the scope of this invention.
- Mixed gas stream 18 enters through the inlet port 22 and exits through the outlet port 24 while purge gas stream 20 enters the chamber 16 through the inlet port 26 and exits through the outlet port 28. Once more, the mixed gas stream 18 and purge gas stream 20 flow counter current to each other.
- the pressure of the purge gas stream 20 is maintained at a pressure, which is approximately equal to the desired pure product delivery pressure.
- the pure product in this case hydrogen, is delivered downstream of the separation module at a desired pressure, for example 15 atmospheres, and the pressure of the purge gas is maintained at this pure product delivery pressure.
- the pressure of the purge gas stream 20 must be slightly greater than the mixed gas stream 18 in the chamber 14 in order to minimize the impact of pinholes or poor seals. If the structure has good seals between the components and the membrane, the pressure criteria can be somewhat less stringent .
- Electrons 46 enter the electrode 42 and migrate to the reaction site 48 within the electrode 42.
- the purge gas stream consists of water vapor, and this water vapor enters the reaction site 48 with the electrons 46 to form hydrogen, identified by numeral 50, and oxygen ions, identified by numeral 52.
- the oxygen ion 52 enters the lattice structure of the separation membrane 12. Increased concentrations of oxygens ions 52 near the reaction site 48 force the oxygen ions 52 to flow to a reaction site 54 contained within the electrode 44.
- Hydrogen, identified by reference numeral 56 from the mixed gas stream 18 within the chamber 14 enters the reaction site 54 and reacts with the oxygen ions 52.
- This reaction produces water, identified by reference numeral 58, and the water vaporizes and enters the mixed gas stream 18 in the chamber 14, at the same time releasing electrons, identified by the reference numeral 60, which leave the electrode 44 and flow through an external circuit 62 , ultimately returning to the electrode 42 to complete the electric circuit.
- the driving force to separate the hydrogen is primarily the electrical power, but maintaining a positive partial pressure driving force in addition to this electrical power can minimize the amount of energy required to drive the system.
- the purge gas flow rate can be decreased because the electrical driving force can move hydrogen from a low partial pressure mixed gas stream 18 to a higher partial pressure of the purge gas 20 in the chamber 16. Therefore, in this embodiment, unlike that shown in Figure 1, it is not necessary that the partial pressure of the hydrogen within the mixed gas stream 18 is higher than the partial pressure of the hydrogen within the purge gas stream 20 along the length of the gas separation membrane 12.
- oxygen in the mixed gas stream could react at the reaction site 54 creating oxygen ions 52 and electrons.
- the electrons 46 and 60 would therefore have flow directions opposite to that shown with respect to the situation where hydrogen is being separated from the mixed gas stream, and the oxygen ions 52 would also flow in the opposite direction.
- the oxygen ions 52 would recombine with the electrons 46 returning from the external circuit 62 to form pure oxygen that would evolve into the purge gas stream, which may typically be comprised of water vapor.
- the inventive counter- flow purge gas has the same benefits in this case as in the example described above using hydrogen.
- FIG 3 shows overall a schematic diagram of a gas purification and separation system.
- reference numerals used in Figure 1 and 2 have been used for corresponding structures and elements shown in Figure 3.
- a mixed gas stream 18 enters through inlet port 22 as stream 34, and becomes a depleted mixed gas stream 36 near the outlet port 24.
- Purge gas stream 20 enters the inlet 26 as stream 38, and flows in counter-current direction to the mixed gas stream 18.
- the purge gas 20 exits through the outlet port 28 as the purge/product gas stream 40.
- the respective flows of the mixed gas stream and the purge gas stream 18 and 20 are isolated by the gas separation membrane 12. This is achieved in accordance with the description above with respect to Figures 1 and 2.
- the purge/product gas stream 40 flows to a regenerative steam generator 68 where heat is removed from the stream 40 and the water vapor in the stream 40 is condensed. After passing through the steam generator 68, the stream enters a heat removal final stage condenser 70 followed by a liquid/gas separator 72. In the liquid/gas separator 72, the pure product gas stream 76 is isolated from the condensed water, identified by reference numeral 74. The pure product gas stream 76 is removed from the stream for use or delivery to a downstream site.
- the water 74 flows through a pump 78 and back into the regenerative steam generator 68, where the liquid water 74 is converted to water vapor by heat transferred from condensing water from the stream 40. If a refrigerant type purge gas is used, an orifice 80 is placed between the pump 78 and the steam generator 68. The water vapor is further heated in a super heater 82 and becomes the purge gas stream 38 that enters the inlet port 26 of the separation module 10. Additional water may be added to the separator 72, if needed.
- Figure 4 shows a conventional fuel cell power system
- Figure 5 shows the fuel cell system of the invention.
- FIG 4(a) there is shown an under-oxidized burner/reformer, or fuel processor, 110.
- the fuel processor 110 receives, for example, hydrocarbon fuels such as methanol, ethanol, diesel and the like, mixes and combusts them so as to produce a hydrogen rich mixed gas product stream.
- the hydrocarbon fuel is introduced through fuel inlet 112, and is conveyed along the fuel line 114, assisted by pump 116.
- a valve 118 is located in the fuel line 114 so as to control the flow of fuel therethrough.
- the fuel line 114 enters the fuel processor 110.
- An air inlet 120 is provided in a turbo generator 122 and the air is forced along air line 124 to the fuel processor 110. Water vapor may be incorporated into the air from line 154.
- the air from air line 124 and the fuel from fuel line 114 are combined, reacted and combusted, preferably in the presence of water, to produce the hydrogen/mixed gas product which exits the fuel processor 110 through the product line 126.
- the product line 126 conveys the hydroge /mixed gas product through downstream shift reactors 170 and 172, heat recovery heat exchangers 173 and 175, and through carbon monoxide polishing unit 176 and eventually to a fuel cell 128 where it is combined with air pumped, through air line 130, the air in air line 130 having as its source the turbo generator 122.
- the fuel cell 128 has an anode exhaust line 132 and a cathode exhaust line 134, each of which connects to a condenser 136 and 138 respectively.
- the condenser 136 connects to a separator 140 while the condenser 138 connects to separator 142, the separators 140 and 142 extracting water from the mixture, with the water being drained off through water lines 144 and 146 respectively.
- the water lines 144 and 146 consolidate into a single water line 148, which conveys the water to steam generator 150. Some of the water, however, is tapped off through water line 152 for introduction into the fuel processor 110, where it is mixed with the hot product gas from the combustion chamber.
- the water reaching the steam generator 150 through the consolidated water line 148 is heated by recovered heat from heat exchangers 173 and 175, and resulting water vapor is supplied through water vapor line 154 to the air line 124, where air and water vapor mix and are subsequently introduced to the fuel processor 110, as described above.
- Each separator 140 and 142 is connected to a combuster 156 by product residue lines 158 and 160, and the product residues are burned in the combuster 156 to produce heat and energy which flow through the line 162 and feeds the turbo generator 122.
- the heat and energy contained within the product flowing through line 162 is processed by the turbo generator and is used to power a generator 164.
- the combuster gas is exhausted through the exhaust line 166 after the turbo generator 122.
- the fuel processor 110 there is a combustion chamber 168 where the air, fuel and water mixture are combusted, and where temperatures reach approximately 2700°F.
- water from line 152 is introduced to quench the product gas down to approximately 700°F.
- Downstream there is provided a high temperature shift region 170 and a low temperature shift region 172, where carbon monoxide is reacted with water to form additional hydrogen and carbon dioxide.
- These shift reactors assist in ridding the system of undesired byproducts of combustion.
- the fuel processor process further comprises a zinc oxide bed 174 where sulfur is extracted from the combusted mixture.
- the product gas exiting the sulfur bed 174 and high temperature shift 170 is cooled by heat exchanger 173 in preparation for entering low temperature shift reactor 172.
- the gas is also cooled, after the low temperature shift reactor 172, by heat exchanger 171. Finally, the carbon monoxide is reduced in the carbon monoxide polishing unit 176 to levels acceptable to the fuel cell 128.
- the hydrogen/mixed gas product in the product line 126 has a fairly low concentration of hydrogen, and may typically comprise only 30% to 40% of the total product gas.
- the combuster 156 receives residual products from the fuel cell 128 via the condensers and separators, and these are combusted so that the product traveling through line 162 are at elevated temperatures.
- the temperature of these products in line 162 may reach approximately 800°F, significantly lower than temperatures reached in corresponding structures of the fuel cell system of the invention, as will be described below.
- FIG. 5 is a diagrammatic flow chart illustrating the components and system of the invention.
- the fuel cell system of the invention offers many advantages for increased efficiency and output, requiring an under-oxidized burner having a nominal or lower power rating than in conventional systems.
- the acceptability of the lower power rating is due to the capacity of the system of the invention to use and produce hydrogen fuels with greater efficiency, and to store hydrogen in a reservoir for subsequent use.
- the under-oxidized burner producing the hydrogen need not operate at erratic high peak power requirements, but can typically operate at more consistent and steady states yet still provide sufficient hydrogen to enable the system to operate at peak power levels of conventional systems.
- an under- oxidized burner/reformer 210 including, generally, a combustion chamber 212.
- the inventive system integrates an innovative purification module 214 downstream of the combustion chamber 212.
- the purification module 214 has a mixed gas side 213 and a purge/product gas side 233.
- the mixed gas side 213 flows in counter flow direction to the purge/product gas side 233.
- the under-oxidized burner 210 is supplied with air, fuel and water which are ignited and thoroughly mixed to produce hydrogen, carbon monoxide and water.
- a fuel inlet 216 is provided and supplies a fuel line 218 which is pumped by a pump-compressor 220 to the combustion chamber 212.
- a valve 222 is provided for controlling the flow of fuel through the fuel line 218.
- the fuel may comprise hydrocarbon fuels, such as methanol, ethanol, diesel or other appropriate fuels.
- An air inlet 224 provides air to a turbo generator 226 and air line 228 conveys the air from the turbo generator 226 to the combustion chamber 212 of the burner 210.
- the air flowing through air line 228 may be supplemented with steam, provided by steam line 230 emanating from another source within the fuel cell system, as will be described further below.
- the steam line 230 has a branch line 232 which provides steam to the purification module 214.
- the burner 210 has located within the combustion chamber 212 structures for thoroughly mixing the air and fuel, received through lines 228 and 218 respectively. These structures typically terminate in an injector nozzle where a thoroughly mixed fuel and air mixture is discharged into the combustion chamber for ignition.
- the mixing structures and injector nozzles are fully described in some of Applicant's other patents, including U.S. Patent Nos . 5,207,185; 5,299,536; 5,441,546; 5,437,123; 5,529,484; 5,546,701, and well as applications USSN 471,404 and USSN 742,383, all of which are incorporated herein by reference.
- the mixed gas stream After the combustion process within the burner 210 has converted the hydrocarbon fuels into hydrogen and carbon monoxide mixed gas stream, the mixed gas stream enters the purification module 214 and flows through the mixed gas side 213. Steam from line 232 enters the purification module 214 and flows through purge/product gas side 233. The mixed gas flow 213 and purge/product gas flow 233 flow in counter flow relationship to each other. Hydrogen from the mixed gas flow 213 is transferred into the purge/product gas flow 233 as described for Figures 1 and 2. Recovery factors of 70 to 90% are preferred.
- the hydrogen/steam mixture exits from the burner 210 through the water/hydrogen line 236 where it is conveyed to a condenser 238 which can also be a recuperative condenser as described in Figure 3.
- a final condenser 240 is provided, the condenser 238 and final condenser 240 constituting a water condenser train.
- the condensers convert the hydrogen/steam into hydrogen/liquid water mixture and a separator 242 is provided for separating and isolating these two components .
- the hydrogen exits the separator 242 through the hydrogen line 244, while the water exits the separator 242 through a water line 246.
- a particular advantage of the invention is that the hydrogen line 244 contains near 100% hydrogen gas, as compared with conventional systems where only 30% to 40% of hydrogen is contained in a hydrogen-product mixture fed to a fuel cell.
- the hydrogen line 244 can be directed either through line 248 to a fuel cell module 250, or through line 252 to a hydrogen storage tank 254.
- the amount of hydrogen gas entering either one of lines 248 and 252 respectively will depend upon the load exerted on the fuel cell 250. If all the hydrogen gas from the separator 242 is needed to meet current load requirements of the fuel cell 250, all of the hydrogen produced will go through the line 248 to the fuel cell 250.
- a cathode exhaust line 260 is provided and conveys the cathode exhaust products from the fuel cell to a catalytic combuster 262.
- the catalytic combuster 262 is also provided, through feed line 264, with depleted gas products from the burner 210. These depleted gas products from the mixed gas side 213 of the purification module include hydrogen gas.
- the catalytic combuster 262 is provided with compressed air through line 266 from the turbo generator 226. The catalytic combuster 262 burns the products received from the burner 210, namely the depleted gas, as well as the cathode exhaust products provided from the fuel cell through line 260.
- the catalytic combuster product gases exit through line 270, at temperatures typically ranging between 1200°F and 1800°F which is, once more, a substantially higher temperature than that produced by conventional systems. As will be recalled with reference to Figure 4(a), the combuster burns products and raises temperatures to approximately 800°F.
- the line 270 supplies the turbo generator 226, and the energy, at least in part, is used to drive the generator 272.
- the line 270, conveying products under pressure, is transmitted to the expander portion 226a of the turbo-generator and the pressure and heat drives the expander.
- the expander outlet gas flows through line 291 to recuperative steam generator 284, condenser 288, and liquid/gas separator 278.
- Water from separator 278 is combined with water from separator 242 and enters pump 286. Water from the pump 286 flows in the line 282 through control valve 289 to steam generator 284. The steam is then sent to line 230.
- the energy, at least in part, used for converting the water to steam in the steam generator 284 is derived from the exhaust product from the turbo-generator 226, which, unlike, conventional systems, is not discharged from the system, but is conveyed through line 291 to the steam generator 284. If additional energy is needed, the recovery energy from condenser 238 can be integrated with the heat supplied by line 291 to generator 284. This excess heat and energy is thus used in the inventive system, compared to conventional equipment where it is discharged. The present system is thus more efficient in utilizing all energy sources, resulting in less waste and lower fuel requirements for the amount of energy produced.
- the steam produced in the steam generator 284 exits through steam line 230, and is fed into the air line 228 where the air and steam combination is transported to the burner 210 and fuel cell 250.
- a steam branch line 232 is provided whereby steam from the steam generator 284 is introduced to the inventive purification module 214.
- the system of the invention has several significant advantages compared to conventional fuel cell systems.
- One difference relates to the start up times of conventional systems versus the system of the invention.
- start up requirements may take at least 2 minutes before hydrogen production is increased to meet the load requirements placed on the fuel cell.
- a typical profile of energy use is highly erratic, with demand for power alternating between high and low points.
- Figure 4(b) of the drawings shows a graph of typical profile uses of energy in conventional systems .
- the system surges as it runs, as load requirements increase or decrease, resulting in higher production of hydrogen.
- the system must be designed to cope with such surging, and to deal with the great variations in demand.
- the system of the invention incorporates a hydrogen storage tank 254.
- the ability of the inventive system to draw on a hydrogen reserve during peak power surges facilitates another particularly advantageous feature of the invention, namely, that the fuel processor can be designed to put out less hydrogen at its peak performance. Since conventional systems with 30 to 40% hydrogen streams have not had the ability to store hydrogen, it has been necessary to provide a fuel processor which is able to output the necessary hydrogen at levels corresponding generally to the peak power requirements. In fact, peak power demands can, in typical systems, be 50kW or more even though the average load may only be 15kW. The net effect of the ability to store hydrogen is that, instead of demands being made on the fuel cell and reformed, the system resorts to stored hydrogen to compensate for the lower levels of production during peak demand.
- the system of the invention therefore permits the fairly regular and consistent output of hydrogen from its fuel processor, whether or not it is needed.
- the hydrogen storage tank comes into operation and constitutes a reservoir of the hydrogen to be drawn upon during peak demand when requirements exceed the output capacity of the fuel processor. Therefore, the fuel processor and/or reformer can be appropriately sized to produce a base load. Apparatus able to produce 15kW instead 50kW can be used not only lowering the cost of the overall system, but also making the net amount of hydrogen produced for a given amount of fuel much more efficient. The actual size of the under-oxidized burner and reformer can also be reduced influencing space saving factors.
- the burner and fuel cell can therefore operate consistently at near maximum efficiency, at the same time having some reserve capacity, due to the ability to store excess hydrogen gas which is not used.
- the fuel processor can be designed to produce hydrogen at steady levels, allowing structures which are 30% or less than the size of fuel cells and/or reformers which need be used in conventional systems.
- the system of the invention is also superior to conventional systems in that it produces substantially higher concentrations of hydrogen.
- the hydrogen/mixed gas in product line 126 contains hydrogen concentrations comprising 30-40% of the mixture.
- hydrogen exiting the burner 210 shown in Figure 5 is near 100% of the mixture. It is extremely difficult to efficiently store the hydrogen/mixed gas combination, where hydrogen concentration is as low as 30-40%. This problem does not arise in the system of the present invention, owing to the near purity of the hydrogen within the mixture exiting the burner.
- the high purity hydrogen also improves the effectiveness of the fuel cell 250 which results in smaller, lower cost fuel cell stack.
- the system of the invention also has the ability to operate the turbo generator at higher temperatures, increasing its efficiency of operation.
- the fuel processor 110 used in conventional systems must of necessity include certain shift processors in the combustion apparatus in order to get rid of undesirable components such as carbon monoxide. These shift reactors result in a substantial reduction in the thermal content, particularly from the high temperature shift region to the low temperature shift region in the fuel processor.
- the system of the invention separates the hydrogen gases from the remainder or depleted gas.
- the hot depleted gas from the purification module 214 is sent directly to the catalytic combustor 262 to produce heat.
- the system allows temperatures as high as 1200° - 1800°F in this context, which not only feeds the expander and generator, but also results in a residual heat and energy which is not exhausted, but recycled to a heat recovery steam generator where water in the system is converted to steam for further use in the hydrogen production process.
- turbo-generator performance increases and the system puts out more energy for each unit of fuel .
- the system of the invention also reduces the complexity of the fuel processing system and the fuel cell system.
- shift reactors 170 and 170 are conventional fuel processing systems.
- the mixed gas side of the purification module 214 can be designed to integrate shift catalysts functions and therefore, the shift reactors 170 and
- steam purging in the separation module is able to provide greater than 85% recovery of hydrogen gas within the mixed stream, supply hydrogen gas to the fuel cell at high pressure, and, as a result of the pressure differentials on each side of the membrane within the module, minimize any adverse effects resulting from pinholes or poor seals, thus making these seals less critical.
- the invention does not require shift catalyst beds and/or sulphur removal beds, necessary in conventional systems to deal with the fuel processes production of undesirable components. Since these undesirable components are not produced in significant quantities, higher temperatures can be maintained within the system, increasing efficiency.
- a typical start up cycle of the fuel cell system of the invention involves a battery spin of the turbo generator to start air flow to the fuel cell and hydrogen is released from the storage tank 254. The time that is required for this start is very short. Air flows to the under-oxidized burner 210 and catalytic combuster 262, which are thermal processes, and therefore, typically require longer, more gradual start up cycles. The fuel flow to the under-oxidized burner 210 starts, and a spark plug within the burner is activated to ignite the mixture within the combustion chamber 212. The burner 210 is operated at a high capacity and high stoichiometric (SR) ratios.
- SR stoichiometric
- the combination of heat to the turbo generator 226 and hydrogen from the storage tank 254 to the fuel cell 250 provides instant vehicle movement, or the instant necessary power output for the particular application.
- steam is formed providing purge gas through line 233 to the hydrogen concentration module, and the system reaches an operating temperature so as to extract hydrogen from the mixed gas stream 213.
- the purification module 214 begins to extract hydrogen from the mixed gas stream 213 and begins to provide hydrogen to the fuel cell 250.
- the fuel cell 250 load decreases, some hydrogen begins to be added to the storage tank 254.
- the hydrogen storage cycle wherein hydrogen is diverted to the storage tank, recharges the hydrogen storage tank, as requirements demand.
- the process gas purification module and the fuel cell system provide effective and efficient utilization of hydrogen from hydrocarbon fuels.
- the under-oxidized burner of the invention in association with the gas purification module, is designed so as to extract optimal quantities of hydrogen from the hydrocarbon fuels. This is achieved by controlling the partial pressure of hydrogen (or other gas being extracted from a mixed gas stream) , on each side of the membrane in a purification module, and by manipulating the overall pressure and partial pressures of the streams flowing on each side of the membrane.
- the invention goes one step further in that, not only are optimal hydrogen concentrations extracted from the hydrocarbon fuels, but also the actual utilization of the hydrogen following this process is optimized. Higher temperatures and pressures are used more effectively for delivery of hydrogen to the fuel cell and for the production of electricity.
- the fuel processor can be smaller, and operated at more consistent levels since fuel cell loads draw not only on the hydrogen production from the fuel processor, but also on a storage tank which is filled and recharged during lower load periods .
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Combustion & Propulsion (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IL13836799A IL138367A0 (en) | 1998-03-12 | 1999-03-10 | Process gas purification and fuel cell system |
JP2000535441A JP2002505943A (en) | 1998-03-12 | 1999-03-10 | Process gas purification and fuel cell system |
CA002322871A CA2322871A1 (en) | 1998-03-12 | 1999-03-10 | Process gas purification and fuel cell system |
AU30762/99A AU3076299A (en) | 1998-03-12 | 1999-03-10 | Process gas purification and fuel cell system |
KR1020007009904A KR20010041687A (en) | 1998-03-12 | 1999-03-10 | Process gas purification and fuel cell system |
EP99912376A EP1062024A2 (en) | 1998-03-12 | 1999-03-10 | Process gas purification and fuel cell system |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US7773398P | 1998-03-12 | 1998-03-12 | |
US60/077,733 | 1998-03-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1999046032A2 true WO1999046032A2 (en) | 1999-09-16 |
WO1999046032A3 WO1999046032A3 (en) | 2000-02-10 |
Family
ID=22139747
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/005238 WO1999046032A2 (en) | 1998-03-12 | 1999-03-10 | Process gas purification and fuel cell system |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1062024A2 (en) |
JP (1) | JP2002505943A (en) |
KR (1) | KR20010041687A (en) |
CN (1) | CN1298319A (en) |
AU (1) | AU3076299A (en) |
CA (1) | CA2322871A1 (en) |
IL (1) | IL138367A0 (en) |
WO (1) | WO1999046032A2 (en) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000014009A1 (en) * | 1998-09-08 | 2000-03-16 | Proton Energy Systems, Inc. | Electrochemical gas purifier |
US6329091B1 (en) | 2000-04-14 | 2001-12-11 | Ford Global Technologies, Inc. | Fuel reformer system for a fuel cell |
US6350394B1 (en) | 1996-12-23 | 2002-02-26 | Egt Developments, Llc | Method and apparatus for total energy fuel conversion systems |
DE10053986A1 (en) * | 2000-10-31 | 2002-05-08 | Forschungszentrum Juelich Gmbh | Introducing and removing hydrogen using an electrically contacted proton conductor, comprises applying a current to the conductor so that protons are generated at an anode and recombining the protons at a cathode to form hydrogen |
FR2820549A1 (en) * | 2001-02-08 | 2002-08-09 | Inst Francais Du Petrole | METHOD AND DEVICE FOR PRODUCING ELECTRICITY IN A FUEL CELL BY OXIDATION OF HYDROCARBONS FOLLOWED BY PARTICLE FILTRATION |
EP1231663A1 (en) * | 2001-02-12 | 2002-08-14 | Delphi Technologies, Inc. | Method and apparatus for gas purification in energy conversion systems |
JP2003034506A (en) * | 2001-07-23 | 2003-02-07 | Toyota Motor Corp | Hydrogen extractor |
JP2003095608A (en) * | 2001-09-21 | 2003-04-03 | Toyota Motor Corp | Start-up method of apparatus for generating hydrogen having hydrogen separation membrane |
US6572837B1 (en) | 2000-07-19 | 2003-06-03 | Ballard Power Systems Inc. | Fuel processing system |
GB2383186A (en) * | 2001-11-24 | 2003-06-18 | Bosch Gmbh Robert | Fuel - cell system |
WO2004004043A1 (en) * | 2002-07-01 | 2004-01-08 | Sfc Smart Fuel Cell Ag | Fluid separating device |
WO2004079846A2 (en) * | 2003-03-05 | 2004-09-16 | Daimlerchrysler Ag | Fuel cell system comprising at least one fuel cell and one gas generating system |
US7060382B2 (en) | 2003-05-15 | 2006-06-13 | Fuelcell Energy, Inc. | Fuel cell system with recycle of anode exhaust gas |
EP2017222A1 (en) | 2007-07-20 | 2009-01-21 | Ifp | New method of purifying hydrogen using a combination of separation units on membranes |
US7537738B2 (en) | 2003-01-21 | 2009-05-26 | Gm Global Technology Operations, Inc. | Fuel processing system having a membrane separator |
US7862938B2 (en) | 2007-02-05 | 2011-01-04 | Fuelcell Energy, Inc. | Integrated fuel cell and heat engine hybrid system for high efficiency power generation |
US8015808B2 (en) | 2001-01-09 | 2011-09-13 | G4 Insights Inc. | Power plant with energy recovery from fuel storage |
US8541637B2 (en) | 2009-03-05 | 2013-09-24 | G4 Insights Inc. | Process and system for thermochemical conversion of biomass |
CN108373233A (en) * | 2018-01-25 | 2018-08-07 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of organic amine wastewater |
US10190066B2 (en) | 2009-11-18 | 2019-01-29 | G4 Insights Inc. | Method and system for biomass hydrogasification |
US10653995B2 (en) | 2009-11-18 | 2020-05-19 | G4 Insights Inc. | Sorption enhanced methanation of biomass |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2352626A1 (en) | 2001-07-12 | 2003-01-12 | Co2 Solution Inc. | Coupling for linking a hydrogen fuel cell to an enzyme bioreactor for processing and sequestering co2 |
CA2353307A1 (en) | 2001-07-13 | 2003-01-13 | Carmen Parent | Device and procedure for processing gaseous effluents |
CA2405635A1 (en) | 2002-09-27 | 2004-03-27 | C02 Solution Inc. | A process and a plant for the production of useful carbonated species and for the recycling of carbon dioxide emissions from power plants |
KR100788195B1 (en) * | 2006-05-26 | 2007-12-26 | 엘지전자 주식회사 | Fuel cell system |
CN101335360B (en) * | 2007-06-29 | 2010-05-19 | 中国科学院金属研究所 | Hydrogen continuous transmission device |
US7837765B2 (en) * | 2007-12-12 | 2010-11-23 | Idatech, Llc | Systems and methods for supplying auxiliary fuel streams during intermittent byproduct discharge from pressure swing adsorption assemblies |
JP5743639B2 (en) * | 2011-03-29 | 2015-07-01 | 新日鉄住金エンジニアリング株式会社 | Carbon dioxide gas separation system |
CN113713643B (en) * | 2021-08-25 | 2023-09-26 | 一汽解放汽车有限公司 | Tail exhaust mixing dilution device of hydrogen fuel cell and hydrogen fuel cell |
CN114622231A (en) * | 2022-03-31 | 2022-06-14 | 中国科学技术大学先进技术研究院 | Ceramic hydrogen pump and hydrogen purification device of hydrogen-oxygen fuel cell |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB990131A (en) * | 1962-07-26 | 1965-04-28 | Engelhard Ind Inc | Method for hydrogen diffusion |
EP0615949A2 (en) * | 1993-03-16 | 1994-09-21 | Tokyo Gas Co., Ltd. | Hydrogen producing apparatus |
GB2283235A (en) * | 1993-10-30 | 1995-05-03 | Rolls Royce & Ass | A fuel processing system for generating hydrogen |
US5562754A (en) * | 1995-06-07 | 1996-10-08 | Air Products And Chemicals, Inc. | Production of oxygen by ion transport membranes with steam utilization |
US5612012A (en) * | 1994-06-08 | 1997-03-18 | Ngk Insulators, Ltd. | Method for removing carbon monoxide from reformed gas |
-
1999
- 1999-03-10 EP EP99912376A patent/EP1062024A2/en not_active Withdrawn
- 1999-03-10 WO PCT/US1999/005238 patent/WO1999046032A2/en not_active Application Discontinuation
- 1999-03-10 JP JP2000535441A patent/JP2002505943A/en not_active Withdrawn
- 1999-03-10 KR KR1020007009904A patent/KR20010041687A/en not_active Application Discontinuation
- 1999-03-10 AU AU30762/99A patent/AU3076299A/en not_active Abandoned
- 1999-03-10 IL IL13836799A patent/IL138367A0/en unknown
- 1999-03-10 CA CA002322871A patent/CA2322871A1/en not_active Abandoned
- 1999-03-10 CN CN99805253A patent/CN1298319A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB990131A (en) * | 1962-07-26 | 1965-04-28 | Engelhard Ind Inc | Method for hydrogen diffusion |
EP0615949A2 (en) * | 1993-03-16 | 1994-09-21 | Tokyo Gas Co., Ltd. | Hydrogen producing apparatus |
GB2283235A (en) * | 1993-10-30 | 1995-05-03 | Rolls Royce & Ass | A fuel processing system for generating hydrogen |
US5612012A (en) * | 1994-06-08 | 1997-03-18 | Ngk Insulators, Ltd. | Method for removing carbon monoxide from reformed gas |
US5562754A (en) * | 1995-06-07 | 1996-10-08 | Air Products And Chemicals, Inc. | Production of oxygen by ion transport membranes with steam utilization |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6350394B1 (en) | 1996-12-23 | 2002-02-26 | Egt Developments, Llc | Method and apparatus for total energy fuel conversion systems |
US6734331B2 (en) | 1996-12-23 | 2004-05-11 | Egt Developments, Llc | Process for producing olefins and diolefins |
US6168705B1 (en) | 1998-09-08 | 2001-01-02 | Proton Energy Systems | Electrochemical gas purifier |
WO2000014009A1 (en) * | 1998-09-08 | 2000-03-16 | Proton Energy Systems, Inc. | Electrochemical gas purifier |
US6329091B1 (en) | 2000-04-14 | 2001-12-11 | Ford Global Technologies, Inc. | Fuel reformer system for a fuel cell |
US6572837B1 (en) | 2000-07-19 | 2003-06-03 | Ballard Power Systems Inc. | Fuel processing system |
DE10053986A1 (en) * | 2000-10-31 | 2002-05-08 | Forschungszentrum Juelich Gmbh | Introducing and removing hydrogen using an electrically contacted proton conductor, comprises applying a current to the conductor so that protons are generated at an anode and recombining the protons at a cathode to form hydrogen |
US8015808B2 (en) | 2001-01-09 | 2011-09-13 | G4 Insights Inc. | Power plant with energy recovery from fuel storage |
EP1231666A1 (en) * | 2001-02-08 | 2002-08-14 | Institut Francais Du Petrole | Method and device for electricity production in a fuel cell by the oxidation of hydrocarbons followed by a filtration of particles |
US6824902B2 (en) | 2001-02-08 | 2004-11-30 | Institut Francais Du Petrole | Process and device for production of electricity in a fuel cell by oxidation of hydrocarbons followed by a filtration of particles |
FR2820549A1 (en) * | 2001-02-08 | 2002-08-09 | Inst Francais Du Petrole | METHOD AND DEVICE FOR PRODUCING ELECTRICITY IN A FUEL CELL BY OXIDATION OF HYDROCARBONS FOLLOWED BY PARTICLE FILTRATION |
EP1231663A1 (en) * | 2001-02-12 | 2002-08-14 | Delphi Technologies, Inc. | Method and apparatus for gas purification in energy conversion systems |
US7037615B2 (en) | 2001-02-12 | 2006-05-02 | Delphi Technologies, Inc. | Trapping method and system for energy conversion devices |
JP2003034506A (en) * | 2001-07-23 | 2003-02-07 | Toyota Motor Corp | Hydrogen extractor |
JP2003095608A (en) * | 2001-09-21 | 2003-04-03 | Toyota Motor Corp | Start-up method of apparatus for generating hydrogen having hydrogen separation membrane |
GB2383186B (en) * | 2001-11-24 | 2004-01-28 | Bosch Gmbh Robert | Fuel - cell system |
GB2383186A (en) * | 2001-11-24 | 2003-06-18 | Bosch Gmbh Robert | Fuel - cell system |
WO2004004043A1 (en) * | 2002-07-01 | 2004-01-08 | Sfc Smart Fuel Cell Ag | Fluid separating device |
EP1383191A1 (en) * | 2002-07-01 | 2004-01-21 | SFC Smart Fuel Cell AG | Fluid separation apparatus |
US7572323B2 (en) | 2002-07-01 | 2009-08-11 | Sfc Smart Fuel Cell Ag | Fluid separating device |
US7537738B2 (en) | 2003-01-21 | 2009-05-26 | Gm Global Technology Operations, Inc. | Fuel processing system having a membrane separator |
WO2004079846A2 (en) * | 2003-03-05 | 2004-09-16 | Daimlerchrysler Ag | Fuel cell system comprising at least one fuel cell and one gas generating system |
WO2004079846A3 (en) * | 2003-03-05 | 2005-06-30 | Daimler Chrysler Ag | Fuel cell system comprising at least one fuel cell and one gas generating system |
US7060382B2 (en) | 2003-05-15 | 2006-06-13 | Fuelcell Energy, Inc. | Fuel cell system with recycle of anode exhaust gas |
US8815462B2 (en) | 2007-02-05 | 2014-08-26 | Fuelcell Energy, Inc. | Fuel cell power production system with an integrated hydrogen utilization device |
US7862938B2 (en) | 2007-02-05 | 2011-01-04 | Fuelcell Energy, Inc. | Integrated fuel cell and heat engine hybrid system for high efficiency power generation |
EP2017222A1 (en) | 2007-07-20 | 2009-01-21 | Ifp | New method of purifying hydrogen using a combination of separation units on membranes |
US8541637B2 (en) | 2009-03-05 | 2013-09-24 | G4 Insights Inc. | Process and system for thermochemical conversion of biomass |
US10190066B2 (en) | 2009-11-18 | 2019-01-29 | G4 Insights Inc. | Method and system for biomass hydrogasification |
US10653995B2 (en) | 2009-11-18 | 2020-05-19 | G4 Insights Inc. | Sorption enhanced methanation of biomass |
CN108373233A (en) * | 2018-01-25 | 2018-08-07 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of organic amine wastewater |
Also Published As
Publication number | Publication date |
---|---|
AU3076299A (en) | 1999-09-27 |
WO1999046032A3 (en) | 2000-02-10 |
CA2322871A1 (en) | 1999-09-16 |
IL138367A0 (en) | 2001-10-31 |
KR20010041687A (en) | 2001-05-25 |
EP1062024A2 (en) | 2000-12-27 |
CN1298319A (en) | 2001-06-06 |
JP2002505943A (en) | 2002-02-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO1999046032A2 (en) | Process gas purification and fuel cell system | |
US7285350B2 (en) | Enhanced solid oxide fuel cell systems | |
KR101713344B1 (en) | High-efficiency dual-stack molten carbonate fuel cell system | |
US6458478B1 (en) | Thermoelectric reformer fuel cell process and system | |
RU2199172C2 (en) | Method for generating electrical energy from natural gas using solid oxyl fuel cell | |
US7045232B1 (en) | Fuel cell system and method for producing electric energy using a fuel cell system | |
US20090136799A1 (en) | Fuel cell system and method for generating electrical energy using a fuel cell system | |
JP3640905B2 (en) | FUEL CELL DEVICE AND METHOD OF OPERATING FUEL CELL DEVICE | |
EP1241723B1 (en) | Water recovery for a fuel cell system | |
US5208113A (en) | Power generation method using molten carbonate fuel cells | |
WO2007078277A2 (en) | Power plant with membrane water gas shift reactor system | |
EP1468463A1 (en) | Desulfurisation of fuel | |
US20130130134A1 (en) | Solid oxide fuel cell steam reforming power system | |
WO2002015309A2 (en) | Electrochemical fuel depletion means for high temperature fuel cell generators | |
US6124050A (en) | Process for operating a high temperature fuel cell installation, and high temperature fuel cell installation | |
JPH05129029A (en) | Power generation system formed by using fuel cell | |
WO2002015310A2 (en) | Segregated exhaust fuel solid fuel cell generator | |
KR20020056123A (en) | Humidifier for fuel cell | |
JP7197374B2 (en) | Hydrogen production system | |
JPH03216964A (en) | Power generating method for molten carbonate fuel cell | |
MXPA00008835A (en) | Process gas purification and fuel cell system | |
JPH03236166A (en) | Power generating method for molten carbonate fuel cell | |
JPS63141268A (en) | Generating unit for natural-gas reformed molten carbonate type fuel cell | |
JPH0821412B2 (en) | Fuel cell power generation method | |
JPH04206158A (en) | Separation-recovery of carbon dioxide by use of molten carbonate type fuel cell and device thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 99805253.1 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE 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 MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
AK | Designated states |
Kind code of ref document: A3 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE 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 MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A3 Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
ENP | Entry into the national phase |
Ref document number: 2322871 Country of ref document: CA Ref document number: 2322871 Country of ref document: CA Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020007009904 Country of ref document: KR Ref document number: IN/PCT/2000/00372/MU Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2000/008835 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 138367 Country of ref document: IL |
|
WWE | Wipo information: entry into national phase |
Ref document number: 506844 Country of ref document: NZ |
|
ENP | Entry into the national phase |
Ref document number: 2000 535441 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 30762/99 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1999912376 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1999912376 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 1020007009904 Country of ref document: KR |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1999912376 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1020007009904 Country of ref document: KR |