EP1294637A2 - Generation d'electricite avec un reacteur a membrane a echange thermique - Google Patents
Generation d'electricite avec un reacteur a membrane a echange thermiqueInfo
- Publication number
- EP1294637A2 EP1294637A2 EP01946649A EP01946649A EP1294637A2 EP 1294637 A2 EP1294637 A2 EP 1294637A2 EP 01946649 A EP01946649 A EP 01946649A EP 01946649 A EP01946649 A EP 01946649A EP 1294637 A2 EP1294637 A2 EP 1294637A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- membrane
- reactor
- hydrogen
- combustion
- reforming
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 158
- 238000010248 power generation Methods 0.000 title abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 85
- 239000001257 hydrogen Substances 0.000 claims abstract description 84
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000002485 combustion reaction Methods 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 48
- 229910001868 water Inorganic materials 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 20
- 238000006057 reforming reaction Methods 0.000 claims abstract description 17
- 238000000629 steam reforming Methods 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 51
- 238000002407 reforming Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 150000002739 metals Chemical class 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 230000009919 sequestration Effects 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 238000005755 formation reaction Methods 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 2
- 229910000510 noble metal Inorganic materials 0.000 claims 2
- 241000182341 Cubitermes group Species 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000003129 oil well Substances 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 241000894007 species Species 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 46
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 16
- 239000000446 fuel Substances 0.000 abstract description 10
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 40
- 239000000047 product Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 239000012466 permeate Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- -1 methane hydrocarbon Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- MEUAVGJWGDPTLF-UHFFFAOYSA-N 4-(5-benzenesulfonylamino-1-methyl-1h-benzoimidazol-2-ylmethyl)-benzamidine Chemical compound N=1C2=CC(NS(=O)(=O)C=3C=CC=CC=3)=CC=C2N(C)C=1CC1=CC=C(C(N)=N)C=C1 MEUAVGJWGDPTLF-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001193 catalytic steam reforming Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002303 thermal reforming Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
- B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
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- B01J35/58—Fabrics or filaments
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
- B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- 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
- C01B3/38—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 catalysts
- C01B3/384—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 catalysts the catalyst being continuously externally heated
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- 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
- C01B3/48—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 followed by reaction of water vapour with carbon monoxide
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- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00256—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles in a heat exchanger for the heat exchange medium separate from the reactor
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- B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
- C01B2203/0288—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
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- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
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- C01B2203/041—In-situ membrane purification during hydrogen production
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- 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
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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Definitions
- This invention relates to heat exchanged hydrogen membrane reactors. More particularly, the invention relates to a hydrogen membrane reactor that employs catalytic or stream refo ⁇ ning and a water gas shift reaction on one side of the membrane, and hydrogen combustion on the other side of the membrane. A portion of the heat of the highly exothermic hydrogen combustion is exchanged through the membrane to supply heat to the reforming reaction. The hydrogen combustion product is used to power a turbine for producing electricity.
- Hydrogen permeable membranes are also generally known in the art, and have been utilized in hydrogen separation in varied applications.
- the present invention utilizes a hydrogen membrane in a novel reactor configuration that is particularly adapted to combust the hydrogen and use its heat of combustion in the hydrogen producing reaction while using the energy of combustion to power a turbine.
- the present invention is directed to a heat exchanged membrane reactor that (A) separates hydrogen from a hydrocarbon source using a membrane, (B) combusts the hydrogen, (C) transmits a portion of the heat of the combusted hydrogen to an endothermic reformer process, (D) uses the product of the hydrogen combustion to power a turbine for power generation.
- the heat exchanged membrane reactor employs thermal or catalytic steam reforming of a hydrocarbon feed to produce hydrogen, which permeates the reactor membrane to the opposite side, where it is combusted. A portion of the heat of combustion is transmitted through the membrane to supply heat to the reforming reaction, a highly endothermic reaction. The combustion product is used to power a turbine for generating electricity.
- a water gas shift reaction is employed on the reformer side of the membrane reactor to convert CO to C0 2 that may be conveniently sequestered.
- the heat-exchanged membrane need withstand elevated temperatures, ranging from about 400°C to about 1400°C, and have hydrogen permeance of at least a portion of the membrane ranging from about 1 day-atmosphere of H ).
- the reforming reaction and at least a portion of the hydrogen combustion occurs proximate to the membrane to facilitate the heat transfer.
- Figure 1 is across sectional view of an embodiment of the heat exchange membrane reactor.
- Figure 2 is a diagram that illustrates the use of the heat exchange membrane reactor powering a gas turbine generator.
- Figure 4 is a cross sectional view of a modular embodiment of the heat exchange membrane reactor.
- FIG. 1 The operation of the heat exchange membrane reactor of the invention may be better understood by reference to the diagram of Figure 1.
- a reforming feed 1 containing hydrocarbon and water and/or steam is supplied to a "reforming zone" 3 of the membrane reactor.
- a reformer effluent 6 is withdrawn or exits from that side.
- Compressed air 8 is fed to the combustion side 5 of the membrane, and combustion effluent 9 is withdrawn or exits from that side.
- the membrane 4 is in the form of a tube and the reforming side 3 is on the outside of the tube, while the combustion side 5 is on the inside of the tube.
- Conventional steam refo ⁇ ning reactions are utilized in the reforming zone 3 to react the hydrocarbon with H 2 0 to form elemental hydrogen and at least CO.
- the water and/or steam and hydrocarbon fuel are supplied at pressures ranging from about 1 bar to about 300 bars, and preferably from about 5 bars to about 40 bars to both facilitate hydrogen permeance through the membrane and help maintain structural integrity of the membrane 4.
- the hydrocarbon feed may comprise any carbon-containing fuel susceptible to thermal or catalytic refomiing and/or shift reaction known in the art to produce hydrogen such as carbon monoxide, methane and propane.
- water feed content ranging from about 1.7 to about 6.0 moles of water per mole of hydrocarbon feed. More preferably, water feed content ranges from about 2 to about 4 moles of water per mole of hydrocarbon feed.
- S/C steam to carbon ratio
- the steam to carbon ratio is between (2-z/x) and (3-z x).
- Steam reforming is a highly endot-hermic reaction. For example, reforming a simple methane hydrocarbon feed
- CH 4 + H 2 0 ⁇ 3H 2 + CO has a heat of reaction of about 88,630 BTU/mole.
- One aspect of the present invention is the utilization of at least a portion of the heat of hydrogen combustion to supply at least a portion of the heat requirements of the reformer's endothermic reaction.
- the refo ⁇ ning reaction preferably occurs proximate to or most preferably, at the reforming zone surface of the membrane.
- a means to accomplish this is to promote the refo ⁇ ning reaction using a catalyst that is contiguous with, or deposited on at least a portion of the membrane 4.
- a refo ⁇ ning catalyst is deposited onto or into a portion of the surface of the membrane.
- Figure 1 shows a catalyst (41, 48) deposited onto the surface of the membrane.
- materials that are suitable as reforming catalysts include nobel metals and nobel metal oxides such as Platinum, Ruthenium, and oxides thereof, transition metals and transition metal oxides and generally elements or oxides of group VIII metals as well as Ag, Ce, Cu, La, Mo, Mg, Sn, Ti, Y and Zn, or combinations thereof.
- Preferred catalyst systems include Ni, NiO, Rh, Pt and combinations thereof. These materials may be deposited or coated on the membrane surface or incorporated into the catalyst surface by means known in the art.
- the feed fuel and water and/or steam feed are at pressures ranging from about one (1) to about three hundred (300) bars, and preferably between about five (5) and forty (40) bars.
- the operating temperature of the membrane will range from about 400°C to about 1400°C with a preferred operating temperature range of about 700°C to about 1300°C. While the adiabatic upper temperature limit is about 2000°C, present membrane and gas turbine technology have an operating limit of about 1400°C.
- the operating temperature on the reforming side of the membrane may be up to about 200°C cooler than the temperature on the combusting side. A sufficient level of hydrogen permeance through the membrane is required in the practice of the invention.
- Hydrogen permeance under operating conditions will range from about one (1) to about one million (10 6 ) moles (m 2 -day-atm H 2 ).
- the permeance referred to is a point permeance that can be defined at each point on the membrane surface and the units atmosphere of H 2 refer to the difference between the hydrogen partial pressure across the membrane.
- hydrogen permeance will be influenced by the hydrogen-pressure differential between the reformer side 3 of the membrane and the combustion side 5 of the membrane, the temperature of the membrane 4 and/or hydrogen gas, and strongly influenced by the composition, thickness and configuration or shape of the membrane and membrane surface(s).
- Suitable membrane materials are ceramics such as alumina and zirconia silicon carbide, silicon nitride, or combinations thereof, including for example, A1 2 0 3 , Zr0 2 , MgO, Ti0 2 , La 2 0 3 , Si0 2 , perovskites, hexaaluminates, and metals such as nickel and high nickel content alloys, and cermets.
- Membranes may be incorporated into a module.
- Membrane modules provide means to combine multiple membrane elements with a gas distribution means and with flow passages or channels that bring the gases into close proximity to the membrane.
- Membrane elements may be fabricated in many ways, including as tubes and flat plates. Module technologies suitable for various membrane elements are known in the art.
- the membrane may be in the form of a flat sheet, tube, hollow fiber, or may be integrated into a monolithic structure.
- the membrane is sealed to or into the module so that the feed and permeate are separated from each other by the membrane.
- the membrane is sealed into the module so that the feed and permeate streams are separated.
- the module provides a method of distributing and collecting separate feed and permeate streams from individual membrane elements.
- the membrane elements may be formed as a symmetric or asymmetric structure.
- the membrane may also have a catalytic functionality incorporated into it.
- Catalyst functionality may be provided as pelletized or powder catalyst, supported or unsupported, that is loaded into the gas passageways proximate to the membrane, or catalyst, supported or unsupported, may be applied directly to the membrane surfaces, or as a porous layer integral with the membrane. Catalyst functionality may be provided in multiple ways and on either or both sides of the membrane.
- heat exchange membrane 4 comprises an asymmetric membrane having a relatively porous support or substrate and a thin separation layer that selectively diffuses hydrogen.
- the porous support illustrated in Figure 1 as 42, provides mechanical strength and structural integrity as well as facile transport of molecules to the separation layer 43.
- the porous support may be composed of multiple layers of material, each with a differing chemical composition or pore size. In a preferred embodiment, the majority of pores in the support are in the range from .05 to 30 ⁇ m.
- Materials that can be used for supports include -tfumina, zirconia, silicon carbide, and porous metals such as porous steel, nickel and alloys such as Hasteloy.
- the support structure is preferably stable under high temperature operating conditions and must not be degraded by molecular species that are utilized or formed in the process (for example steam).
- the membrane 4 illustrated in Figure 1 is comprised of catalyst (41,48), porous support 42, and permselective layers 43.
- Catalysts 41 and 48 may comprise two or more catalysts, one serving to catalyze the steam reforming reaction, the second to catalyze the water gas shift reaction.
- a thin selective difiEusion layer, illustrated in Figure 1 as 43, may be positioned on or into the combustion side surface of the membrane. This is most preferable when, for example, hydrocarbon feeds contain materials that would be deleterious to such material.
- the thin selective diffusion layer may comprise a thin film of metal such as nickel, or ferrous alloys or inorganic materials such as alumina, zirconia, yttrium stabilized zirconia, silicon carbide, silicon nitride, perovskites and hexaaluminates ranging in thickness from about 100 angstroms to 500 microns.
- metal such as nickel, or ferrous alloys or inorganic materials such as alumina, zirconia, yttrium stabilized zirconia, silicon carbide, silicon nitride, perovskites and hexaaluminates ranging in thickness from about 100 angstroms to 500 microns.
- the asymmetric configuration facilitates high hydrogen permeance while ma t-tining hydrogen selectively and structured integrity under the contemplated operating temperatures and pressures.
- the reaction is mildly exothermic having a heat of reaction of approximately -17,700 BTU/mole.
- water gas shift is accomplished in two stages, at high and low temperature, respectively.
- the reaction is conducted with chromium promoted iron catalyst at an inlet temperature of about 370°C.
- Reaction exothermically raises the temperature to about 430°C at the exit.
- a second stage of low temperature shift is then employed because equilibrium toward hydrogen is improved at lower temperature.
- permeation of hydrogen through the membrane is used to drive the equilibrium, instead of using lower temperature. This permits deleting the low temperature shift portion, and permits the user to run the high temperature shift at higher temperatures.
- the catalyst used for steam reforming is also used to catalyze the shift reaction, and shift and reforming reactions occur in parallel according to their individual rates at locations along the refo ⁇ ning side of the membrane.
- the feed flow of fuel and steam on the reformer side is in a direction opposite to the feed flow of air on the combustor side.
- Counterflow is preferred because it matches the cooling of the carbon dioxide to the pre-heating of the combustion air, and is also preferred because it matches the hottest portion of the combustion side with the reforming reaction, which is endothermic.
- Other arrangements such as co-flow or crossflow, both generally known in the art, may be used, for example for mechanical or chemical reasons.
- the catalyst for the water gas shift reaction is contiguous with or deposited on at least a portion of the surface of the heat exchange membrane.
- steam reforming chemistry occurs first, illustrated as zone 71 in Figure 1, and shift reactions occur second, illustrated as zone 72.
- zone 71 steam-reforming reactions occur in the area 31 that is proximate to the membrane, and/or catalyzed by steam reforming catalyst 41.
- zone 72 shift reactions occur in the area 32 that is proximate to the membrane, and/or catalyzed by shift catalyst 48.
- heat 62 released by the shift reaction may be conducted to the combustion side 52 where it may provide preheat for the incoming air stream 8.
- Combustion of hydrogen in the region 51 of zone 71 provides heat 61 that is conducted to side 31 to provide the heat of the reforming reaction.
- the hydrogen selectivity be at least 3:1 with respect to other gases such as nitrogen, oxygen, methane, CO, C0 2 and H 2 0.
- the foregoing selectivity ratio is at least about 100: 1. More preferred is a selectivity ratio of at least about 10000:1.
- the hydrogen produced or liberated in the refomiing reaction and water gas shift reaction permeates the heat exchange membrane 4 to the combustion side 5 of the reactor.
- the hydrogen is then combusted proximate to the heat exchange membrane 4. This is done to facilitate transfer of the heat of combustion of the hydrogen through the heat exchange membrane 4, to supply heat to the refo ⁇ ning reaction.
- at least a portion of the surface or surface region of the combustion side surface of the heat exchange membrane contains a catalyst for the combustion of hydrogen. This catalyst is most preferably on a portion of the surface or surface region of the membrane 4 that is juxtaposed the region where the stream reforming reaction occurs.
- Catalysts that are suitable for use in the oxidation of hydrogen (i.e., combustion) of the invention include mixtures of metals and/or metal oxides from the transition elements as well as from groups 2a, 3 a, and 4a of the periodic table (including Lanthanides and Actinides).
- Such catalysts may take on the conventional format of catalyst on support, however at the high temperature of operation utilized for the present invention, catalyst may take the form of a single mixed-metal oxide formulation, such as a substituted perovskite or hexaaluminate.
- Catalyst systems developed for catalytic combustion in gas turbines are particularly useful in the present invention (for example, see Catalysis Today. Volume 47, Nos. 1-2(1999)).
- perovskite supports such as LaCr0 3 (more generally MlM-20 3 - ⁇ , where Ml and M2 are each an element or mixture of elements, for example including Fe, Ni, Co, Cr, Ag, Sr, Ba, Ti, Ce, La, Mn, Zr).
- Substituted hexaaluminate, perovskite, or mixed metal oxide supports may, in themselves, provide adequate catalytic activity for high temperature oxidation of hydrogen.
- a catalytic agent may be dispersed onto the support.
- Preferred catalyst materials include metals and oxides of elements in groups 6b, 7b, and 8. More preferred catalyst materials include metals and oxides of elements in groups 6b, 7b, and 8. More preferred catalyst materials are the group 8 metals and oxides, in particular metals and oxides of Fe, Rh, Pd, and Pt. Metals and oxides of Fe and Pd are most preferred for reasons of least volatility at high temperatures.
- the hydrogen combustion reaction produces energy.
- this energy is utilized to power a turbine for the production of electricity.
- compressed air 8 is fed to the combustion side of the reactor.
- the pressure of the compressed air may range from about three (3) bars to about three hundred (300) bars and preferably between about eight (8) bars and about fifty (50) bars.
- the combusted fuel is hydrogen
- the combustion produces substantially no carbon dioxide product to be of concern regarding the greenhouse effect on the environment.
- effluent 9 contain substantial amounts of carbon monoxide or unburnt hydrocarbons of concern to the environment.
- the use of hydrogen as fuel provides wide process latitude regarding combustion stoichiometty and temperature. Combustion at relatively lean, cool (compared to stoichiometric combustion) conditions in proximity to the membrane will produce substantially no nitrogen oxide products.
- the combustion energy powers a turbine for the production of electricity.
- FIG. 2 there is illustrated a heat exchange membrane reactor powered turbine for the production of electricity.
- the membrane reactor has a reformer side 3 and combustion side 5 separated by a heat exchange membrane 4.
- a hydrocarbon plus water (steam) feed 1 is supplied to the reformer side of the reactor.
- Hydrogen produced in the refo ⁇ ning reaction and the water gas shift reaction permeates membrane 4 to the combustion side 3 of the reactor.
- Compressed air 8 is fed to the combustion side 3 of the reactor where hydrogen from the reformer reaction and water gas shift reaction has permeated to.
- the hydrogen is combusted; its combustion energy released into combustion product 9, which is directed to turbine expander 204.
- all or a fraction (215) of the reforming-side reaction product 6 is combined with combustion effluent 9 as a combined stream 203 that is directed to the turbine expander 204.
- Turbine expander 204 produces power on shaft 206, which power provides the compressive energy to compress air stream 201 via compressor 202, and which power is used to produce electricity in generator 207.
- the expanded combustor effluent 205 contains waste heat that can be recovered by raising steam and preheating feeds.
- waste heat boiler 212 removes heat from the combustor effluent 205, and provides that heat to boiler feed water 211 to raise steam 213 that is fed to the reforming side of the reactor. Cooled combustor effluent 208 may be discharged to the atmosphere. .
- the reforming effluent 6 may be used in several ways. In a preferred embodiment, it is cooled in heat exchanger 216, increased in pressure via compressor 220, and finally sequestered as stream 221. Depending on steam/carbon ratios and other operating parameters, liquid water may need to be removed at some point in the cooling, compressing and sequestering of the refo ⁇ ning effluent. Such removal is well known in the art. In some embodiments, a portion 217 of the cooled refo ⁇ ning effluent is made into a higher-pressure stream 219 via compressor 218 and is recycled to the reformer feed.
- the combined reformer feed 1 consists of hydrocarbon feed 214, steam 213, and optionally recycled reformer effluent 219.
- Heat exchanger 232 could be a furnace or could be heat recovery from effluent streams such as 6 or 205, some combination of furnace and heat recovery. A ⁇ anging such heat recovery is well known in the art.
- a differential pressure may exist between reforming side and the combustion side of the membrane.
- Differential pressure is characterized in two ways; the magnitude of the pressure difference and the sign of the pressure difference (which stream is higher pressure). Both of these characteristics may vary with application.
- the reformer it will be prefe ⁇ ed for the reformer to be at higher pressure than the combustor.
- the objective is to combust methane and leave a sequesterable C0 2 stream
- it may be prefe ⁇ ed to have the reforming side at substantially higher pressure than the combustion side.
- the pressure of the reformer is higher than the combustor, the magnitude of that pressure difference is prefe ⁇ ed to be less than about 100 bar.
- the combustor it will be prefe ⁇ ed for the combustor to be at higher pressure than the reformer.
- the objective is to use a low pressure fuel gas as turbine fuel without expending the cost of compressing that fuel gas
- it may be prefe ⁇ ed to have the reforming side at substantially lower pressure than the combustion side.
- a near-surface combustion of hydrogen on the combustor side creates a local low H 2 partial pressure, which enables transfer of the H 2 from the low-pressure reformer side to the high-pressure combustor side.
- the pressure of the combustor is higher than the reformer, the magnitude of that pressure difference is prefe ⁇ ed to be less than about 50 bar.
- the differential pressure ( ⁇ P) between reforming side and the combustion side of the membrane be less than about 5 bars.
- the differential pressure ( ⁇ P) between reforming side and the combustion side of the membrane be less than about 20% of the higher of the two pressures.
- the present invention may operate with feeds that may contain hydrocarbons, oxygenates, CO, C0 2 , nitrogen, hydrogen, H 2 S, sulfides, mercaptans, and thiophenes. Other trace components may also be present in the feed.
- the product from the reformer side will contain C0 2 and H 2 0.
- a substantial portion of the H 2 0 exiting the reformer originates as feed.
- the C0 2 in the gas exiting the reformer is the sum of the net amount produced in the refo ⁇ ning reaction and the amount originating with the feed.
- Other components that can be present are products that can be produced in the reforming reaction such as CO and hydrogen.
- the nitrogen level in the reformer product will be determined by the nitrogen level in the feed.
- the level of H 2 S in the product gas from the reformer will be determined by the amount of sulfur in the feed.
- a significant C0 2 concentration can be produced when the feed contains less than about 35 mole % nitrogen and, in a prefe ⁇ ed embodiment, less than 5 mole % nitrogen.
- product C0 2 may be economically disposed, stored, or utilized in underground formations.
- product C0 2 may be utilized as an enhanced recovery fluid in oil reservoirs or may be sequestered in depleted oil or gas reservoirs.
- Certain aquifer formations are suitable for storing or sequestering C0 2 . Because of the pressures in underground formations, in most cases the C0 2 has to be injected at high pressures.
- the cost of compression is substantially reduced when the stream exiting the reformer is substantially composed of C0 2 .
- Another aspect of the invention is the potential to operate the membrane combustor in a mode that produces less NO x .
- NO x production in combustion is generally associated with high temperatures. It is possible to operate the membrane combustor at temperatures lower than those normally required to sustain a flame. Lower temperature operation is possible because hydrogen is burned in the membrane combustor rather than a hydrocarbon. Hydrogen can be combusted under conditions where hydrocarbons will not normally react. The combustion of hydrogen may also be facilitated by a catalyst, allowing reaction at highly rich or lean conditions.
- the membrane combustor is operated in a mode designed primarily for NO x reduction, it may be possible to combine the product streams exiting the reformer and combustion sides. Recombination of these streams may occur within the membrane module or after the streams exit the membrane module and before they are fed into a gas turbine.
- Example 1 By way of illustration, the following exemplify embodiments of the present invention.
- Example 1
- methane is combusted in heat exchanged membrane reactor, the reactor feeds and effluents being integrated with a gas turbine for power generation.
- the gas turbine is comprised of an air compressor 302, a power turbine 304, a shaft 306 and a generator set 307.
- Air 301 enters the compressor 302 and leaves as a pressurized stream 358 at a pressure of about 35 atmospheres absolute and a temperature of about 600°C.
- the air travels through the heat exchanged membrane reactor on the combustion side 355 where some of the oxygen reacts with hydrogen that has permeated the membrane 354.
- the combustion effluent 359 goes to the power turbine 304 where it is expanded to an atmospheric pressure stream 305 at a temperature of about 417°C.
- Component flow rates for streams 358 and 359 are shown in Table 1. Under these conditions the compressor 302 uses 100 MW of power and the turbine 304 yields 157 MW for a net gas turbine power yield 307 of 57 Megawatts.
- the refo ⁇ ning side 353 of the heat exchanged membrane reactor is fed by a methane/steam stream 351 at a steam/methane mole ratio of 2.5 and preheated to 490°C.
- the methane is completely converted to hydrogen and C0 2 , the hydrogen permeating to the combustion side 355.
- the C0 2 and a residual amount of steam comprise the product stream 356 of the reforming side 353.
- Component flow rates for streams 351 and 356 are shown in Table 1. In the present example, 1.326 kg/sec of H 2 is created and permeated through the membrane 354. Table 1
- the reformer feed 351 is preheated by recovering heat from several sources.
- the power turbine exhaust 305 at about 417°C is used in a waste heat boiler 312 to make steam 313 from boiler feed water 311.
- the cooled exhaust 308, now at about 325°C is then used in heat exchanger 336 to heat the methane fuel 314 from pipeline temperatures of about 25°C to about 250°C, leaving the final flue-gas 335 at about 316°C .
- the heated methane 330 and the steam 313, both at about 250°C are combined into a feed stream 331, which is heated in heat exchanger 332 against the reformer effluent stream 356.
- the resulting preheated reformer feed 351 is at about 490°C, while the cooled reformer effluent stream 333 is at about 300°C.
- This reformer effluent stream 333 is further cooled in air fin heat exchanger 316 to condense water and cool to about 50°C.
- Compressor 320 is used to raise this C0 2 stream to a high-pressure stream 321 suitable for sequestration.
- the gas turbine net power 307 of 57 MW represents about 43% of the lower heating value of the methane feed 314. This compares favorably with the cycle efficiency of the gas turbine as used with a normal combustor. Because the cooled C0 2 effluent 334 is highly concentrated and at high pressure, the additional work required to compress to sequestration pressures is rninimal. For example, compression to 160 bar would require less than a megawatt of power. Also, the flue gas 335 at about 317°C would be suitable for generation of additional power via combined cycle operation.
- the membrane combustor module shown in Figure 4 is formed from asymmetric tubular membranes 401.
- the tubular membranes are sealed into the module in a geometry similar to a tube in shell heat exchanger.
- Each tubular membrane is sealed at each end into a plate (403 and 405) in a manner such that gas can pass directly through the plate into the interior 407 of each tube.
- the plates (403 and 405) are in turn sealed into a ceramic tube 409 that forms the shell of the module.
- the ceramic tube 409 has fittings (411 and 413) that allow gas to be flowed inside the shell.
- At the ends of the module there are flanges (417 and 419) that allow the module to be sealed to inlet and exit pipes.
- Compressed air 415 in the pressure range of 5 to 40 atmospheres is fed into the shell through fitting 411.
- the compressed air 415 entering the shell is in the temperature range from 25° to 1000° Centigrade. It is prefe ⁇ ed that the compressed air be in the temperature range from 200 to 600 °C. In general air will heat to these temperature ranges when it is compressed.
- the oxygen in the compressed air reacts with hydrogen permeating the asymmetric tubular membranes 401, releasing heat and forming water vapor. It may be desirable to catalytically assist the reaction of oxygen and hydrogen.
- the reaction is catalyzed with a platinum catalyst that is dispersed on the exterior surface 423 of the asymmetric membranes 401.
- the catalyst can be deposited from solution using standard dispersed metal catalyst preparation methods. When the catalyst is incorporated on the membrane surface 423, there is a tendency to have more of the exothermic water forming reactions occur on the membrane surface. This improves the thermal integration with the steam refo ⁇ ning and shift reactions that occur on the interior surface of the asymmetric membrane.
- other methods may be used to incorporate catalyst into the shell side 421 of the membrane. Catalyst can be incorporated into the shell space of the module 421 as pellets, monoliths or as a coating covering the entire interior shell surface.
- a catalyst it is preferable to have a substantial portion of the hydrogen permeating the membrane react with oxygen in the compressed air.
- the compressed air travels down the length of the module from the inlet port 411 to the exit port 413, it heats up.
- the air and water vapor exiting the module 425 are preferably at a temperature in the range from 700 to 1400 °C. This hot high-pressure air and water vapor stream 425 is fed to a gas turbine where electric power is produced.
- a feed 427 containing H2O and methane is flowed in a direction that is countercu ⁇ ent to the hot high pressure air and water vapor stream 425.
- the hydrocarbons and sulfur species in the feed 427 come from natural gas.
- the feed 427 also contains a portion of the reformed gas exiting 429 the tubular membranes.
- the reformed gas 429 is primarily composed of CO2 and H2O. A portion of this gas is recycled back to the input 427 to add C02 to the feed.
- the addition of C02 helps suppress carbon deposition within the tubular membrane. In particular, it helps control carbon deposition caused by the Boudart reaction.
- the molar ratio of H2O to CH4 in the feed also known as the steam/methane ratio can range from 1 to 6.
- the steam/methane ratio is prefe ⁇ ed to be greater than 2.
- the steam/methane ratio is between 1 and 2, all of the carbon cannot be converted to CO2 and a syngas product can be produced.
- the feed 427 pressure of the gas mixture used to fuel the membrane combustor can be in the range from 1-200 atmospheres. It is prefe ⁇ ed that the gas mixture be in the range from 2-50 atmospheres.
- the inlet temperature of the feed 427 can be in the range from 20-700 °C. It is more prefe ⁇ ed that the feed is a single-phase, gaseous stream at temperature above 250°C.
- the feed gas 427 As the feed gas 427 travels countercu ⁇ ently to the compressed air stream (415 and 425), it heats up. As the feed gas heats up it begins to react to form hydrogen.
- the initial reaction will be predominantly a steam reforming reaction that can be promoted by a catalyst.
- CO formed by the initial steam reforming reaction is converted to hydrogen and CO2 with a water gas shift reaction.
- This reaction can be catalyzed with a catalyst that is different from the catalyst use to promote the refomiing reaction.
- the catalyst for these reactions can be on the inner surface of the tubular membrane, within the wall of the tubular membrane of introduced as catalyst pellets within the interior 407 of the tubular membrane.
- the membrane combustor module is formed from tubular membrane elements 401.
- the tubular membranes can have an inner diameter in the range from .1 to 25 millimeters and a wall thickness of .1-10 millimeters. It is prefe ⁇ ed that the tube wall 431 be porous. The porous wall improves transport of hydrogen across the membrane and also provides structural strength. The most prevalent pore size is in the range from .01 to 100 ⁇ m.
- the porous tube is made by sintering alpha alumina powder.
- a thin membrane that is permselective for hydrogen is formed near or on the inner or outer surface of the tube.
- the permselective hydrogen membrane is formed on the outer surface of the tube.
- the hydrogen selective membrane in this example is a 1 ⁇ m thick layer of dense alpha alumina. At the operating temperature of the membrane combustor module, the alpha alumina readily transports hydrogen.
- This example follows the same flow diagram and conditions as Example 1, except that it has been adjusted for a feed that has a high level of C0 2 .
- the feed in this case has a molar C0 2 /CH 4 ratio of 2.65.
- the high level of C0 2 in the feed results in a higher heat capacity for the reformer effluent 356, which, in turn, means that the reformer feed 351 may be heated to a higher temperature.
- a reformer feed temperature of 610°C is achieved, as shown in Table 2 below.
- the added C0 2 diluent results in additional small changes in the heat balance that result in a the need for slightly higher methane feed rate, but also provide a slightly higher flow rate to the power turbine. The combination of these changes results in an efficiency decrease of about 0.4% relative to Example 1.
- power is extracted from a highly C0 2 -diluted stream while maintaining the C0 2 at high concentration and pressure suitable for subsequent sequestration, and without substantial loss in efficiency.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Catalysts (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US606887 | 2000-06-29 | ||
US09/606,887 US6830596B1 (en) | 2000-06-29 | 2000-06-29 | Electric power generation with heat exchanged membrane reactor (law 917) |
PCT/US2001/019917 WO2002002460A2 (fr) | 2000-06-29 | 2001-06-22 | Generation d'electricite avec un reacteur a membrane a echange thermique |
CA2414657A CA2414657C (fr) | 2000-06-29 | 2002-12-18 | Production d'electricite avec reacteur a membrane a echange de chaleur |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1294637A2 true EP1294637A2 (fr) | 2003-03-26 |
Family
ID=32991653
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01946649A Withdrawn EP1294637A2 (fr) | 2000-06-29 | 2001-06-22 | Generation d'electricite avec un reacteur a membrane a echange thermique |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1294637A2 (fr) |
JP (1) | JP2004502623A (fr) |
CA (1) | CA2414657C (fr) |
WO (1) | WO2002002460A2 (fr) |
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US11492255B2 (en) | 2020-04-03 | 2022-11-08 | Saudi Arabian Oil Company | Steam methane reforming with steam regeneration |
US11492254B2 (en) | 2020-06-18 | 2022-11-08 | Saudi Arabian Oil Company | Hydrogen production with membrane reformer |
US11578016B1 (en) | 2021-08-12 | 2023-02-14 | Saudi Arabian Oil Company | Olefin production via dry reforming and olefin synthesis in a vessel |
US11583824B2 (en) | 2020-06-18 | 2023-02-21 | Saudi Arabian Oil Company | Hydrogen production with membrane reformer |
US11617981B1 (en) | 2022-01-03 | 2023-04-04 | Saudi Arabian Oil Company | Method for capturing CO2 with assisted vapor compression |
US11639290B2 (en) | 2020-06-04 | 2023-05-02 | Saudi Arabian Oil Company | Dry reforming of methane with carbon dioxide at elevated pressure |
US11718575B2 (en) | 2021-08-12 | 2023-08-08 | Saudi Arabian Oil Company | Methanol production via dry reforming and methanol synthesis in a vessel |
US11787759B2 (en) | 2021-08-12 | 2023-10-17 | Saudi Arabian Oil Company | Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel |
US11999619B2 (en) | 2020-06-18 | 2024-06-04 | Saudi Arabian Oil Company | Hydrogen production with membrane reactor |
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US7527661B2 (en) * | 2005-04-18 | 2009-05-05 | Intelligent Energy, Inc. | Compact devices for generating pure hydrogen |
DE102004019263B4 (de) * | 2003-04-29 | 2009-11-26 | Presting, Hartmut, Dr.Rer.Nat. | Vorrichtung zur Erzeugung von nahezu reinem Wasserstoff durch Reformierung und Verfahren zur Herstellung der Vorrichtung |
WO2005075344A1 (fr) * | 2004-02-09 | 2005-08-18 | Ngk Insulators, Ltd. | PROCEDE DE REFORMAGE D'HYDROCARBURES AVEC DU DIOXYDE DE CARBONE par L'UTILISATION D'UN REACTEUR A MEMBRANE SELECTIVEMENT PERMEABLE |
US7752848B2 (en) | 2004-03-29 | 2010-07-13 | General Electric Company | System and method for co-production of hydrogen and electrical energy |
US7572432B2 (en) * | 2004-04-13 | 2009-08-11 | General Electric Company | Method and article for producing hydrogen gas |
NO20051891D0 (no) * | 2005-04-19 | 2005-04-19 | Statoil Asa | Prosess for produksjon av elektrisk energi og CO2 fra et hydrokarbon rastoff |
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AU2007246958A1 (en) * | 2006-05-08 | 2007-11-15 | Bp P.L.C. | Process for hydrogen production |
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US7802434B2 (en) * | 2006-12-18 | 2010-09-28 | General Electric Company | Systems and processes for reducing NOx emissions |
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US11492255B2 (en) | 2020-04-03 | 2022-11-08 | Saudi Arabian Oil Company | Steam methane reforming with steam regeneration |
US11322766B2 (en) | 2020-05-28 | 2022-05-03 | Saudi Arabian Oil Company | Direct hydrocarbon metal supported solid oxide fuel cell |
US11639290B2 (en) | 2020-06-04 | 2023-05-02 | Saudi Arabian Oil Company | Dry reforming of methane with carbon dioxide at elevated pressure |
US11492254B2 (en) | 2020-06-18 | 2022-11-08 | Saudi Arabian Oil Company | Hydrogen production with membrane reformer |
US11583824B2 (en) | 2020-06-18 | 2023-02-21 | Saudi Arabian Oil Company | Hydrogen production with membrane reformer |
US11999619B2 (en) | 2020-06-18 | 2024-06-04 | Saudi Arabian Oil Company | Hydrogen production with membrane reactor |
US11578016B1 (en) | 2021-08-12 | 2023-02-14 | Saudi Arabian Oil Company | Olefin production via dry reforming and olefin synthesis in a vessel |
US11718575B2 (en) | 2021-08-12 | 2023-08-08 | Saudi Arabian Oil Company | Methanol production via dry reforming and methanol synthesis in a vessel |
US11787759B2 (en) | 2021-08-12 | 2023-10-17 | Saudi Arabian Oil Company | Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel |
US11617981B1 (en) | 2022-01-03 | 2023-04-04 | Saudi Arabian Oil Company | Method for capturing CO2 with assisted vapor compression |
Also Published As
Publication number | Publication date |
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CA2414657A1 (fr) | 2004-06-18 |
JP2004502623A (ja) | 2004-01-29 |
CA2414657C (fr) | 2011-05-24 |
WO2002002460A3 (fr) | 2002-05-16 |
WO2002002460A2 (fr) | 2002-01-10 |
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