RU2008102365A - Производство водорода с использованием электрохимического риформинга и регенерации электролита - Google Patents
Производство водорода с использованием электрохимического риформинга и регенерации электролита Download PDFInfo
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- RU2008102365A RU2008102365A RU2008102365/15A RU2008102365A RU2008102365A RU 2008102365 A RU2008102365 A RU 2008102365A RU 2008102365/15 A RU2008102365/15 A RU 2008102365/15A RU 2008102365 A RU2008102365 A RU 2008102365A RU 2008102365 A RU2008102365 A RU 2008102365A
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- 239000003792 electrolyte Substances 0.000 title claims abstract 13
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract 6
- 239000001257 hydrogen Substances 0.000 title claims abstract 6
- 238000004519 manufacturing process Methods 0.000 title claims abstract 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims 6
- 230000008929 regeneration Effects 0.000 title claims 5
- 238000011069 regeneration method Methods 0.000 title claims 5
- 238000002407 reforming Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract 34
- 239000000203 mixture Substances 0.000 claims abstract 33
- 229910052751 metal Inorganic materials 0.000 claims abstract 16
- 239000002184 metal Substances 0.000 claims abstract 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 6
- 239000003054 catalyst Substances 0.000 claims abstract 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract 6
- 239000000126 substance Substances 0.000 claims abstract 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract 4
- 150000001298 alcohols Chemical class 0.000 claims abstract 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims abstract 3
- 150000001720 carbohydrates Chemical class 0.000 claims abstract 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract 3
- -1 contacting Chemical class 0.000 claims abstract 3
- 239000008151 electrolyte solution Substances 0.000 claims abstract 3
- 239000002028 Biomass Substances 0.000 claims abstract 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims abstract 2
- 229920002472 Starch Polymers 0.000 claims abstract 2
- 150000001299 aldehydes Chemical class 0.000 claims abstract 2
- 239000000956 alloy Substances 0.000 claims abstract 2
- 229910045601 alloy Inorganic materials 0.000 claims abstract 2
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 2
- 235000010980 cellulose Nutrition 0.000 claims abstract 2
- 229920002678 cellulose Polymers 0.000 claims abstract 2
- 235000019441 ethanol Nutrition 0.000 claims abstract 2
- 150000002170 ethers Chemical class 0.000 claims abstract 2
- 150000002576 ketones Chemical class 0.000 claims abstract 2
- 239000007791 liquid phase Substances 0.000 claims abstract 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract 2
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract 2
- 235000019698 starch Nutrition 0.000 claims abstract 2
- 235000000346 sugar Nutrition 0.000 claims abstract 2
- 150000008163 sugars Chemical class 0.000 claims abstract 2
- 229910052723 transition metal Inorganic materials 0.000 claims abstract 2
- 150000003624 transition metals Chemical class 0.000 claims abstract 2
- 238000010521 absorption reaction Methods 0.000 claims 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 3
- 239000006227 byproduct Substances 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 claims 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 2
- 150000001642 boronic acid derivatives Chemical class 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 150000002739 metals Chemical class 0.000 claims 2
- 150000004885 piperazines Chemical class 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- 229910052581 Si3N4 Inorganic materials 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000011324 bead Substances 0.000 claims 1
- 229910052792 caesium Inorganic materials 0.000 claims 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- 235000014633 carbohydrates Nutrition 0.000 claims 1
- 229910000420 cerium oxide Inorganic materials 0.000 claims 1
- 239000003245 coal Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 239000004020 conductor Substances 0.000 claims 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 claims 1
- 150000002333 glycines Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 229910052741 iridium Inorganic materials 0.000 claims 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 239000012811 non-conductive material Substances 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 229910052702 rhenium Inorganic materials 0.000 claims 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims 1
- 229910052703 rhodium Inorganic materials 0.000 claims 1
- 239000010948 rhodium Substances 0.000 claims 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 1
- 229910052701 rubidium Inorganic materials 0.000 claims 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910010271 silicon carbide Inorganic materials 0.000 claims 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
Classifications
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- 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
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
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- B01J8/224—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/10—Preparation of bicarbonates from carbonates
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Abstract
1. Способ производства газообразного водорода, включающий в себя приведение в контакт, в жидкой фазе, по меньшей мере, одного окисляемого органического вещества в присутствии смеси, содержащей, по меньшей мере, один проводящий катализатор и водный раствор электролита на основе карбоната щелочного металла, где композиция, по меньшей мере, одного бикарбоната получается посредством взаимодействия указанного электролита и регенерируется, и указанное, по меньшей мере, одно окисляемое органическое вещество включает в себя окисленный углеводород. ! 2. Способ по п.1, в котором указанный окисленный углеводород выбирается из группы, состоящей из сахаридов, целлюлоз, крахмалов, сахаров, спиртов, простых эфиров, карбоновых кислот, альдегидов, кетонов, биомассы и их смесей. ! 3. Способ по п.2, в котором указанный спирт выбирается из группы, состоящей из C1-C6 спиртов и их смесей. ! 4. Способ по п.3, в котором указанный спирт выбирается из метанола, этанола и их смесей. ! 5. Способ по п.2, в котором указанный простой эфир выбирается из простого диметилового эфира, простого метилэтилового эфира, простого диэтилового эфира и их смесей. ! 6. Способ по п.2, в котором указанный окисленный углеводород представляет собой смесь метанола и простого диметилового эфира. ! 7. Способ по п.1, в котором указанный электролит на основе щелочного металла выбирается из группы, состоящей из гидроксидов, карбонатов, бикарбонатов металлов и их смесей. ! 8. Способ по п.1, в котором указанный катализатор выбирается из группы, состоящей из соединений, комплексов, сплавов и их смесей, содержащих, по меньшей мере, один металл, выбранный из переходных металлов Группы VIII Перио�
Claims (26)
1. Способ производства газообразного водорода, включающий в себя приведение в контакт, в жидкой фазе, по меньшей мере, одного окисляемого органического вещества в присутствии смеси, содержащей, по меньшей мере, один проводящий катализатор и водный раствор электролита на основе карбоната щелочного металла, где композиция, по меньшей мере, одного бикарбоната получается посредством взаимодействия указанного электролита и регенерируется, и указанное, по меньшей мере, одно окисляемое органическое вещество включает в себя окисленный углеводород.
2. Способ по п.1, в котором указанный окисленный углеводород выбирается из группы, состоящей из сахаридов, целлюлоз, крахмалов, сахаров, спиртов, простых эфиров, карбоновых кислот, альдегидов, кетонов, биомассы и их смесей.
3. Способ по п.2, в котором указанный спирт выбирается из группы, состоящей из C1-C6 спиртов и их смесей.
4. Способ по п.3, в котором указанный спирт выбирается из метанола, этанола и их смесей.
5. Способ по п.2, в котором указанный простой эфир выбирается из простого диметилового эфира, простого метилэтилового эфира, простого диэтилового эфира и их смесей.
6. Способ по п.2, в котором указанный окисленный углеводород представляет собой смесь метанола и простого диметилового эфира.
7. Способ по п.1, в котором указанный электролит на основе щелочного металла выбирается из группы, состоящей из гидроксидов, карбонатов, бикарбонатов металлов и их смесей.
8. Способ по п.1, в котором указанный катализатор выбирается из группы, состоящей из соединений, комплексов, сплавов и их смесей, содержащих, по меньшей мере, один металл, выбранный из переходных металлов Группы VIII Периодической таблицы элементов, и необязательно дополнительно содержит, по меньшей мере, один металл, выбранный металлов Группы IB, Групп IIB, Групп VIIB, и их смесей.
9. Способ по п.8, в котором указанный катализатор выбирается из группы, состоящей из платины, никеля, палладия, родия, иридия, кобальта, рутения, железа и их смесей, и необязательно дополнительно содержит металл, выбранный из группы, состоящей из меди, цинка, рения и серебра.
10. Способ по п.8, в котором указанный катализатор находится на носителе в виде проводящего или непроводящего материала, выбранного из группы, состоящей из металлов, оксидов металлов, окиси кремния, окиси алюминия, окиси кремния - окиси алюминия, окиси циркония, окиси титана, окиси церия, угля, карбида кремния, нитрида кремния, борида кремния и их смесей, или в нем, указанный носитель необязательно находится в форме, выбранной из группы, состоящей из шариков, порошков, экструдированных подложек с покрытиями, монолитов и их смесей.
11. Способ по п.1, в котором указанное окисляемое органическое вещество и указанный щелочной электролит взаимодействуют в присутствии воды.
12. Способ по п.7, в котором указанный щелочной электролит выбирается из группы, состоящей из гидроксидов, карбонатов, бикарбонатов щелочных металлов или щелочноземельных металлов и их смесей, и указанный металл щелочного электролита выбирается из группы, состоящей из натрия, лития, калия, цезия, рубидия и их смесей.
13. Способ по п.1, в котором указанная стадия реакции осуществляется при температуре примерно от 150°C и примерно до 350°C.
14. Способ по п.1, дополнительно включающий в себя стадию по существу отделения водорода, образующегося в течение стадии приведения в контакт от побочных продуктов реакции.
15. Способ по п.14, в котором указанное разделение представляет собой стадию поглощения, указанный побочный продукт содержит CO2 и указанное поглощение включает в себя приведение в контакт указанного водорода и CO2 с водным раствором, содержащим поглощающее количество соединения, выбранного из группы, состоящей из, по меньшей мере, одного карбоната щелочного металла, по меньшей мере, одного карбоната щелочноземельного металла и их смесей, при температуре примерно от 100°C примерно до 350°C, и при этом поглощая в реакции указанный CO2 и получая бикарбонат металла как дополнительный побочный продукт.
16. Способ по п.15, в котором указанная стадия поглощения включает в себя дополнительное использование, по меньшей мере, одного ускоряющего агента, выбранного из группы, состоящей из аминов, боратов, арсенатов, глицинов, пиперазинов и их смесей.
17. Способ по п.1, в котором указанное давление составляет примерно от 10 атм. примерно до 100 атм.
18. Способ по п.1, в котором указанный электролит регенерируется в реакторе посредством приведения в контакт указанной композиции электролита с паром, где указанная смесь дополнительно содержит, по меньшей мере, один ускоряющий агент, выбранный из группы, состоящей из аминов, боратов, арсенатов, глицинов, пиперазинов и их смесей.
19. Способ по п.18, в котором указанный металл выбирается из группы, состоящей из щелочных металлов и щелочноземельных металлов.
20. Способ по п.18, в котором регенерация осуществляется при давлении примерно от 0,3 атм. примерно до 200 атм.
21. Способ по п.15, в котором композиция, содержащая бикарбонат металла, из указанной стадии поглощения приводится в контакт с паром в реакторе для регенерации указанного карбоната металла.
22. Способ по п.15, в котором композиции, содержащие бикарбонат металла, как из указанной стадии поглощения, так и из указанной стадии производства водорода, вступают в контакт с паром в реакторе для регенерации указанного карбоната металла.
23. Способ по п.1, осуществляемый непрерывно.
24. Способ по п.1, осуществляемый в первом реакторе, указанный электролит регенерируется во втором реакторе, и указанный регенерированный электролит вводится в указанный первый реактор.
25. Способ по п.24, в котором регенерация осуществляется при температуре примерно от 85°C примерно до 200°C.
26. Способ по п.1, в котором:
(A) газообразный водород генерируется в реакторе, имеющем верхнюю часть и нижнюю часть, где указанное, по меньшей мере, одно окисляемое органическое вещество вводится в указанный реактор в точке, расположенной по существу посредине между указанной верхней частью и нижней частью;
(B) указанный щелочной раствор электролита, содержащий, по меньшей мере, один карбонат металла, вводится в реактор в точке, по существу, в верхней части указанного реактора, так что потоки указанного электролита и указанного газообразного водорода по существу являются противоточными друг другу, что приводит к получению, по меньшей мере, одной композиции бикарбоната металла;
(C) указанная, по меньшей мере, одна композиция бикарбоната металла регенерируется, и указанное, по меньшей мере, одно окисляемое органическое вещество включает в себя окисленный углеводород.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8318130B2 (en) | 2005-06-23 | 2012-11-27 | Cop Energy Technologies Llc | Hydrogen production using electrochemical reforming and electrolyte regeneration |
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