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RU2014118792A - METHOD FOR PRODUCING HYDROGEN AND OXYGEN BY ELECTROLYSIS OF WATER VAPOR - Google Patents

METHOD FOR PRODUCING HYDROGEN AND OXYGEN BY ELECTROLYSIS OF WATER VAPOR Download PDF

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RU2014118792A
RU2014118792A RU2014118792/04A RU2014118792A RU2014118792A RU 2014118792 A RU2014118792 A RU 2014118792A RU 2014118792/04 A RU2014118792/04 A RU 2014118792/04A RU 2014118792 A RU2014118792 A RU 2014118792A RU 2014118792 A RU2014118792 A RU 2014118792A
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anode
cathode
proton
electrolyte
oxidation
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Беатрис САЛА
Фредерик ГРАССЕ
Оливьер ЛАКРУА
Абделкадер СИРА
Камал РАМУНИ
Мишель КЕДДАМ
Хисаси ТАКЕНУТИ
Доминик ГЕРИО
Баруди БЕНДЖЕРИУ
Филипп КОЛОМБАН
ДЕР ЛИ Ари ВАН
Хосе Грегорио САНЧЕС
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Арева
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
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    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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Abstract

1. Способ получения адсорбатов водорода и кислорода электролизом водяного пара при 200°C-800°C с применением электролитической ячейки (30), включающей твердый электролит (31), который изготовлен из проводящей протоны керамики, при этом указанный электролит (31) расположен между анодом (32) и катодом (33), причем каждый из указанных анода и катода включает проводящую протоны керамику, а соотношение электроактивной поверхности к геометрической поверхности каждого из них равно по меньшей мере 10, при этом указанный способ включает следующие этапы:- циркуляция тока между анодом (32) и катодом (33), при этом плотность тока составляет не менее 500 мА/см;- введение воды в виде пара, подаваемого под давлением к аноду (32);- окисление указанной воды в виде пара на аноде (32);- получение высоко реакционноспособного кислорода на аноде (32) после указанного окисления;- получение протонированных частиц в электролите (31) после указанного окисления;- миграция указанных протонированных частиц в электролите (31);- восстановление указанных протонированных частиц на поверхности катода (33) в виде реакционноспособных атомов водорода.2. Способ по предыдущему пункту, отличающийся тем, что указанное соотношение между электроактивной поверхностью и геометрической поверхностью указанных катода и анода составляет не менее 100.3. Способ по одному из предыдущих пунктов, отличающийся тем, что указанная плотность тока составляет не менее 1 A/см.4. Способ по п. 1, отличающийся тем, что парциальное и относительное давление водяного пара предпочтительно составляет не менее 1 бар и предпочтительно не менее 10 бар.5. Способ по п. 1, отличающийся тем, что циркуляция тока происход1. A method of producing hydrogen and oxygen adsorbates by electrolysis of water vapor at 200 ° C-800 ° C using an electrolytic cell (30) including a solid electrolyte (31), which is made of proton-conducting ceramics, while said electrolyte (31) is located between anode (32) and cathode (33), and each of said anode and cathode includes proton-conducting ceramics, and the ratio of the electroactive surface to the geometric surface of each of them is at least 10, while the specified method includes the following steps: - current circulation between anode (32) and cathode (33), while the current density is not less than 500 mA / cm; - introduction of water in the form of steam supplied under pressure to the anode (32); - oxidation of the specified water in the form of steam at the anode (32) ; - obtaining highly reactive oxygen at the anode (32) after said oxidation; - obtaining protonated particles in electrolyte (31) after said oxidation; - migration of said protonated particles into the electrolyte roll (31); - reduction of the indicated protonated particles on the cathode surface (33) in the form of reactive hydrogen atoms. 2. The method according to the previous paragraph, characterized in that said ratio between the electroactive surface and the geometric surface of said cathode and anode is at least 100.3. The method according to one of the previous paragraphs, characterized in that the specified current density is at least 1 A / cm. 4. A method according to claim 1, characterized in that the partial and relative pressure of the water vapor is preferably at least 1 bar and preferably at least 10 bar. The method according to claim 1, characterized in that the current circulation occurs

Claims (15)

1. Способ получения адсорбатов водорода и кислорода электролизом водяного пара при 200°C-800°C с применением электролитической ячейки (30), включающей твердый электролит (31), который изготовлен из проводящей протоны керамики, при этом указанный электролит (31) расположен между анодом (32) и катодом (33), причем каждый из указанных анода и катода включает проводящую протоны керамику, а соотношение электроактивной поверхности к геометрической поверхности каждого из них равно по меньшей мере 10, при этом указанный способ включает следующие этапы:1. The method of producing hydrogen and oxygen adsorbates by electrolysis of water vapor at 200 ° C-800 ° C using an electrolytic cell (30) comprising a solid electrolyte (31), which is made of proton-conducting ceramic, said electrolyte (31) being located between an anode (32) and a cathode (33), each of which anode and cathode include proton-conducting ceramics, and the ratio of the electroactive surface to the geometric surface of each of them is at least 10, while this method includes the following steps: - циркуляция тока между анодом (32) и катодом (33), при этом плотность тока составляет не менее 500 мА/см2;- current circulation between the anode (32) and the cathode (33), while the current density is at least 500 mA / cm 2 ; - введение воды в виде пара, подаваемого под давлением к аноду (32);- the introduction of water in the form of steam supplied under pressure to the anode (32); - окисление указанной воды в виде пара на аноде (32);- oxidation of the indicated water in the form of steam at the anode (32); - получение высоко реакционноспособного кислорода на аноде (32) после указанного окисления;- obtaining highly reactive oxygen at the anode (32) after the specified oxidation; - получение протонированных частиц в электролите (31) после указанного окисления;- obtaining protonated particles in the electrolyte (31) after the specified oxidation; - миграция указанных протонированных частиц в электролите (31);- migration of these protonated particles in the electrolyte (31); - восстановление указанных протонированных частиц на поверхности катода (33) в виде реакционноспособных атомов водорода.- restoration of these protonated particles on the surface of the cathode (33) in the form of reactive hydrogen atoms. 2. Способ по предыдущему пункту, отличающийся тем, что указанное соотношение между электроактивной поверхностью и геометрической поверхностью указанных катода и анода составляет не менее 100.2. The method according to the preceding paragraph, characterized in that said ratio between the electroactive surface and the geometric surface of said cathode and anode is at least 100. 3. Способ по одному из предыдущих пунктов, отличающийся тем, что указанная плотность тока составляет не менее 1 A/см2.3. The method according to one of the preceding paragraphs, characterized in that the specified current density is at least 1 A / cm 2 . 4. Способ по п. 1, отличающийся тем, что парциальное и относительное давление водяного пара предпочтительно составляет не менее 1 бар и предпочтительно не менее 10 бар.4. The method according to p. 1, characterized in that the partial and relative pressure of water vapor is preferably at least 1 bar and preferably at least 10 bar. 5. Способ по п. 1, отличающийся тем, что циркуляция тока происходит между анодом и катодом, каждый из которых изготовлен из металлокерамики, включающей смесь проводящей протоны керамики и проводникового материала.5. The method according to p. 1, characterized in that the current circulation occurs between the anode and cathode, each of which is made of cermet, comprising a mixture of proton-conducting ceramics and conductive material. 6. Способ по п. 1, отличающийся тем, что указанный проводниковый материал представляет собой пассивируемый материал с высокой температурой плавления, способный содержать по меньшей мере 40% хрома.6. The method according to p. 1, characterized in that said conductive material is a passivated material with a high melting point, capable of containing at least 40% chromium. 7. Способ по п. 1, отличающийся тем, что циркуляция тока происходит между анодом и катодом, каждый из которых включает проводящую протоны керамику, образованную из перовскита, легированного лантаноидом с одной или несколькими степенями окисления.7. The method according to p. 1, characterized in that the current circulation occurs between the anode and cathode, each of which includes proton-conducting ceramics formed from perovskite doped with lanthanide with one or more oxidation states. 8. Способ по п. 1, отличающийся тем, что он включает следующие этапы:8. The method according to p. 1, characterized in that it includes the following steps: - введение диоксида углерода CO2 и/или монооксида углерода CO на катоде электролитической ячейки;- the introduction of carbon dioxide CO 2 and / or carbon monoxide CO at the cathode of the electrolytic cell; - восстановление CO2 и/или CO, введенного на катоде, посредством указанных полученных реакционноспособных атомов водорода;- reduction of CO 2 and / or CO introduced at the cathode by means of the obtained reactive hydrogen atoms obtained; - образование соединений типа CXHyOZ, где x≥1, 0<y≤(2x+2) и 0≤z≤2x, после восстановления CO2 и/или CO.- the formation of compounds of type CXHyOZwhere x≥1, 0 <y≤ (2x + 2) and 0≤z≤2x, after recovery of CO2 and / or CO. 9. Способ по п. 1, отличающийся тем, что он включает следующие этапы:9. The method according to p. 1, characterized in that it includes the following steps: - введение азотсодержащих соединений на катоде электролитической ячейки;- the introduction of nitrogen-containing compounds at the cathode of the electrolytic cell; - восстановление указанных азотсодержащих соединений, введенных на катоде, посредством указанных полученных реакционноспособных атомов водорода.- the restoration of these nitrogen-containing compounds introduced at the cathode, through these obtained reactive hydrogen atoms. 10. Способ по п. 1, отличающийся тем, что указанные азотсодержащие соединения представляют собой соединения типа NOx, где x≥1, при этом указанный способ включает этап образования соединений типа NtOyHz, где t составляет не менее 1, y не менее 0, а z не менее ноля, после восстановления NOx.10. The method according to p. 1, characterized in that these nitrogen-containing compounds are compounds of the type NO x , where x≥1, while this method includes the step of forming compounds of the type N t O y H z , where t is at least 1, y is not less than 0, and z is not less than zero, after the reduction of NO x . 11. Способ по п. 9, отличающийся тем, что указанные азотсодержащие соединения представляют собой соединения N2, при этом указанный способ включает этап образования соединений типа NxHy, где x ≥1 и y≥0, который приводит к образованию NH3 после восстановления N2.11. The method according to p. 9, characterized in that said nitrogen-containing compounds are N 2 compounds, said method comprising the step of forming compounds of the type N x H y , where x ≥ 1 and y≥0, which leads to the formation of NH 3 after recovery of N 2 . 12. Способ по п. 1, отличающийся тем, что указанные реакционноспособные атомы водорода применяют для проведения этапа гидрокрекинга на катоде.12. The method according to p. 1, characterized in that the said reactive hydrogen atoms are used to carry out the hydrocracking step at the cathode. 13. Способ по п. 1, отличающийся тем, что указанные реакционноспособные атомы водорода применяют для превращения ароматических соединений на катоде.13. The method according to p. 1, characterized in that the said reactive hydrogen atoms are used to convert aromatic compounds at the cathode. 14. Способ по п. 1, отличающийся тем, что он включает этап, заключающийся в осуществлении реакции указанного высоко реакционноспособного кислорода с соединением, введенным на аноде, таким образом, что последнее подвергается окислению.14. The method according to p. 1, characterized in that it includes a step consisting in the implementation of the reaction of the specified highly reactive oxygen with the compound introduced on the anode, so that the latter undergoes oxidation. 15.Электролитическая ячейка для осуществления способа по одному из предыдущих пунктов, включающая:15. The electrolytic cell for implementing the method according to one of the preceding paragraphs, including: - твердый электролит, изготовленный из проводящей протоны керамики;- solid electrolyte made from proton-conducting ceramics; - анод, включающий проводящую протоны керамику, при этом каждый из указанных анода и катода имеет соотношение между электроактивной поверхностью и геометрической поверхностью, равное по меньшей мере 10;- an anode comprising proton-conducting ceramics, wherein each of said anode and cathode has a ratio between the electroactive surface and the geometric surface of at least 10; - катод, содержащий проводящую протоны керамику, при этом указанный электролит расположен между указанным анодом и указанным катодом;- a cathode containing proton-conducting ceramics, wherein said electrolyte is located between said anode and said cathode; - средства для введения воды в виде пара, который подают под давлением на аноде;- means for introducing water in the form of steam, which is supplied under pressure at the anode; - средства для инициации циркуляции тока между анодом и катодом, при этом плотность тока составляет не менее 500 мА/см2. - means for initiating the circulation of current between the anode and cathode, while the current density is at least 500 mA / cm 2 .
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