RU2003126180A - Катализатор и способ парового риформинга - Google Patents
Катализатор и способ парового риформинга Download PDFInfo
- Publication number
- RU2003126180A RU2003126180A RU2003126180/15A RU2003126180A RU2003126180A RU 2003126180 A RU2003126180 A RU 2003126180A RU 2003126180/15 A RU2003126180/15 A RU 2003126180/15A RU 2003126180 A RU2003126180 A RU 2003126180A RU 2003126180 A RU2003126180 A RU 2003126180A
- Authority
- RU
- Russia
- Prior art keywords
- catalyst
- reaction chamber
- hydrocarbon
- porous
- spinel
- Prior art date
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- 238000000034 method Methods 0.000 title claims 40
- 239000003054 catalyst Substances 0.000 title claims 32
- 238000000629 steam reforming Methods 0.000 title claims 8
- 238000006243 chemical reaction Methods 0.000 claims 48
- 239000004215 Carbon black (E152) Substances 0.000 claims 28
- 229930195733 hydrocarbon Natural products 0.000 claims 28
- 150000002430 hydrocarbons Chemical class 0.000 claims 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 16
- 239000011148 porous material Substances 0.000 claims 15
- 229910052596 spinel Inorganic materials 0.000 claims 13
- 239000011029 spinel Substances 0.000 claims 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 13
- 229910052703 rhodium Inorganic materials 0.000 claims 10
- 239000010948 rhodium Substances 0.000 claims 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 10
- 229910052739 hydrogen Inorganic materials 0.000 claims 9
- 239000001257 hydrogen Substances 0.000 claims 9
- 229910052741 iridium Inorganic materials 0.000 claims 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims 8
- 229910052751 metal Inorganic materials 0.000 claims 8
- 239000002184 metal Substances 0.000 claims 8
- 229910052759 nickel Inorganic materials 0.000 claims 8
- 229910052763 palladium Inorganic materials 0.000 claims 8
- 229910052697 platinum Inorganic materials 0.000 claims 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 7
- 239000000126 substance Substances 0.000 claims 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 6
- 229910052707 ruthenium Inorganic materials 0.000 claims 6
- 150000002431 hydrogen Chemical class 0.000 claims 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 2
- 239000000395 magnesium oxide Substances 0.000 claims 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 2
- 239000006262 metallic foam Substances 0.000 claims 2
- 229910052726 zirconium Inorganic materials 0.000 claims 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910020068 MgAl Inorganic materials 0.000 claims 1
- 229910039444 MoC Inorganic materials 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000000446 fuel Substances 0.000 claims 1
- 230000016507 interphase Effects 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000002407 reforming Methods 0.000 claims 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims 1
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- 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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- B01J21/005—Spinels
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Claims (50)
1. Способ парового риформинга, включающий прохождение водяного пара и углеводорода через реакционную камеру, где реакционная камера содержит шпинель-содержащий катализатор, который имеет активные участки на поверхности, содержащие вещество, выбранное из группы, состоящей из родия, иридия, никеля, палладия, платины, рутения, карбида группы IVb и их комбинаций, где скорость прохождения водяного пара и углеводорода контролируют таким образом, чтобы время пребывания в реакционной камере составляло менее 0,1 с, где температура в реакционной камере находится в диапазоне от 500 до 1000°С, где после прохождения через реакционную камеру, по меньшей мере, 60% вышеуказанного углеводорода превращают в продукты.
2. Способ по п. 1, где селективность по водороду составляет, по меньшей мере, 60%.
3. Способ по п. 2, где активные участки на поверхности катализатора содержат родий.
4. Способ по п. 2, отличающийся тем, что выход водорода составляет, по меньшей мере, 0,7 ммоль·с-1 см-3.
5. Способ по п. 2, отличающийся тем, что время контакта составляет от 10 до 25 мс.
6. Способ по п. 5, где углеводород представляет собой C1-С10-алкан.
7. Способ по п. 5, где углеводород представляет собой метан, и, по меньшей мере, 95% метана превращают в продукты с селективностью по водороду, составляющей, по меньшей мере, 95%.
8. Катализатор, содержащий:
(а) первую пористую структуру с пористой поверхностью и размером пор, составляющим, по меньшей мере, около 0,1 мкм;
(b) пористый межфазный слой, который содержит шпинель со второй пористой поверхностью и размером пор менее указанного выше размера пор первой пористой структуры, причем этот пористый межфазный слой имеет толщину менее 4 мм и расположен на указанной выше пористой структуре;
(c) катализатор риформинга, выбранный из группы, состоящей из родия, иридия, никеля, палладия, платины, рутения, карбида группы IVb и их комбинаций, расположенный на второй пористой поверхности.
9. Катализатор по п. 8, где карбид выбран из группы, включающей карбид вольфрама, карбид молибдена и их комбинации.
10. Катализатор по п. 8, где пористый носитель представляет собой металлические пену или войлок.
11. Катализатор по п. 10, где катализатор имеет пористость 30-95% и где, по меньшей мере, 50% объема пор составляют поры, размер которых варьирует от 0,3 до 200 мкм.
12. Катализатор, содержащий слой оксида алюминия, металл, находящийся на поверхности катализатора, слой шпинели, расположенный между слоем оксида алюминия и металлом, отличающийся тем, что слой шпинели находится в прямом контакте со слоем оксида алюминия, и металл выбран из группы, включающей родий, иридий, никель, платину, палладий и рутений.
13. Катализатор по п. 12, где слой оксида алюминия представляет собой оксид алюминия, нанесенный на пористый металлический носитель.
14. Катализатор по п. 12, где слой шпинели расположен между слоем оксида магния и слоем оксида алюминия, и указанный выше металл расположен на слое оксида магния.
15. Катализатор по п. 12, который не демонстрирует пониженную конверсию углеводорода через 1000 ч парового риформинга при соотношении водяного пара к углероду, равном 3, времени контакта 20 мс, давлении 120 фунтов на квадратный дюйм и температуре 850°С.
16. Катализатор по п. 12, где слой шпинели имеет площадь поверхности 20-500 м2/г.
17. Катализатор по п. 12, где шпинель имеет формулу MgAl2O4.
18. Катализатор по п. 12, где слой шпинели имеет толщину менее 40 мкм.
19. Способ парового риформинга, включающий прохождение водяного пара и углеводорода через реакционную камеру, где реакционная камера содержит шпинель-содержащий катализатор, который имеет активные участки на поверхности, содержащие вещество, выбранное из группы, состоящей из родия, иридия, никеля, палладия, платины, рутения, карбида группы VIb и их комбинаций, где скорость прохождения водяного пара и углеводорода контролируют таким образом, чтобы время пребывания в реакционной камере составляло менее 0,1 с, где температура в реакционной камере находится в диапазоне от 500 до 1000°С, и где получают, по меньшей мере, 0,5 ммоль газообразного водорода в секунду на кубический сантиметр объема реакционной камеры.
20. Способ по п. 19, где конверсия углеводорода составляет, по меньшей мере, 50%.
21. Способ по п. 20, где селективность по водороду составляет, по меньшей мере, 50%.
22. Способ по п. 21, где получают, по меньшей мере, 0,7 ммоль газообразного водорода в секунду на кубический сантиметр объема реакционной камеры.
23. Способ по п. 22, где температура в реакционной камере составляет 650-900°С.
24. Способ по п. 23, где углеводород представляет собой в основном метан и где конверсия углеводорода составляет, по меньшей мере, 90% равновесной конверсии.
25. Способ по п. 24, где время контакта варьирует от 5 до 100 мс.
26. Способ по п. 23, где время контакта составляет менее 25 мс и где селективность по водороду составляет, по меньшей мере, 85%.
27. Способ по п. 26, где получают от 0,5 до 2 ммоль газообразного водорода в секунду на кубический сантиметр объема реакционной камеры.
28. Способ по п. 22, где конверсия углеводорода составляет, по меньшей мере, 90%.
29. Способ по п. 28, где селективность по водороду составляет, по меньшей мере, 85% и где селективность по СО не изменяется через 7 часов непрерывной реакции.
30. Способ парового риформинга, включающий прохождение водяного пара и углеводорода через реакционную камеру, где реакционная камера содержит шпинель-содержащий катализатор, который имеет активные участки на поверхности, содержащие вещество, выбранное из группы, состоящей из родия, иридия, никеля, палладия, платины, рутения, карбида группы VIb и их комбинаций, где скорость прохождения водяного пара и углеводорода контролируют таким образом, чтобы время пребывания в реакционной камере составляло менее 0,1 с, где температура в реакционной камере находится в диапазоне от 500 до 1000°С, где после прохождения через реакционную камеру, по меньшей мере, 50% вышеуказанного углеводорода превращают в продукты.
31. Способ парового риформинга, включающий прохождение водяного пара и углеводорода через реакционную камеру, где реакционная камера содержит катализатор, который имеет активные участки на поверхности, содержащие вещество, выбранное из группы, состоящей из родия, иридия, никеля, палладия, платины, рутения, карбида группы VIb и их комбинаций, где скорость прохождения водяного пара и углеводорода контролируют таким образом, чтобы время пребывания в реакционной камере составляло менее около 0,1 с, где после прохождения через реакционную камеру конверсия углеводорода достигает, по меньшей мере, 50% равновесной конверсии.
32. Способ по п. 31, где реакционная камера содержит катализатор, который имеет активные участки на поверхности, содержащие вещество, выбранное из группы, состоящей из родия, иридия, никеля, палладия, платины и их комбинаций, и где, по меньшей мере, 50% указанного выше углеводорода превращают в продукты после прохождения через реакционную камеру.
33. Способ по п. 32, где температура в реакционной камере находится в диапазоне от 500°С до 1000°С.
34. Способ по п. 32, где катализатор содержит шпинель в качестве носителя.
35. Способ по п. 31, где катализатор содержит циркониевый носитель.
36. Способ по п. 31, где катализатор содержит первую пористую структуру с пористой поверхностью и размером пор, составляющим, по меньшей мере, 0,1 мкм, и пористый межфазный слой со второй пористой поверхностью и размером пор, который меньше размера пор первой пористой структуры.
37. Способ по п. 36, где пористый межфазный слой представляет собой шпинель.
38. Способ по п. 36, где первая пористая структура представляет собой металлическую пену или металлический войлок, а пористый межфазный слой представляет собой оксид алюминия.
39. Способ по п. 32, где катализатор имеет пористость от 30 до 95%, и, по меньшей мере, 50% объема пор катализатора составляют поры, размер которых варьирует от 0.3 до 200 мкм.
40. Способ по п. 33, где конверсия углеводорода составляет, по меньшей мере, 90% равновесной конверсии, и селективность по водороду составляет, по меньшей мере, 85%.
41. Способ по п. 40, где катализатор содержит активные участки на поверхности, содержащие родий.
42. Способ парового риформинга, включающий прохождение водяного пара и углеводорода через реакционную камеру, содержащую катализатор, включающий первую пористую структуру с пористой поверхностью и размером пор, составляющим, по меньшей мере, 0,1 мкм, пористый межфазный слой со второй пористой поверхностью и размером пор, который меньше размера пор первой пористой структуры, и металлический катализатор.
43. Способ по п. 42, где скорость прохождения водяного пара и углеводорода контролируют таким образом, чтобы время пребывания в реакционной камере составляло менее примерно 0,1 с, где после прохождения через реакционную камеру конверсия углеводорода составляет, по меньшей мере, 50% равновесной конверсии.
44. Способ по п. 43, где катализатор имеет активные участки на поверхности, содержащие вещество, выбранное из группы, состоящей из родия, иридия, никеля, палладия, платины и их комбинаций.
45. Способ по п. 43, где пористый межфазный слой представляет собой вещество, выбранное из группы, состоящей из оксида алюминия, шпинели и циркония.
46. Способ парового риформинга, включающий прохождение водяного пара и углеводорода через реакционную камеру, содержащую катализатор, имеющий пористость от 30 до 95% и, по меньшей мере, 50% объема пор которого составляют поры, размер которых варьирует от 0,3 до 200 мкм, и включающий металлический катализатор.
47. Способ по п. 42, где скорость прохождения водяного пара и углеводорода контролируют таким образом, чтобы время контакта в реакционной камере варьировало от 5 до 100 мс, и где после прохождения через реакционную камеру конверсия углеводорода составляет, по меньшей мере, 50% равновесной конверсии.
48. Способ по п. 46, где выход водорода составляет, по меньшей мере, 0,7 ммоль·с-1 см-3.
49. Способ по п. 31, где выход водорода составляет от 0,5 до 2 ммоль·с-1 см-3 при времени контакта от 10 до 25 мс.
50. Способ по п. 31, где углеводород представляет собой синтетическое топливо, полученное в результате процесса Фишера-Тропша и где после прохождения через реакционную камеру конверсия углеводорода достигает, по меньшей мере, 70% равновесной конверсии.
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US09/788293 | 2001-02-16 | ||
US09/788,293 US6607678B2 (en) | 1999-08-17 | 2001-02-16 | Catalyst and method of steam reforming |
US10/076,881 US7335346B2 (en) | 1999-08-17 | 2002-02-13 | Catalyst and method of steam reforming |
US10/07681 | 2002-02-13 |
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EP (1) | EP1360145A2 (ru) |
JP (1) | JP2005502570A (ru) |
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AU (1) | AU2002248435A1 (ru) |
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CA (1) | CA2438714C (ru) |
MX (1) | MXPA03007345A (ru) |
NO (1) | NO20033482L (ru) |
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GB0125035D0 (en) | 2001-10-18 | 2001-12-12 | Accentus Plc | Catalytic reactor |
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GB0129054D0 (en) | 2001-12-05 | 2002-01-23 | Accentus Plc | Catalytic reactor and process |
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EP1795260A1 (fr) | 2005-12-07 | 2007-06-13 | L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Catalyseur constitué d'un support solide, d'un oxyde, et d'une phase active métallique greffée sur l'oxyde, procédé pour sa préparation et application |
CN1323756C (zh) * | 2005-12-28 | 2007-07-04 | 浙江大学 | 纳米碳化钼/三氧化二铝复合催化剂的制备方法 |
EP1808229A1 (en) | 2006-01-12 | 2007-07-18 | L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Process for the preparation of a catalytic specie using electro-deposition. |
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KR100903271B1 (ko) * | 2007-10-11 | 2009-06-17 | 한국에너지기술연구원 | 자열개질에 의한 천연가스로부터 피셔-트롭쉬 액화공정용합성가스(h2/co≒2)제조에 사용되는 개질촉매 및 그제조방법과 이를 이용한 피셔-트롭쉬 액화공정용합성가스의 제조방법 |
WO2009119748A1 (ja) * | 2008-03-26 | 2009-10-01 | 京セラ株式会社 | 多孔質セラミック部材およびその製法ならびにフィルタ |
WO2011065187A1 (ja) * | 2009-11-25 | 2011-06-03 | 株式会社エフ・シ-・シ- | 触媒担体又は触媒及びその製造方法 |
KR101437072B1 (ko) * | 2011-12-26 | 2014-09-03 | 한국화학연구원 | 효율적인 이산화탄소 전환 촉매 및 이의 제조 방법 |
JP6198032B2 (ja) * | 2012-11-21 | 2017-09-20 | 日産自動車株式会社 | 水素生成用触媒及び水素生成用触媒を用いたシステム |
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CN108636414A (zh) * | 2018-05-23 | 2018-10-12 | 广东工业大学 | 一种组合物、双金属催化剂的制备方法及其应用 |
KR102436299B1 (ko) | 2020-09-16 | 2022-08-26 | 울산대학교 산학협력단 | 다공성 알루미나 담체에 담지된 니켈을 포함하는 복합체 및 이의 제조방법 |
JP2023546069A (ja) | 2020-10-13 | 2023-11-01 | エクソンモービル テクノロジー アンド エンジニアリング カンパニー | サイクル・フロー・リアクターにおける改質用触媒系 |
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- 2002-02-15 KR KR10-2003-7010802A patent/KR20030077629A/ko not_active Application Discontinuation
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NO20033482D0 (no) | 2003-08-06 |
AU2002248435A1 (en) | 2002-09-04 |
US20030017105A1 (en) | 2003-01-23 |
WO2002066371A3 (en) | 2003-03-06 |
NO20033482L (no) | 2003-10-07 |
BR0207275A (pt) | 2004-09-14 |
CA2438714A1 (en) | 2002-08-29 |
US7335346B2 (en) | 2008-02-26 |
JP2005502570A (ja) | 2005-01-27 |
WO2002066371A2 (en) | 2002-08-29 |
CA2438714C (en) | 2012-07-17 |
EP1360145A2 (en) | 2003-11-12 |
KR20030077629A (ko) | 2003-10-01 |
MXPA03007345A (es) | 2003-12-04 |
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