RU2003126180A - Катализатор и способ парового риформинга - Google Patents

Катализатор и способ парового риформинга Download PDF

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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
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Prior art keywords
catalyst
reaction chamber
hydrocarbon
porous
spinel
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RU2003126180/15A
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English (en)
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Анна Ли И. ТОНКОВИЧ (US)
Анна Ли И. ТОНКОВИЧ
Йонг ВАНГ (US)
Йонг Ванг
Дэвид П. ВАНДЕРВЕЙЛ (US)
Дэвид П. ВАНДЕРВЕЙЛ
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Баттелл Мемориал Инститьют (US)
Баттелл Мемориал инститьют
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Priority claimed from US09/788,293 external-priority patent/US6607678B2/en
Application filed by Баттелл Мемориал Инститьют (US), Баттелл Мемориал инститьют filed Critical Баттелл Мемориал Инститьют (US)
Publication of RU2003126180A publication Critical patent/RU2003126180A/ru

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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 C110-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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