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RU2018109758A - Катализаторы для обработки выхлопного газа - Google Patents

Катализаторы для обработки выхлопного газа Download PDF

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Publication number
RU2018109758A
RU2018109758A RU2018109758A RU2018109758A RU2018109758A RU 2018109758 A RU2018109758 A RU 2018109758A RU 2018109758 A RU2018109758 A RU 2018109758A RU 2018109758 A RU2018109758 A RU 2018109758A RU 2018109758 A RU2018109758 A RU 2018109758A
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RU
Russia
Prior art keywords
catalyst
molecular sieve
exhaust gas
layer
catalyst according
Prior art date
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RU2018109758A
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English (en)
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RU2731218C2 (ru
RU2018109758A3 (ru
Inventor
Ксиаолай ЧЖЕНГ
Мишель ДЕЕБА
Ксиаофан ЙАНГ
Ки ФУ
Кнут ВАССЕРМАНН
Макото НАГАТА
Йасухару КАННО
Хироки НАКАЙАМА
Original Assignee
Басф Корпорейшн
Н.Е. Кемкэт Корпорейшн
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Publication of RU2018109758A publication Critical patent/RU2018109758A/ru
Publication of RU2018109758A3 publication Critical patent/RU2018109758A3/ru
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Publication of RU2731218C2 publication Critical patent/RU2731218C2/ru

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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
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    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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    • B01D53/9413—Processes characterised by a specific catalyst
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Claims (46)

1. Катализатор, эффективный для уменьшения NOx, углеводородов и монооксида углерода из выхлопного газа бензинового двигателя, причем катализатор содержит:
подложку, имеющую первый и второй материал, расположенные на ней, где первый материал является эффективным для катализа селективного каталитического восстановления оксидов азота в присутствии аммиака, а второй материал является эффективным для уменьшения углеводородов и монооксида углерода;
где выполняется одно или оба из следующего: а) первый материал содержит молекулярное сито, промотированное медью или железом, в количестве от около 0,01% до около 2% из расчета на оксид на основе массы молекулярного сита; и b) второй материал содержит по меньшей мере один оксид металла, выбранного из Ni, Fe, Mn, Со и Cu, на подложке, выбранной из оксида Се, Ce-Zr, Zr, Mn, Pr и их комбинаций;
где первый материал и второй материал по существу свободны от металла платиновой группы.
2. Катализатор по п. 1, в котором подложка представляет собой сотообразную подложку, и в котором первый материал и второй материал смешаны в одном слое на подложке.
3. Катализатор по п. 1, в котором первый материал находится в первом слое, а второй материал находится во втором слое на подложке.
4. Катализатор по п. 3, в котором подложка имеет длину по оси и конец выше по ходу потока и конец ниже по ходу потока, и в котором первый слой расположен на конце выше по ходу потока, а второй слой расположен на конце ниже по ходу потока.
5. Катализатор по п. 3, в котором подложка имеет длину по оси и конец выше по ходу потока и конец ниже по ходу потока, и в котором первый слой расположен на конце ниже по ходу потока, а второй слой расположен на конце выше по ходу потока.
6. Катализатор по п. 3, в котором первый слой находится непосредственно на подложке, а второй слой по меньшей мере частично покрывает первый слой.
7. Катализатор по п. 3, в котором второй слой находится непосредственно на подложке, а первый слой по меньшей мере частично покрывает второй слой.
8. Катализатор по п. 1, в котором подложка представляет собой фильтр с проточными стенками, имеющий входные проходы и выходные проходы.
9. Катализатор по п. 8, в котором первый материал расположен на входных проходах, а второй материал расположен на выходных проходах.
10. Катализатор по п. 8, в котором второй материал расположен на входных проходах, а первый материал расположен на выходных проходах.
11. Катализатор по п. 1, в котором молекулярное сито представляет собой мелкопористое молекулярное сито, имеющее максимальный размер кольца из восьми тетраэдрических атомов и двойной блок с 6-ти-членными кольцами (d6r).
12. Катализатор по п. 1, в котором молекулярное сито выбрано из группы, состоящей из типов каркасных структур AEI, AFT, AFX, СНА, ЕАВ, ЕМТ, ERI, FAU, GME, JSR, KFI, LEV, LTL, LTN, MOZ, MSO, MWW, OFF, SAS, SAT, SAV, SBS, SBT, SFW, SSF, SZR, TSC, и WEN.
13. Катализатор по п. 1, в котором молекулярное сито выбрано из группы, состоящей из типов каркасных структур СНА, AEI, AFX, ERI, KFI, и LEV.
14. Катализатор по п. 1, в котором молекулярное сито выбрано из группы, состоящей из типов каркасных структур AEI, СНА, и AFX.
15. Катализатор по п. 1, в котором молекулярное сито содержит молекулярное сито с типом каркасной структуры СНА.
16. Катализатор по п. 15, в котором молекулярное сито выбрано из SSZ-13, SSZ-62, природного шабазита, цеолита K-G, Linde D, Linde R, LZ-218, LZ-235, LZ-236, ZK-14, SAPO-34, SAPO-44, SAPO-47, ZYT-6 и Ti-SAPO-34.
17. Катализатор по п. 16, в котором молекулярное сито представляет собой SSZ-13, имеющий молярное соотношение диоксида кремния и оксида алюминия от около 10 до около 75.
18. Катализатор по п. 16, в котором молекулярное сито промотировано менее чем около 2 мас. % меди из расчета на оксид на основе массы медь-промотированного молекулярного сита.
19. Катализатор по п. 16, в котором молекулярное сито промотировано медью в количестве от около 0,5% до около 2 мас. % из расчета на оксид на основе медь-промотированного молекулярного сита, и где в FTP испытательном цикле, катализатор эффективен для превращения по меньшей мере около 30% оксидов азота в выхлопном газе посредством селективного каталитического восстановления оксидов азота в присутствии аммиака после воздействия условиями старения при прекращении подачи топлива двигателю при температуре от около 850°С в течение более чем десяти часов.
20. Катализатор по п. 1, в котором второй материал содержит по меньшей мере один оксид металла, выбранного из Ni, Fe, Mn, Со, и Cu.
21. Катализатор по п. 1, в котором второй материал содержит оксид Ni.
22. Катализатор по п. 1, в котором второй материал содержит оксид Ni, расположенный на подложке, содержащей оксид Се.
23. Катализатор по п. 18, в котором второй материал содержит оксид Ni, расположенный на подложке, содержащей оксид Се.
24. Катализатор по п. 23, в котором первый материал находится в первом слое, а второй материал находится во втором слое, где первый слой и второй слой расположены на подложке в виде зонированной конфигурации, и где первый слой покрывает второй слой.
25. Катализатор по п. 1, в котором по меньшей мере один оксид металла, выбранного из Ni, Fe, Mn, Со и Cu, присутствует в количестве от около 0,1 до около 30 мас. %, из расчета на оксид на основе массы подложки.
26. Катализатор по п. 25, в котором по меньшей мере один оксид металла, выбранного из Ni, Fe, Mn, Со и Cu, присутствует в количестве от около 2 до около 10 мас. %, из расчета на оксид на основе массы подложки.
27. Система для обработки выхлопного газа, включающая:
бензиновый двигатель, работающий при стехиометрических условиях;
трехкомпонентный катализатор превращения (TWC) ниже по ходу потока от двигателя, где катализатор TWC эффективен для превращения монооксида углерода, углеводородов и оксидов азота, и где катализатор TWC содержит по меньшей мере один металл платиновой группы, выбранный из платины, палладия и родия; и
второй катализатор, содержащий катализатор по любому из п.п. 1-26, расположенный ниже по ходу потока от катализатора TWC.
28. Система для обработки выхлопного газа по п. 27, в которой катализатор TWC расположен в первом вплотную смонтированном положении ниже по ходу потока от двигателя, а второй катализатор расположен во втором вплотную смонтированном положении непосредственно ниже по ходу потока от катализатора TWC.
29. Система для обработки выхлопного газа по п. 27, в которой катализатор TWC расположен в вплотную смонтированном положении ниже по ходу потока от двигателя, а второй катализатор расположен в положении поднизом ниже по ходу потока от катализатора TWC.
30. Система для обработки выхлопного газа по п. 27, в которой второй катализатор подвергается воздействию обедненного и обогащенного выхлопного газа, имеющего температуру выше 800°С.
31. Система для обработки выхлопного газа по п. 27, дополнительно включающая:
катализатор селективного каталитического восстановления (SCR) ниже по ходу потока от двигателя, причем катализатор SCR содержит медь и второе молекулярное сито, имеющее максимальный размер кольца из восьми тетраэдрических атомов и двойной блок с 6-ти-членными кольцами (d6r), где медь присутствует в количестве от около 0,01% до около 2 мас. % из расчета на оксид на основе массы второго молекулярного сита, и где SCR эффективен для катализа селективного каталитического восстановления оксидов азота в присутствии аммиака в условиях работы двигателя при стехиометрических условиях.
32. Система для обработки выхлопного газа по п. 31, в которой второе молекулярное сито включает молекулярное сито с типом каркасной структуры СНА.
33. Система для обработки выхлопного газа по п. 31, в которой второе молекулярное сито выбрано из SSZ-13, SSZ-62, природного шабазита, цеолита K-G, Linde D, Linde R, LZ-218, LZ-235, LZ-236, ZK-14, SAPO-34, SAPO-44, SAPO-47, ZYT-6, и Ti-SAPO-34.
34. Система для обработки выхлопного газа по п. 33, в которой второе молекулярное сито представляет собой SSZ-13, имеющий молярное соотношение диоксида кремния и оксида алюминия от около 10 до около 75.
35. Система для обработки выхлопного газа по п. 31, в которой двигатель производит выхлопной газ с температурой по меньшей мере 850°С.
36. Система для обработки выхлопного газа по п. 35, в которой второе молекулярное сито имеет площадь поверхности более 400 м2/г после воздействия выхлопного газа в течение 2 часов.
37. Система для обработки выхлопного газа по п. 35, в которой второе молекулярное сито имеет площадь состаренной поверхности после воздействия выхлопного газа в течение 2 часов около 75% от площади свежей поверхности, где площадь свежей поверхности представляет собой площадь поверхности молекулярного сита до воздействия выхлопного газа.
38. Способ обработки выхлопного газа из бензинового двигателя, работающего при стехиометрических условиях, включающий:
приведение в контакт выхлопного газа с трехкомпонентным катализатором (TWC), эффективным для превращения монооксида углерода, углеводородов и оксидов азота, где катализатор TWC содержит металл платиновой группы, выбранный из палладия и родия, и вторым катализатором, содержащим катализатор по любому из п.п. 1-26, где второй катализатор расположен ниже по ходу потока от катализатора TWC.
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