RU2016122895A - Бета-молекулярное сито, способ его получения и катализатор гидрирования, содержащий данное сито - Google Patents

Бета-молекулярное сито, способ его получения и катализатор гидрирования, содержащий данное сито Download PDF

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RU2016122895A
RU2016122895A RU2016122895A RU2016122895A RU2016122895A RU 2016122895 A RU2016122895 A RU 2016122895A RU 2016122895 A RU2016122895 A RU 2016122895A RU 2016122895 A RU2016122895 A RU 2016122895A RU 2016122895 A RU2016122895 A RU 2016122895A
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zeolite
amount
hydrogenation catalyst
alumina
carrier
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RU2016122895A
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RU2641702C2 (ru
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Чан ЛЮ
Фэнлай ВАН
Кэци ВАН
Янцзе ДУ
Хон ЧЖАО
Минхуа ГУАНЬ
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Чайна Петролиум энд Кемикал Корпорейшн
Фушун Ресерч Инститьют оф Петролиум энд Петрокемикалс, Синопек Корп
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Claims (21)

1. Цеолит β, имеющий молярное отношение SiO2/Al2O3, составляющее 30-150, предпочтительно 40-150 и более предпочтительно 60-120; количество некаркасного алюминия, составляющее не более 2%, предпочтительно не более 1%, исходя из общего количества алюминия; количество Si(0A1)-координированных атомов кремния не менее 95%, предпочтительно 96-99%, исходя из количества атомов кремния в каркасной структуре.
2. Цеолит β по п. 1, имеющий относительную кристалличность, составляющую 100%-140%.
3. Цеолит β по п. 1 или 2, содержащий кислотные центры, определенные с помощью ИК-спектроскопии, в количестве 0,1-0,5 ммоль/г, и кислотные центры умеренной силы в количестве не менее 80%, исходя из общего количества кислотных центров, определенных с помощью метода NH3-ТПД; предпочтительно содержащий кислотные центры, определенные с помощью ИК-спектроскопии, в количестве 0,15-0,45 ммоль/г, и кислотные центры умеренной силы в количестве 85-95%, исходя из общего количества кислотных центров, определенных методом NH3-ТПД.
4. Цеолит β по п. 1, имеющий содержание Na2O не более 0,15 мас. %, предпочтительно не более 0,10 мас. %.
5. Цеолит β по п. 1, имеющий площадь поверхности по БЭТ, составляющую 400-800 м2/г, и общий объем пор, составляющий 0,30-0,50 мл/г.
6. Способ получения цеолита β, включающий:
1) приведение исходного порошка цеолита β в контакт с движущимся водяным паром нормального давления при температуре 500-650°C в течение 5-10 ч, и
2) приведение продукта со стадии (1) в контакт с гексафторсиликатом аммония, затем фильтрацию, промывку и сушку с получением цеолита β.
7. Способ по п. 6, в котором на стадии (1) используют программирование температуры со скоростью нагрева 50-150°C/ч; когда достигают температуры 250-450°C, начинают введение водяного пара и продолжают нагрев до температуры 500-650°C, а затем поддерживают температуру в течение 5-10 ч.
8. Способ по п. 6 или 7, в котором на стадии (1) водяной пар пропускают через исходный порошок цеолита β с расходом 50-100 л/ч на килограмм исходного порошка цеолита β.
9. Способ по п. 6, в котором исходный порошок цеолита β на стадии (1) имеет молярное отношение SiO2/Al2O3, составляющее 22,5-28,5, и содержание Na2O, составляющее 1,0-3,0 мас. %.
10. Способ по п. 6, в котором концентрация водного раствора гексафторсиликата аммония, используемого на стадии (2), составляет 10-60 г/100 мл раствора и объемное отношение жидкость/твердое тело для водного раствора гексафторсиликата аммония и цеолита β составляет от 3:1 до 15:1.
11. Способ по п. 6, в котором условия приведения в контакт включают температуру 40-120°C и время 0,5-8,0 ч.
12. Катализатор гидрирования, содержащий активный в отношении гидрирования металлический компонент и носитель, где носитель содержит цеолит β по любому из пп. 1-5.
13. Катализатор гидрирования по п. 12, в котором носитель катализатора гидрирования дополнительно содержит оксид алюминия, при этом количество цеолита β составляет 5-40%, а количество оксида алюминия составляет 60-95%, исходя из массы носителя.
14. Катализатор гидрирования по п. 12, в котором носитель катализатора гидрирования дополнительно содержит аморфный алюмосиликат и оксид алюминия, при этом количество цеолита β составляет 3-20%, количество
аморфного алюмосиликата составляет 10-70%, а количество оксида алюминия составляет 15-70%, исходя из массы носителя.
15. Катализатор гидрирования по п. 14, в котором содержание SiO2 в аморфном алюмосиликате составляет 5-40 мас. %, аморфный алюмосиликат имеет объем пор, составляющий 0,6-1,1 мл/г, и площадь поверхности по БЭТ, составляющую 300-500 м2/г.
16. Катализатор гидрирования по п. 12, в котором носитель катализатора гидрирования дополнительно содержит цеолит Y и оксид алюминия, при этом количество цеолита β составляет 5-20%, количество цеолита Y составляет 10-40%, а количество оксида алюминия составляет 40-85%, исходя из массы носителя.
17. Катализатор гидрирования по п. 16, в котором цеолит Y имеет площадь поверхности по БЭТ, составляющую 850-950 м2/г, общий объем пор, составляющий 0,43-0,55 мл/г, молярное отношение SiO2/Al2O3, составляющее 20-150, параметр ячейки, составляющий 2,425-2,433 нм, и количество кислотных центров, определенных с помощью ИК-спектроскопии, составляющее 0,1-0,4 ммоль/г.
18. Катализатор гидрирования по любому из пп. 12-17, в котором активные в отношении гидрирования металлические компоненты представляют собой металл VIB группы и металл VIII группы; метал VIB группы представляет собой молибден и/или вольфрам, а металл VIII группы представляет собой кобальт и/или никель, и катализатор гидрирования содержит, исходя из общего количества катализатора, металл VIB группы в количестве 10-30 мас. %, исходя из его оксида, и металл VIII группы в количестве 4-8 мас. %, исходя из его оксида.
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