EA026722B1 - Способ получения катализатора на основе модифицированного фосфором цеолита и применение такого катализатора - Google Patents

Способ получения катализатора на основе модифицированного фосфором цеолита и применение такого катализатора Download PDF

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EA026722B1
EA026722B1 EA201490358A EA201490358A EA026722B1 EA 026722 B1 EA026722 B1 EA 026722B1 EA 201490358 A EA201490358 A EA 201490358A EA 201490358 A EA201490358 A EA 201490358A EA 026722 B1 EA026722 B1 EA 026722B1
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Eurasian Patent Office
Prior art keywords
zeolite
phosphorus
catalyst
steam
stage
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EA201490358A
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English (en)
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EA201490358A1 (ru
Inventor
Николай Нестеренко
Дельфине Миноукс
Синди Адам
Жан-Пьер Дат
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Тотал Ресерч & Технолоджи Фелай
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Publication of EA201490358A1 publication Critical patent/EA201490358A1/ru
Publication of EA026722B1 publication Critical patent/EA026722B1/ru

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    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
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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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B01J29/655—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract

Заявляемое изобретение в первом варианте реализации относится к способу получения катализатора на основе модифицированного фосфором цеолита, включающему следующие стадии в указанной последовательности: а) обеспечить цеолит, в структуру которого входит хотя бы одно десятичленное кольцо; b) обработать указанный цеолит паром, с) ввести в цеолит по меньшей мере 0,1 мас.% фосфора, применяя сухую импрегнацию или парофазное химическое осаждение, d) смешать цеолит, указанный на стадии с), как минимум с одним из связующих компонентов и структуронаправляющих агентов; е) сформовать полученную смесь; i) обработать модифицированный фосфором цеолит паром - стадия, называемая также приведением в равновесное состояние. Во втором варианте реализации фосфор может быть введён любым способом, и на стадии i) показатель интенсивности парообработки (X) составляет по меньшей мере 2. Во втором варианте реализации модифицированный фосфором цеолит подвергают обработке паром при температуре выше 625°С, преимущественно в диапазоне от 700 до 800°С. Настоящее изобретение также относится к применению указанного катализатора для дегидратации спиртов, крекинга олефинов с выделением более лёгких олефинов, в конверсии МТО и алкилировании ароматических углеводородов спиртами с олефинами и/или спиртами.

Description

С07С1/20 (2006.01)
(54) СПОСОБ ПОЛУЧЕНИЯ КАТАЛИЗАТОРА НА ОСНОВЕ МОДИФИЦИРОВАННОГО ФОСФОРОМ ЦЕОЛИТА И ПРИМЕНЕНИЕ ТАКОГО КАТАЛИЗАТОРА
(31) 11176391.8 (56) ЕР-А1-2348004
(32) 2011.08.03 ЧО-А1-2009098262 ЕР-А1-2082802
(33) ЕР ЕР-А2-0511013
(43) 2014.06.30 υδ-Α-4356338
(86) РСТ/ЕР2012/064582 (87) \\О 2013/017499 2013.02.07

Claims (16)

  1. ФОРМУЛА ИЗОБРЕТЕНИЯ
    1. Способ получения катализатора на основе модифицированного фосфором цеолита, включающий следующие стадии в указанной последовательности:
    a) обеспечивают цеолит, в структуру которого входит хотя бы одно десятичленное кольцо;
    b) обрабатывают указанный цеолит паром;
    c) вводят в цеолит по меньшей мере 0,1 мас.% источника фосфора, применяя сухую импрегнацию или парофазное химическое осаждение;
    ά) смешивают цеолит, указанный на стадии с), как минимум с одним из связующих компонентов и структуронаправляющих агентов;
    е) формуют полученную смесь;
    ί) обрабатывают модифицированный фосфором цеолит паром в диапазоне температур от 625 до 870°С.
  2. 2. Способ по п.1, характеризующийся тем, что введение источника фосфора на стадии с) выполняют первичным смачиванием или импрегнацией первичным смачиванием.
  3. 3. Способ по п.1, характеризующийся тем, что обработку паром на стадии ί) выполняют в диапазоне температур от 700 до 800°С.
  4. 4. Способ получения катализатора на основе модифицированного фосфором цеолита, включающий следующие стадии в указанной последовательности:
    a) обеспечивают цеолит, в структуру которого входит хотя бы одно десятичленное кольцо;
    b) обрабатывают указанный цеолит паром;
    c) вводят в цеолит по меньшей мере 0,1 мас.% источника фосфора;
    ά) смешивают цеолит, указанный в стадии с), как минимум с одним из связующих компонентов и структуронаправляющих агентов;
    е) формуют полученную смесь;
    ί) выполняют обработку модифицированного фосфором цеолита паром при показателе интенсивности парообработки (X) не менее 2, при этом X (интенсивность паровой обработки) = Уэксперим. услАстанд. усл., где стандартным условием для деалюминизации (V) является пропаривание при 600°С и 100%-ной концентрации пара при атмосферном давлении в течение 2 ч.
  5. 5. Способ по п.4, характеризующийся тем, что обработку паром на стадии ί) выполняют в диапазоне температур от 625 до 870°С.
  6. 6. Способ по любому из предыдущих пунктов, характеризующийся тем, что формованный цеолит (или молекулярное сито) на стадии Ь) содержит меньше 100 вмд (весовая миллионная доля/\\ррт) натрия.
  7. 7. Способ по любому из пп.1-5, характеризующийся тем, что формованный цеолит (или молекулярное сито) на стадии Ь) содержит меньше 1000 вмд натрия.
  8. 8. Способ по любому из предыдущих пунктов, для осуществления которого цеолит выбирают из ΜΡΙ, ΜΤΤ, РЕК, ΜΕΕ, ΤΟΝ, ΜΑΑ, ΕυΟ, ΜΡδ, преимущественно используют ΖδΜ-5 с атомным отношением δί/Ά1 в пределах от 11 до 30, полученный без прямого введения органического темплата (шабло- 12 026722 на).
  9. 9. Способ по п.8, характеризующийся тем, что в качестве цеолита используют МЫ с атомным отношением δί/Άί в пределах от 30 до 200.
  10. 10. Способ по любому из предыдущих пунктов, характеризующийся тем, что содержание фосфора в катализаторе составляет от 0,5 до 30 мас.%.
  11. 11. Способ по любому из предшествующих пунктов, характеризующийся тем, что на стадии й) дополнительно вводят металлсодержащее соединение, где металл М представлен одним или более щёлочно-земельным или редкоземельным металлом, предпочтительно выбранным из Мд, Са, δτ, Ва, Ьа, Се.
  12. 12. Способ по любому из предыдущих пунктов, характеризующийся тем, что катализатор (цеолит + связующее) имеет объём пор между 30 и 1000 А, по меньшей мере, при удельном объёме по СГС 0,25 см3/г.
  13. 13. Способ дегидратации спиртов с конвертацией, по меньшей мере, выбранного спирта в соответствующий олефин с тем же числом атомов углерода, характеризующийся тем, что его ведут в присутствии катализатора, полученного способом по любому из пп.1-12.
  14. 14. Способ крекинга олефинов с выделением более лёгких олефинов, характеризующийся тем, что его ведут в присутствии катализатора, полученного способом по любому из пп.1-12.
  15. 15. Способ крекинга метанола или диметилового эфира с получением лёгких олефинов, таких как этилен и пропилен, характеризующийся тем, что его ведут в присутствии катализатора, полученного способом по любому из пп.1-12.
  16. 16. Способ алкилирования ароматических углеводородов спиртами или олефинами, характеризующийся тем, что его ведут в присутствии катализатора, полученного способом по любому из пп.1-12.
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