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RU2009116476A - ISOMERIZATION PROCESS USING METAL-MODIFIED SMALL-CRYSTAL MTT MOLECULAR Sieve - Google Patents

ISOMERIZATION PROCESS USING METAL-MODIFIED SMALL-CRYSTAL MTT MOLECULAR Sieve Download PDF

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RU2009116476A
RU2009116476A RU2009116476/04A RU2009116476A RU2009116476A RU 2009116476 A RU2009116476 A RU 2009116476A RU 2009116476/04 A RU2009116476/04 A RU 2009116476/04A RU 2009116476 A RU2009116476 A RU 2009116476A RU 2009116476 A RU2009116476 A RU 2009116476A
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dewaxing
group
kpa
psi
molecular sieve
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RU2009116476/04A
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Russian (ru)
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RU2493236C2 (en
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Стейси И. ЗОУНЗ (US)
Стейси И. Зоунз
Камала КРИШНА (US)
Камала Кришна
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ШЕВРОН Ю. Эс. Эй. ИНК. (US)
ШЕВРОН Ю. Эс. Эй. ИНК.
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    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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    • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
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  • Chemical & Material Sciences (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

1. Способ депарафинизации углеводородного сырья с получением изомеризованного продукта, сырье содержит линейные цепочечные и слабо разветвленные парафины, содержащие от 10 или более атомов углерода, включающий осуществление контакта сырья в условиях изомеризации в присутствии водорода с катализатором, включающим молекулярное сито, имеющее топологию структуры МТТ и диаметр кристаллитов приблизительно от 200 до приблизительно 400 Е в самом длинном направлении, катализатор содержит, по меньшей мере, один металл, выбранный из группы, включающей Ca, Cr, Mg, La, Na, Pr, Sr, K и Nd, и, по меньшей мере, один металл VIII группы. ! 2. Способ по п.1, где МТТ молекулярное сито выбрано из группы, включающей SSZ-32, ZSM-23, EU-13, ISI-4 и KZ-1. ! 3. Способ по п.1, где указанное сырье выбрано из группы, включающей гидрированные или гидрокрекированные газойли, гидрированные рафинаты смазочных масел, светлые продукты, сырье для смазочных масел, синтетические масла, парафиновые отеки, синтетические масла Фишера-Тропша, полиолефины с высокой температурой текучести, нормальные альфа-олефиновые воски, парафиновые гачи, очищенные от масла воски, микрокристаллические воски и их смеси. ! 4. Способ по п.1, где металлы VIII группы выбраны из группы, включающей платину и палладий и их смеси. ! 5. Способ по п.1, где указанный контакт осуществляют при температуре 232-427°С (450-800°F) и давлении в интервале от приблизительно 103,4 кПа (15 фунт/кв. дюйм) до приблизительно 20,685 кПа (3000 фунт/кв. дюйм). ! 6. Способ по п.5, где указанное давление находится в интервале от приблизительно 689,5 кПа (100 фунт/кв. дюйм) до приблизительно 17237 кПа (2500 фунт/кв. дюйм). !7. Способ по п.5, где часовая объемная скорость жидкости в 1. A method for dewaxing hydrocarbon feedstock to obtain an isomerized product, the feedstock contains linear chain and weakly branched paraffins containing from 10 or more carbon atoms, comprising contacting the feedstock under isomerization conditions in the presence of hydrogen with a catalyst comprising a molecular sieve having the MTT structure topology and the crystallite diameter is from about 200 to about 400 E in the longest direction, the catalyst contains at least one metal selected from the group consisting of Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd, and, at least one metal of group VIII. ! 2. The method of claim 1, wherein the MTT molecular sieve is selected from the group consisting of SSZ-32, ZSM-23, EU-13, ISI-4, and KZ-1. ! 3. The method according to claim 1, wherein said feedstock is selected from the group consisting of hydrogenated or hydrocracked gas oils, hydrogenated lubricating oil raffinates, light products, lubricating oil feedstocks, synthetic oils, paraffin edemas, Fischer-Tropsch synthetic oils, high temperature polyolefins fluidity, normal alpha-olefin waxes, slack wax, de-oiled waxes, microcrystalline waxes, and mixtures thereof. ! 4. The method of claim 1, wherein the Group VIII metals are selected from the group consisting of platinum and palladium and mixtures thereof. ! 5. The method of claim 1, wherein said contact is performed at a temperature of 232-427 ° C (450-800 ° F) and a pressure in the range of about 103.4 kPa (15 psi) to about 20.685 kPa (3000 psi). ! 6. The method of claim 5, wherein said pressure ranges from about 689.5 kPa (100 psi) to about 17237 kPa (2500 psi). ! 7. The method according to claim 5, where the hourly space velocity of the liquid in

Claims (25)

1. Способ депарафинизации углеводородного сырья с получением изомеризованного продукта, сырье содержит линейные цепочечные и слабо разветвленные парафины, содержащие от 10 или более атомов углерода, включающий осуществление контакта сырья в условиях изомеризации в присутствии водорода с катализатором, включающим молекулярное сито, имеющее топологию структуры МТТ и диаметр кристаллитов приблизительно от 200 до приблизительно 400 Е в самом длинном направлении, катализатор содержит, по меньшей мере, один металл, выбранный из группы, включающей Ca, Cr, Mg, La, Na, Pr, Sr, K и Nd, и, по меньшей мере, один металл VIII группы.1. The method of dewaxing hydrocarbon feedstock to obtain an isomerized product, the feedstock contains linear chain and weakly branched paraffins containing from 10 or more carbon atoms, comprising contacting the feedstock under isomerization conditions in the presence of hydrogen with a catalyst comprising a molecular sieve having an MTT structure topology and crystallite diameter from about 200 to about 400 U in the longest direction, the catalyst contains at least one metal selected from the group including s Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd, and at least one metal from group VIII. 2. Способ по п.1, где МТТ молекулярное сито выбрано из группы, включающей SSZ-32, ZSM-23, EU-13, ISI-4 и KZ-1.2. The method according to claim 1, where the MTT molecular sieve is selected from the group comprising SSZ-32, ZSM-23, EU-13, ISI-4 and KZ-1. 3. Способ по п.1, где указанное сырье выбрано из группы, включающей гидрированные или гидрокрекированные газойли, гидрированные рафинаты смазочных масел, светлые продукты, сырье для смазочных масел, синтетические масла, парафиновые отеки, синтетические масла Фишера-Тропша, полиолефины с высокой температурой текучести, нормальные альфа-олефиновые воски, парафиновые гачи, очищенные от масла воски, микрокристаллические воски и их смеси.3. The method according to claim 1, where the specified raw material is selected from the group comprising hydrogenated or hydrocracked gas oils, hydrogenated raffinates of lubricating oils, light products, raw materials for lubricating oils, synthetic oils, paraffin edema, synthetic Fischer-Tropsch oils, high temperature polyolefins fluidity, normal alpha olefin waxes, paraffin waxes, oil-free waxes, microcrystalline waxes and mixtures thereof. 4. Способ по п.1, где металлы VIII группы выбраны из группы, включающей платину и палладий и их смеси.4. The method according to claim 1, where the metals of group VIII are selected from the group comprising platinum and palladium and mixtures thereof. 5. Способ по п.1, где указанный контакт осуществляют при температуре 232-427°С (450-800°F) и давлении в интервале от приблизительно 103,4 кПа (15 фунт/кв. дюйм) до приблизительно 20,685 кПа (3000 фунт/кв. дюйм).5. The method according to claim 1, where the specified contact is carried out at a temperature of 232-427 ° C (450-800 ° F) and a pressure in the range from about 103.4 kPa (15 psi) to about 20.685 kPa (3000 psi). 6. Способ по п.5, где указанное давление находится в интервале от приблизительно 689,5 кПа (100 фунт/кв. дюйм) до приблизительно 17237 кПа (2500 фунт/кв. дюйм).6. The method according to claim 5, where the specified pressure is in the range from approximately 689.5 kPa (100 psi) to approximately 17237 kPa (2500 psi). 7. Способ по п.5, где часовая объемная скорость жидкости во время осуществления контакта составляет от приблизительно 0,1 до приблизительно 20.7. The method according to claim 5, where the hourly space velocity of the liquid during the implementation of the contact is from about 0.1 to about 20. 8. Способ по п.7, где часовая объемная скорость жидкости составляет от 0,5 до приблизительно 5.8. The method according to claim 7, where the hourly space velocity of the liquid is from 0.5 to about 5. 9. Способ по п.1, где углеводородное сырье гидрируют перед изомеризацией при температуре в интервале от 163 до 427°С (325-800°F).9. The method according to claim 1, where the hydrocarbon feed is hydrogenated before isomerization at a temperature in the range from 163 to 427 ° C (325-800 ° F). 10. Способ по п.1, дополнительно включающий стадию гидроочистки с последующей изомеризацией.10. The method according to claim 1, further comprising a hydrotreatment step followed by isomerization. 11. Способ по п.10, где гидроочистку проводят при температуре в интервале от приблизительно 163 до приблизительно 310°С (от 325 до приблизительно 590°F) и давлении в интервале от приблизительно 2068 кПа (300 фунт/кв. дюйм) до приблизительно 20685 кПа (3000 фунт/кв. дюйм).11. The method according to claim 10, where the hydrotreating is carried out at a temperature in the range from about 163 to about 310 ° C (from 325 to about 590 ° F) and a pressure in the range from about 2068 kPa (300 psi) to about 20685 kPa (3000 psi). 12. Способ по п.1, дополнительно включающий гидроочистку изомеризованного продукта.12. The method according to claim 1, further comprising hydrotreating the isomerized product. 13. Способ депарафинизации, включающий изомеризационную депарафинизацию углеводородного сырья, содержащего, по меньшей мере, 5 мас.% воска, над катализатором с получением двух или нескольких изомеризованных продуктов, кипящих при 343°С (650°F) или выше, каждый изомеризованный продукт имеет13. A dewaxing process comprising isomerizing dewaxing of a hydrocarbon feed containing at least 5 wt.% Wax over a catalyst to produce two or more isomerized products boiling at 343 ° C. (650 ° F) or higher, each isomerized product has а) температуру текучести между 0 и -30°С иa) pour point between 0 and -30 ° C and b) соответствующий индекс вязкости 95 или выше,b) an appropriate viscosity index of 95 or higher, где прямая линия, построенная к зависимости температур текучести на оси х и индексов вязкости на оси y, дает наклон для y ноль или меньше.where the straight line plotted for the dependence of yield temperatures on the x axis and viscosity indices on the y axis gives the slope for y of zero or less. 14. Способ депарафинизации по п.13, где углеводородное сырье имеет, по меньшей мере, 10 мас.% воска.14. The dewaxing method of claim 13, wherein the hydrocarbon feed has at least 10 wt.% Wax. 15. Способ депарафинизации по п.13, где углеводородное сырье имеет кинематическую вязкость при 100°С 2,5 мм2 с или больше.15. The dewaxing method of claim 13, wherein the hydrocarbon feed has a kinematic viscosity at 100 ° C. of 2.5 mm 2 s or more. 16. Способ депарафинизации по п.13, где катализатор включает молекулярное сито, имеющее топологию структуры МТТ и диаметр кристаллитов приблизительно от 200 до приблизительно 400 Е в самом длинном направлении.16. The dewaxing method of claim 13, wherein the catalyst comprises a molecular sieve having an MTT structure topology and a crystallite diameter of from about 200 to about 400 U in the longest direction. 17. Способ депарафинизации по п.16, где катализатор дополнительно включает, по меньшей мере, один металл, выбранный из группы, включающей Ca, Cr, Mg, La, Na, Pr, Sr, K и Nd.17. The dewaxing method according to clause 16, wherein the catalyst further comprises at least one metal selected from the group consisting of Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd. 18. Способ депарафинизации по п.17, где катализатор дополнительно включает, по меньшей мере, один металл VIII группы.18. The dewaxing method according to claim 17, wherein the catalyst further comprises at least one Group VIII metal. 19. Способ депарафинизации по п.13, где два или несколько изомеризованных продукта, кипящих при 343°С (650°F) или выше имеют соответствующий индекс вязкости 104 или выше.19. The dewaxing method of claim 13, wherein the two or more isomerized products boiling at 343 ° C (650 ° F) or higher have a corresponding viscosity index of 104 or higher. 20. Способ депарафинизации по п.13, где выход двух или нескольких изомеризованных продуктов, кипящих при 343°С (650°F) или выше составляет 90 мас.% или больше в расчете на сырье.20. The dewaxing method of claim 13, wherein the yield of two or more isomerized products boiling at 343 ° C (650 ° F) or higher is 90% by weight or more based on the feed. 21. Способ депарафинизации по п.20, где выход составляет 94 мас.% или больше.21. The dewaxing method according to claim 20, where the yield is 94 wt.% Or more. 22. Способ депарафинизации по п.13, где наклон прямой составляет меньше, чем -0,05.22. The dewaxing method of claim 13, wherein the slope of the straight line is less than -0.05. 23. Способ депарафинизации, включающий изомеризационную депарафинизацию углеводородного сырья, содержащего, по меньшей мере, 5 мас.% воска, над катализатором с получением двух или нескольких изомеризованных продуктов, кипящих при 343°С (650°F) или выше, каждый изомеризованный продукт имеет23. A dewaxing method comprising isomerizing dewaxing of a hydrocarbon feed containing at least 5 wt.% Wax over a catalyst to produce two or more isomerized products boiling at 343 ° C. (650 ° F) or higher, each isomerized product has а) температуру текучести между 0 и -30°С иa) pour point between 0 and -30 ° C and b) соответствующий индекс вязкости 95 или выше,b) an appropriate viscosity index of 95 or higher, где прямая линия, построенная по зависимости температур текучести на оси х и индексов вязкости на оси y, дает наклон для y ноль или меньше, и где выход двух или нескольких изомеризованных продуктов, кипящих при 343°С (650°F) или выше, составляет 90 мас.% или выше в расчете на сырье.where the straight line, constructed from the dependence of yield temperatures on the x axis and viscosity indices on the y axis, gives a slope for y of zero or less, and where the yield of two or more isomerized products boiling at 343 ° C (650 ° F) or higher is 90 wt.% Or higher based on raw materials. 24. Способ депарафинизации по п.23, где молекулярное сито имеет топологию МТТ структуры.24. The dewaxing method according to item 23, where the molecular sieve has the topology of the MTT structure. 25. Способ депарафинизации по п.23, где молекулярное сито имеет размер кристаллитов приблизительно 200-400 Е. 25. The dewaxing method according to item 23, where the molecular sieve has a crystallite size of approximately 200-400 E.
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