RU2008146028A - Способы и системы для получения многоатомных спиртов - Google Patents
Способы и системы для получения многоатомных спиртов Download PDFInfo
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- RU2008146028A RU2008146028A RU2008146028/04A RU2008146028A RU2008146028A RU 2008146028 A RU2008146028 A RU 2008146028A RU 2008146028/04 A RU2008146028/04 A RU 2008146028/04A RU 2008146028 A RU2008146028 A RU 2008146028A RU 2008146028 A RU2008146028 A RU 2008146028A
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- catalytic material
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- 238000000034 method Methods 0.000 title claims abstract 29
- 150000001298 alcohols Chemical class 0.000 title 1
- 230000003197 catalytic effect Effects 0.000 claims abstract 40
- 239000000463 material Substances 0.000 claims abstract 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 21
- 239000001301 oxygen Substances 0.000 claims abstract 21
- 239000012527 feed solution Substances 0.000 claims abstract 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 14
- 239000001257 hydrogen Substances 0.000 claims abstract 14
- 239000000203 mixture Substances 0.000 claims abstract 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract 12
- 229910052742 iron Inorganic materials 0.000 claims abstract 12
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract 9
- 239000000243 solution Substances 0.000 claims abstract 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 5
- 239000000956 alloy Substances 0.000 claims abstract 5
- 229910045601 alloy Inorganic materials 0.000 claims abstract 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract 5
- 229910052702 rhenium Inorganic materials 0.000 claims abstract 5
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract 5
- 150000001299 aldehydes Chemical class 0.000 claims abstract 4
- 150000001875 compounds Chemical class 0.000 claims abstract 4
- 150000002576 ketones Chemical class 0.000 claims abstract 4
- 239000002994 raw material Substances 0.000 claims abstract 4
- 150000005846 sugar alcohols Polymers 0.000 claims abstract 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract 3
- 239000010941 cobalt Substances 0.000 claims abstract 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052802 copper Inorganic materials 0.000 claims abstract 3
- 239000010949 copper Substances 0.000 claims abstract 3
- 230000003993 interaction Effects 0.000 claims abstract 3
- 239000007788 liquid Substances 0.000 claims abstract 3
- 229910052751 metal Inorganic materials 0.000 claims abstract 3
- 239000002184 metal Substances 0.000 claims abstract 3
- 239000008346 aqueous phase Substances 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 2
- 238000002407 reforming Methods 0.000 claims abstract 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 25
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 16
- 239000002638 heterogeneous catalyst Substances 0.000 claims 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 9
- 235000011187 glycerol Nutrition 0.000 claims 9
- 229910052697 platinum Inorganic materials 0.000 claims 8
- 239000003054 catalyst Substances 0.000 claims 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 4
- OGRZPYBWAVRXFO-UHFFFAOYSA-N [C].CC(O)CO Chemical compound [C].CC(O)CO OGRZPYBWAVRXFO-UHFFFAOYSA-N 0.000 claims 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 2
- 239000001569 carbon dioxide Substances 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 238000011065 in-situ storage Methods 0.000 claims 2
- 229910052741 iridium Inorganic materials 0.000 claims 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims 2
- 229910052763 palladium Inorganic materials 0.000 claims 2
- 229910052703 rhodium Inorganic materials 0.000 claims 2
- 239000010948 rhodium Substances 0.000 claims 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 2
- 229910052723 transition metal Inorganic materials 0.000 claims 2
- 150000003624 transition metals Chemical class 0.000 claims 2
- 230000001588 bifunctional effect Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
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- C07C27/06—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds by hydrogenation of oxides of carbon
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Abstract
1. Способ получения кислородсодержащего соединения из водного сырьевого раствора, включающего воду и по меньшей мере один водорастворимый кислородсодержащий углеводород, имеющий два или более атомов углерода, при этом способ включает стадии ! а) получения водорода при реформинге в водной фазе (РВФ) путем приведения кислородсодержащего углеводорода в первой части водного сырьевого раствора в контакт с первым каталитическим материалом, включающим по меньшей мере один металл Группы VIII при ! 1) температуре примерно от 80 до 400°С; ! 2) массовой часовой объемной скорости по меньшей мере примерно 1,0 г кислородсодержащего углеводорода на грамм первого каталитического материала в час, и ! 3) давлении, при котором вода и кислородсодержащие углеводороды находятся в форме конденсированных жидкостей, и ! б) взаимодействия водорода РВФ с кислородсодержащим углеводородом во второй части сырьевого раствора для восстановления кислородсодержащего углеводорода в присутствии второго каталитического материала, причем второй каталитический материал является отличным от первого каталитического материала и его выбирают из группы, состоящей из железа, рутения, меди, рения, кобальта, никеля, их сплавов и их смесей, при ! 1) температуре примерно от 100 до 300°С, и ! 2) давлении примерно от 1,38 до 8,27 МПа избыт. (от 200 до 1200 фунт/кв. дюйм избыт.), ! с получением продукта реакции, включающего по меньшей мере одно восстановленное кислородсодержащее углеводородное соединение, выбранное из группы, состоящей из многоатомного спирта, кетона, альдегида, карбоновой кислоты и спирта. ! 2. Способ по п.1, в котором вторая часть сырьевого раствора дополнител
Claims (30)
1. Способ получения кислородсодержащего соединения из водного сырьевого раствора, включающего воду и по меньшей мере один водорастворимый кислородсодержащий углеводород, имеющий два или более атомов углерода, при этом способ включает стадии
а) получения водорода при реформинге в водной фазе (РВФ) путем приведения кислородсодержащего углеводорода в первой части водного сырьевого раствора в контакт с первым каталитическим материалом, включающим по меньшей мере один металл Группы VIII при
1) температуре примерно от 80 до 400°С;
2) массовой часовой объемной скорости по меньшей мере примерно 1,0 г кислородсодержащего углеводорода на грамм первого каталитического материала в час, и
3) давлении, при котором вода и кислородсодержащие углеводороды находятся в форме конденсированных жидкостей, и
б) взаимодействия водорода РВФ с кислородсодержащим углеводородом во второй части сырьевого раствора для восстановления кислородсодержащего углеводорода в присутствии второго каталитического материала, причем второй каталитический материал является отличным от первого каталитического материала и его выбирают из группы, состоящей из железа, рутения, меди, рения, кобальта, никеля, их сплавов и их смесей, при
1) температуре примерно от 100 до 300°С, и
2) давлении примерно от 1,38 до 8,27 МПа избыт. (от 200 до 1200 фунт/кв. дюйм избыт.),
с получением продукта реакции, включающего по меньшей мере одно восстановленное кислородсодержащее углеводородное соединение, выбранное из группы, состоящей из многоатомного спирта, кетона, альдегида, карбоновой кислоты и спирта.
2. Способ по п.1, в котором вторая часть сырьевого раствора дополнительно включает кислородсодержащие углеводороды, полученные путем приведения сырьевого раствора в контакт с первым каталитическим материалом.
3. Способ по любому из пп.1 и 2, в котором вторую часть сырьевого раствора приводят в контакт с водородом РВФ и вторым каталитическим материалом при давлении выше 2,52 МПа избыт. (365 фунт/кв. дюйм избыт.).
4. Способ по п.1, в котором первый каталитический материал включает по меньшей мере один переходный металл, выбираемый из группы, состоящей из платины, никеля, палладия, рутения, родия, рения, иридия, их сплавов и их смесей.
5. Способ по п.1, в котором второй каталитический материал выбирают из группы, состоящей из железа, никеля, рутения и кобальта.
6. Способ по п.1, в котором второй каталитический материал представляет собой железо.
7. Способ по п.1, в котором первый каталитический материал и второй каталитический материал объединяют с образованием каталитической смеси.
8. Способ по п.1, в котором первый каталитический материал включает по меньшей мере один переходный металл, выбираемый из группы, состоящей из платины, никеля, палладия, рутения, родия, рения, иридия, их сплавов и их смесей, а второй каталитический материал представляет собой железо.
9. Способ по п.1, в котором молярное отношение первого каталитического материала ко второму каталитическому материалу составляет от 5:1 до 1:5.
10. Способ по п.1, в котором первую часть сырьевого раствора и вторую часть сырьевого раствора приводят в контакт с первым каталитическим материалом и вторым каталитическим материалом в реакционном сосуде при температуре от 200 до 270°С.
11. Способ по п.1, в котором первый каталитический материал представляет собой платину, а второй каталитический материал представляет собой железо.
12. Способ по п.1, в котором первый каталитический материал закрепляют на носителе.
13. Способ по п.12, в котором носитель представляет собой активированный уголь.
14. Способ по п.1, в котором первый каталитический материал и второй каталитический материал объединяют с образованием каталитической смеси и каталитическую смесь закрепляют на носителе из активированного угля так, что носитель включает 5 мас.% первого и второго каталитических материалов.
15. Способ по п.1, в котором вторую часть сырьевого раствора приводят в контакт со вторым каталитическим материалом при массовой часовой объемной скорости от 1,0 до 5,0 г кислородсодержащего углеводорода на грамм второго каталитического материала в час.
16. Способ по п.1, в котором вторую часть сырьевого раствора приводят в контакт со вторым каталитическим материалом при температуре от 120 до 300°С, а первую часть сырьевого раствора приводят в контакт с первым каталитическим материалом при температуре от 200 до 270°С.
17. Способ по п.1, в котором вторую часть сырьевого раствора приводят во взаимодействие с водородом РВФ и водородом, поступающим извне, где молярное отношение водорода РВФ к водороду, поступающему извне, составляет по меньшей мере 3:1.
18. Способ по п.1, в котором сырьевой раствор включает по меньшей мере 20 мас.% глицерина.
19. Способ по п.1, в котором первый каталитический материал и второй каталитический материал объединяют с образованием каталитической смеси и сырьевой раствор приводят в контакт с каталитической смесью при давлении от 0,50 до 8,96 МПа избыт. (от 72 до 1300 фунт/кв. дюйм избыт.) и массовой часовой объемной скорости от 1,0 до 5,0 г глицерина на грамм каталитической смеси в час, и где продукт реакции включает пропиленгликоль.
20. Способ по п.1, в котором продукт реакции имеет выход пропиленгликоля по углероду 40% или выше.
21. Способ по п.1, в котором продукт реакции включает диоксид углерода, пропиленгликоль и по меньшей мере один из следующих продуктов: второй двухатомный спирт, карбоновая кислота, альдегид, кетон и спирт.
22. Способ получения пропиленгликоля, включающий стадию приведения гетерогенного катализатора, включающего платину и железо, в контакт с водным сырьевым раствором, включающим воду и глицерин, при
а) температуре примерно от 100 до 300°С;
б) массовой часовой объемной скорости по меньшей мере примерно 1 г глицерина на грамм гетерогенного катализатора в час, и
в) давлении, при котором вода и кислородсодержащие углеводороды остаются в форме конденсированных жидкостей,
с образованием реакционного продукта, включающего пропиленгликоль.
23. Способ по п.22, в котором
а) гетерогенный катализатор состоит по существу из 5 мас.% железа и платины в молярном отношении 1:1 на носителе из активированного угля;
б) сырье включает по меньшей мере 20 мас.% глицерина;
в) сырье приводят в контакт с гетерогенным катализатором при массовой часовой объемной скорости от 1,0 до 5,0 г глицерина на грамм гетерогенного катализатора в час и давлении 1,72-2,76 МПа избыт. (250-400 фунт/кв. дюйм избыт.);
г) водный сырьевой раствор приводят в контакт с гетерогенным катализатором в присутствии водорода, полученного in situ, или
д) продукт реакции имеет выход пропиленгликоля по углероду 40% или выше.
24. Способ по п.22, в котором
а) гетерогенный катализатор состоит по существу из 5 мас.% железа и платины в молярном отношении 1:1 на носителе из активированного угля;
б) сырье включает по меньшей мере 20 мас.% глицерина;
в) сырье приводят в контакт с гетерогенным катализатором при массовой часовой объемной скорости от 1,0 до 5,0 г глицерина на грамм гетерогенного катализатора в час и давлении 1,72-2,76 МПа избыт. (250-400 фунт/кв. дюйм избыт.);
г) водный сырьевой раствор приводят в контакт с гетерогенным катализатором в присутствии водорода, полученного in situ, и
д) продукт реакции имеет выход пропиленгликоля по углероду 40% или выше.
25. Способ по любому из пп.22-24, в котором водный сырьевой раствор приводят в контакт с гетерогенным катализатором без подачи водорода из внешнего источника по отношению водному сырью.
26. Композиция веществ, включающая воду, глицерин, карбоновую кислоту, диоксид углерода, пропиленгликоль и каталитическую композицию, включающую платину и железо.
27. Реакционная система для получения кислородсодержащих соединений из водного сырьевого раствора, содержащего водорастворимый многоатомный спирт, включающая
а) первый реакционный слой, включающий первый катализатор, содержащий по меньшей мере один металл Группы VIII, и скомпонованный для контактирования с первой частью сырьевого раствора в конденсированной фазе, и
б) второй реакционный слой, включающий каталитический материал, выбранный из группы, состоящей из железа, рутения, меди, рения, кобальта, никеля, их сплавов и их смесей, и скомпонованный так, чтобы принимать вторую часть сырьевого раствора;
в) реакционная система отличается тем, что
1) второй реакционный слой расположен и скомпонован так, чтобы принимать водород, образуемый в первом реакционном слое, и
2) реакционная система обеспечивает получение продукта реакции, содержащего по меньшей мере одно кислородсодержащее соединение, выбранное из группы, состоящей из многоатомного спирта, кетона, альдегида, карбоновой кислоты и спирта, при отсутствии введения водорода в реакционный поток.
28. Реакционная система по п.27, в которой первый каталитический материал включает платину.
29. Реакционная система по п.27 или 28, в которой второй каталитический материал включает железо.
30. Реакционная система по п.27, в которой первый реакционный слой и второй реакционный слой размещены в одном реакционном сосуде и реакционный сосуд имеет конфигурацию, выбранную из группы, состоящей из следующих конфигураций:
а) первый реакционный слой уложен над вторым реакционным слоем;
б) второй реакционный слой уложен над первым реакционным слоем, и
в) первый реакционный слой и второй реакционный слой объединены с образованием бифункционального реакционного слоя.
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