RU2015125559A - Катализатор гидроочистки, содержащий подложку, полученную из алюмогеля, и способ получения такого катализатора - Google Patents
Катализатор гидроочистки, содержащий подложку, полученную из алюмогеля, и способ получения такого катализатора Download PDFInfo
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- RU2015125559A RU2015125559A RU2015125559A RU2015125559A RU2015125559A RU 2015125559 A RU2015125559 A RU 2015125559A RU 2015125559 A RU2015125559 A RU 2015125559A RU 2015125559 A RU2015125559 A RU 2015125559A RU 2015125559 A RU2015125559 A RU 2015125559A
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims 26
- 239000000758 substrate Substances 0.000 title claims 11
- 238000004519 manufacturing process Methods 0.000 title 1
- 229910052751 metal Inorganic materials 0.000 claims 14
- 239000002184 metal Substances 0.000 claims 14
- 238000000034 method Methods 0.000 claims 7
- 238000010438 heat treatment Methods 0.000 claims 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 5
- 238000010304 firing Methods 0.000 claims 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 4
- 238000010335 hydrothermal treatment Methods 0.000 claims 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 3
- 230000002378 acidificating effect Effects 0.000 claims 3
- 239000007864 aqueous solution Substances 0.000 claims 3
- 229910052750 molybdenum Inorganic materials 0.000 claims 3
- 239000011733 molybdenum Substances 0.000 claims 3
- 229910052698 phosphorus Inorganic materials 0.000 claims 3
- 239000011574 phosphorus Substances 0.000 claims 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 239000012670 alkaline solution Substances 0.000 claims 2
- 229910001593 boehmite Inorganic materials 0.000 claims 2
- 239000010941 cobalt Substances 0.000 claims 2
- 229910017052 cobalt Inorganic materials 0.000 claims 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims 2
- 150000002739 metals Chemical class 0.000 claims 2
- 230000000737 periodic effect Effects 0.000 claims 2
- 239000002243 precursor Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000003929 acidic solution Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000011260 aqueous acid Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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Claims (25)
1. Катализатор, содержащий подложку, по меньшей мере один металл, выбранный из группы VIB, и по меньшей мере один металл, выбранный из группы VIII периодической системы элементов, причем содержание металла группы VIB, выраженного на оксиды, составляет от 6 до 25 вес.% от общего веса катализатора, содержание металла группы VIII, выраженное на оксиды, составляет от 0,5 до 7 вес.% от общего веса катализатора, подложка содержит по меньшей мере 90 вес.% оксида алюминия, который получен из размешанного и экструдированного геля бемита, и причем удельная поверхность указанного катализатора составляет от 60 до 250 м2/г.
2. Катализатор по п. 1, причем содержание металла группы VIB, выраженное на оксиды, составляет от 7 до 20 вес.% от общего веса указанного катализатора, а содержание металла группы VIII, выраженное на оксиды, составляет от 0,5 до 5 вес.% от общего веса катализатора.
3. Катализатор по п. 1 или 2, причем подложка из оксида алюминия содержит оксид алюминия в модификации гамма, дельта или тета, по отдельности или в смеси.
4. Катализатор по п. 1 или 2, включающий, дополнительно, фосфор, причем содержание фосфора, выраженное в P2O5, составляет от 1 до 10 вес.% от общего веса катализатора.
5. Катализатор по п. 1 или 2, в котором металл группы VIb выбран из молибдена и вольфрама.
6. Катализатор по п. 1 или 2, в котором металл группы VIII выбран из кобальта и никеля.
7. Катализатор по п. 1 или 2, в котором металл группы VIb является молибденом, а металл группы VIII является кобальтом.
8. Катализатор по п. 7, содержащий, дополнительно, фосфор, для которого плотность молибдена, выраженная в числе атомов молибдена на нм2 катализатора, составляет от 3 до 5, атомное отношение Co/Mo составляет от 0,3 до 0,5, и атомное отношение P/Mo составляет от 0,1 до 0,3.
9. Катализатор по п. 1 или 2, где удельная поверхность катализатора составляет от 60 до 150 м2/г.
10. Катализатор по п. 1 или 2, где удельная поверхность катализатора составляет от 150 до 200 м2/г.
11. Катализатор по п. 1 или 2, где удельная поверхность катализатора составляет от 200 до 250 м2/г.
12. Способ получения катализатора по одному из предыдущих пунктов, включающий следующие стадии, на которых:
a) приводят в контакт водный раствор кислых солей алюминия с щелочным раствором, или водный раствор основных солей алюминия с кислым раствором, не содержащим алюминия, или водный раствор кислых солей алюминия с щелочным раствором солей алюминия, с образованием геля бемита,
b) размешивают указанный гель, полученный на стадии a), в кислой или основной среде, с получением пасты;
c) формуют пасту, полученную на стадии b), с получением подложки в форме экструдата,
d) проводят термообработку подложки из оксида алюминия, полученной на стадии c), чтобы получить удельную поверхность подложки в интервале от 60 до 300 м2/г,
e) пропитывают подложку из оксида алюминия, полученную на стадии d), раствором, содержащим по меньшей мере один предшественник металла, выбранного из группы VIB, и по меньшей мере один предшественник металла, выбранного из группы VIII периодической системы элементов,
f) проводят термообработку указанной подложки, пропитанной металлами на стадии e), чтобы получить удельную поверхность катализатора в интервале от 60 до 250 м2/г.
13. Способ по п. 12, в котором термообработка на стадии d) включает по меньшей мере одну стадию гидротермической обработки и по меньшей мере одну стадию обжига, причем стадию обжига проводят после гидротермической обработки, и гидротермическую обработку осуществляют в камере в присутствии воды при температуре от 100 до 300°C в течение 0,5-8 часов, а стадию обжига осуществляют на воздухе при температуре от 400 до 1500°C в течение 1-8 часов.
14. Способ по п. 13, в котором гидротермическая обработка
включает стадию пропитки подложки водным раствором кислоты до нагревания указанной подложки, пропитанной в камере.
15. Способ по п. 12, в котором термообработка на стадии d) представляет собой только стадию обжига, осуществляемую на воздухе при влагосодержании воздуха от 0 до 50 вес.%, при температуре от 400 до 1500°C в течение 1-8 часов.
16. Способ по одному из пп. 12-15, в котором сушку подложки, полученной на стадии c), проводят перед стадией термообработки d).
17. Способ по п. 12, в котором термическая обработка на стадии f) включает по меньшей мере одну стадию сушки при температуре от 80 до 200°C подложки, пропитанной металлами, за которой необязательно следует стадия обжига при температуре выше 400°C.
18. Способ гидродесульфирования фракции бензина, в котором приводят в контакт водород и указанную фракцию бензина с катализатором по одному из пп. 1-11 или полученным по одному из пп. 12-17, при температуре от 200 до 400°C, полном давлении от 1 до 3 МПа и часовой объемной скорости (VVH) от 1 до 10 час-1.
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FR1203236A FR2998488B1 (fr) | 2012-11-29 | 2012-11-29 | Catalyseur d hydrotraitement a partir d alumine gel et methode de preparation d un tel catalyseur |
FR12/03236 | 2012-11-29 | ||
PCT/FR2013/052861 WO2014083273A1 (fr) | 2012-11-29 | 2013-11-26 | Catalyseur d'hydrotraitement comprenant un support obtenu a partir d'un gel d'alumine et methode de preparation d'un tel catalyseur |
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FR3075072B1 (fr) * | 2017-12-14 | 2021-11-26 | Ifp Energies Now | Catalyseur d'hydrodesulfuration selective des essences de fcc |
CN115279491B (zh) * | 2020-05-14 | 2023-12-12 | 庄信万丰股份有限公司 | 用于联芳生产的催化剂 |
CN114471619B (zh) * | 2020-10-26 | 2023-09-01 | 中国石油化工股份有限公司 | 一种重整生成油加氢脱烯烃催化剂及其制备方法 |
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FR3122105B1 (fr) * | 2021-04-21 | 2023-11-24 | Ifp Energies Now | Catalyseur contenant du phosphore et du sodium et son utilisation dans un procede d’hydrodesulfuration |
WO2023170700A1 (en) | 2022-03-11 | 2023-09-14 | Hindustan Petroleum Corporation Limited | Naphtha hydrotreating catalyst and process of preparation thereof |
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CN104812480B (zh) | 2017-05-10 |
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FR2998488B1 (fr) | 2015-02-06 |
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DK2925433T3 (da) | 2020-03-30 |
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WO2014083252A1 (fr) | 2014-06-05 |
BR112015011811B1 (pt) | 2020-09-29 |
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WO2014083273A1 (fr) | 2014-06-05 |
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