RU2006105480A - Высокотемпературное прокаливание молекулярно-ситовых катализаторов с повышенной селективностью с целью модификации активности и диффузионных свойств - Google Patents
Высокотемпературное прокаливание молекулярно-ситовых катализаторов с повышенной селективностью с целью модификации активности и диффузионных свойств Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract 21
- 238000009792 diffusion process Methods 0.000 title claims abstract 11
- 239000003054 catalyst Substances 0.000 title claims 2
- 230000000694 effects Effects 0.000 title claims 2
- 238000004080 punching Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract 27
- 229910052751 metal Inorganic materials 0.000 claims abstract 13
- 239000002184 metal Substances 0.000 claims abstract 13
- 230000004888 barrier function Effects 0.000 claims abstract 10
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims abstract 8
- 238000001354 calcination Methods 0.000 claims abstract 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000010521 absorption reaction Methods 0.000 claims abstract 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract 4
- 239000012013 faujasite Substances 0.000 claims abstract 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract 2
- 239000011230 binding agent Substances 0.000 claims abstract 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000003837 high-temperature calcination Methods 0.000 claims abstract 2
- 229910052680 mordenite Inorganic materials 0.000 claims abstract 2
- 229910052710 silicon Inorganic materials 0.000 claims abstract 2
- 239000010703 silicon Substances 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000010457 zeolite Substances 0.000 claims abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 6
- 229930195733 hydrocarbon Natural products 0.000 claims 6
- 150000002430 hydrocarbons Chemical class 0.000 claims 6
- 238000006243 chemical reaction Methods 0.000 claims 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 150000001491 aromatic compounds Chemical class 0.000 claims 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 2
- 238000007323 disproportionation reaction Methods 0.000 claims 2
- 238000006317 isomerization reaction Methods 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- -1 polysiloxanes Polymers 0.000 claims 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 230000029936 alkylation Effects 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 claims 1
- 238000004523 catalytic cracking Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 238000002407 reforming Methods 0.000 claims 1
- 229910052702 rhenium Inorganic materials 0.000 claims 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims 1
- 150000004756 silanes Chemical class 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000011282 treatment Methods 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
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- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/00—Catalysts comprising molecular sieves
- 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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- B01J29/00—Catalysts comprising molecular sieves
- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/44—Noble metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
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- C07—ORGANIC CHEMISTRY
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- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
- C07C5/2708—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with crystalline alumino-silicates, e.g. molecular sieves
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/123—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of only one hydrocarbon
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/44—Noble metals
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Abstract
1. Способ модифицирования каталитически активного молекулярного сита, который включаета) повышение селективности указанного каталитически активного молекулярного сита путем контактирования с кремнийсодержащим агентом повышения селективности, иб) прокаливание каталитически активного молекулярного сита повышенной селективности в атмосфере, практически не содержащей паров воды, при высокотемпературных условиях прокаливания, включающих температуры выше 700°С, причем условия эффективны для снижения кислотной активности, измеренной как величина альфа, и увеличения диффузионного барьера указанного каталитически активного молекулярного сита, измеренного как скорость поглощения 2,3-диметилбутана, по сравнению с подвергнутым процедуре повышения селективности каталитически активным молекулярным ситом.2. Способ по п.1, где указанный диффузионный барьер увеличен по крайней мере на 25%.3. Способ по п.2, где указанный диффузионный барьер увеличен по крайней мере на 35%.4. Способ по п.3, где указанный диффузионный барьер увеличен по крайней мере на 50%.5. Способ по п.1, где указанное каталитически активное молекулярное сито выбирают из группы, включающей ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, цеолит бета, МСМ-22, МСМ-36, МСМ-49, МСМ-56, морденит, МСМ-58, синтетический фожазит, природный фожазит, МСМ-41, ALPO-5, VPI-5, SAPO-5, SAPO-11, SAPO-30, SAPO-31, SAPO-34, ITQ-2, ITQ-3, ITQ-12, и ITQ-13.6. Способ по п.5, где указанное каталитически активное молекулярное сито представляет собой ZSM-5 со связующим из оксида кремния.7. Способ по п.1, где указанное каталитически активное молекулярное сито дополнительно включает металл, выбранный из группы, включающей металл группы VIIIA, мет
Claims (18)
1. Способ модифицирования каталитически активного молекулярного сита, который включает
а) повышение селективности указанного каталитически активного молекулярного сита путем контактирования с кремнийсодержащим агентом повышения селективности, и
б) прокаливание каталитически активного молекулярного сита повышенной селективности в атмосфере, практически не содержащей паров воды, при высокотемпературных условиях прокаливания, включающих температуры выше 700°С, причем условия эффективны для снижения кислотной активности, измеренной как величина альфа, и увеличения диффузионного барьера указанного каталитически активного молекулярного сита, измеренного как скорость поглощения 2,3-диметилбутана, по сравнению с подвергнутым процедуре повышения селективности каталитически активным молекулярным ситом.
2. Способ по п.1, где указанный диффузионный барьер увеличен по крайней мере на 25%.
3. Способ по п.2, где указанный диффузионный барьер увеличен по крайней мере на 35%.
4. Способ по п.3, где указанный диффузионный барьер увеличен по крайней мере на 50%.
5. Способ по п.1, где указанное каталитически активное молекулярное сито выбирают из группы, включающей ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, цеолит бета, МСМ-22, МСМ-36, МСМ-49, МСМ-56, морденит, МСМ-58, синтетический фожазит, природный фожазит, МСМ-41, ALPO-5, VPI-5, SAPO-5, SAPO-11, SAPO-30, SAPO-31, SAPO-34, ITQ-2, ITQ-3, ITQ-12, и ITQ-13.
6. Способ по п.5, где указанное каталитически активное молекулярное сито представляет собой ZSM-5 со связующим из оксида кремния.
7. Способ по п.1, где указанное каталитически активное молекулярное сито дополнительно включает металл, выбранный из группы, включающей металл группы VIIIA, металл группы VIIA, металл группы VIA, металл группы VB, металл группы IVB, металл группы IIB, металл группы IIA, и металл группы IB Периодической таблицы.
8. Способ по п.7, где указанный металл представляет собой гидрирующий металл, выбранный из группы, включающей платину, палладий, железо, никель, галлий, цинк, молибден, и рений.
9. Способ по п.1, где указанный агент повышения селективности выбирают из группы, включающей полисилоксаны, силоксаны, силаны, дисиланы и алкоксисиланы.
10. Способ по п.1, где повышение селективности проводят посредством двух-шести обработок указанным агентом повышения селективности.
11. Способ по п.1, где указанное прокаливание проводят при условиях, эффективных для обеспечения каталитически активного молекулярного сита, имеющего величину альфа менее 700, и диффузионный барьер, измеренный как скорость поглощения 2,3-диметилбутана, составляющий менее 270 (D/(r2×106 с)).
12. Способ по п.11, где указанное прокаливание проводят при условиях, эффективных для обеспечения каталитически активного молекулярного сита, имеющего величину альфа, составляющую от 25 до 200, и диффузионный барьер, измеренный как скорость поглощения 2,3-диметилбутана, составляющий менее 150 (D/(r2×106 с)).
13. Способ по п.11, где указанное прокаливание проводят при условиях, эффективных для обеспечения каталитически активного молекулярного сита, имеющего величину альфа, составляющую от 5 до 25.
14. Способ по п.1, где указанное прокаливание проводят при температурах, составляющих от более 700 до 1200°С в течение 0,1-12 ч.
15. Способ структурно-селективной конверсии углеводорода, который включает: контактирование углеводородного сырья при условиях конверсии углеводорода с катализатором, включающим каталитически активное молекулярное сито, полученное в соответствии с любым из пп.1-14.
16. Способ по п.15, где указанную структурно-селективную конверсию углеводорода выбирают из группы, включающей каталитический крекинг, диспропорционирование ароматических соединений, изомеризацию ароматических соединений, алкилирование ароматических соединений, каталитическую депарафинизацию, и реформинг нафты.
17. Способ по п.15, где указанная структурно-селективная конверсия углеводорода представляет собой диспропорционирование толуола.
18. Способ по п.15, где указанная структурно-селективная конверсия углеводорода представляет собой изомеризацию ксилола.
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US10/625,322 US7238636B2 (en) | 2003-07-23 | 2003-07-23 | High temperature calcination of selectivated molecular sieve catalysts for activity and diffusional modification |
US10/625,322 | 2003-07-23 |
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EP (1) | EP1663484A1 (ru) |
JP (1) | JP4711960B2 (ru) |
KR (1) | KR101048577B1 (ru) |
CN (1) | CN1835798A (ru) |
CA (1) | CA2533157C (ru) |
RU (1) | RU2006105480A (ru) |
TW (1) | TW200523024A (ru) |
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KR101048577B1 (ko) | 2011-07-12 |
US7238636B2 (en) | 2007-07-03 |
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TW200523024A (en) | 2005-07-16 |
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