CN112547118A - Isomerization combined catalyst and hydroisomerization method - Google Patents
Isomerization combined catalyst and hydroisomerization method Download PDFInfo
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- CN112547118A CN112547118A CN201910909990.3A CN201910909990A CN112547118A CN 112547118 A CN112547118 A CN 112547118A CN 201910909990 A CN201910909990 A CN 201910909990A CN 112547118 A CN112547118 A CN 112547118A
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- Prior art keywords
- molecular sieve
- catalyst
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- ats
- combined
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 136
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000006317 isomerization reaction Methods 0.000 title claims description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 147
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 147
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 31
- 239000003921 oil Substances 0.000 claims description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 7
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002199 base oil Substances 0.000 abstract description 5
- 239000010687 lubricating oil Substances 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 57
- 239000000203 mixture Substances 0.000 description 52
- 239000000499 gel Substances 0.000 description 38
- 229910001868 water Inorganic materials 0.000 description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 28
- 239000003795 chemical substances by application Substances 0.000 description 28
- 229910052698 phosphorus Inorganic materials 0.000 description 28
- 239000011574 phosphorus Substances 0.000 description 28
- 229910052593 corundum Inorganic materials 0.000 description 27
- 229910001845 yogo sapphire Inorganic materials 0.000 description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 25
- 239000010703 silicon Substances 0.000 description 25
- 229910052710 silicon Inorganic materials 0.000 description 25
- 229910052782 aluminium Inorganic materials 0.000 description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 23
- -1 hydroxycarbonates Chemical class 0.000 description 21
- 238000001035 drying Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- 239000003292 glue Substances 0.000 description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 18
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 15
- 230000008025 crystallization Effects 0.000 description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 14
- 239000012071 phase Substances 0.000 description 13
- 235000011007 phosphoric acid Nutrition 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 12
- 239000007790 solid phase Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 230000032683 aging Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000614 phase inversion technique Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000002149 hierarchical pore Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- UVNBJCILWKEGHE-UHFFFAOYSA-N C(CC)NCCC.C(CC)NCCC Chemical compound C(CC)NCCC.C(CC)NCCC UVNBJCILWKEGHE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CNGGOAOYPQGTLH-UHFFFAOYSA-N [O-2].[O-2].[Mg+2].[Al+3] Chemical compound [O-2].[O-2].[Mg+2].[Al+3] CNGGOAOYPQGTLH-UHFFFAOYSA-N 0.000 description 1
- FXMRESIWAQPEFX-UHFFFAOYSA-N [Si+2]=O.[O-2].[Zr+4].[O-2].[Al+3] Chemical compound [Si+2]=O.[O-2].[Zr+4].[O-2].[Al+3] FXMRESIWAQPEFX-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- HPSLPPYQRGNWII-UHFFFAOYSA-N aluminum magnesium oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Al+3].[Si+2]=O HPSLPPYQRGNWII-UHFFFAOYSA-N 0.000 description 1
- UQCBLNXYKBXQFH-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) titanium(4+) Chemical compound [Si+2]=O.[O-2].[Ti+4].[O-2].[Al+3] UQCBLNXYKBXQFH-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates (APO compounds)
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/304—Pour point, cloud point, cold flow properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of hydroisomerization, in particular to a combined catalyst and a hydroisomerization method. The combined catalyst comprises a first catalyst and a second catalyst, wherein the first catalyst contains a molecular sieve with AST configuration. The Fischer-Tropsch wax modification is carried out by adopting the combined catalyst to produce the lubricating oil base oil, so that a good pour point depression effect can be obtained, and the lubricating oil base oil has high yield and high viscosity index.
Description
Technical Field
The invention relates to a combined catalyst and application thereof in isomerization of a hydrocarbon oil raw material, in particular to an isomerization catalyst composition and a hydrocarbon oil raw material hydroisomerization method.
Background
The molecular sieve material has high acidity and high specific surface area, has strong chemical stability and hydrothermal stability, is difficult to be corroded and dissolved by reactants to be damaged, and is an excellent acidic catalyst. Compared with the commonly used homogeneous catalysts, the molecular sieve material catalyst can be directly recycled without separation, and simultaneously, the environment and products are not polluted, so that the preparation of the molecular sieve with special performance is an important research direction in the chemical field.
CN104353484A discloses a preparation method of a cheap strong-acid hierarchical pore Beta zeolite, relating to a preparation method of a hierarchical pore Beta zeolite. CN103964458A discloses a Beta zeolite with high silica-alumina ratio hierarchical pore canals and a preparation method thereof. CN103073020A discloses a hierarchical pore zeolite molecular sieve and a preparation method and application thereof. CN104891526A discloses a preparation method of a mesoporous molecular sieve with high hydrothermal stability. CN1703490A discloses a catalyst combination method for producing lube base oil. The invention relates to a process for converting waxes containing heavy components to high quality lube basestocks by using a linear mesoporous molecular sieve having a near circular pore structure with an average diameter of 0.50nm to 0.65nm, wherein the difference between the maximum and minimum diameters is 0.05nm or less, followed by a molecular sieve beta zeolite catalyst. Both catalysts comprise one or more group VIII metals. For example, a cascaded two-bed catalyst system consisting of a first bed Pt/ZSM-48 catalyst followed by a second bed Pt/beta catalyst facilitates the treatment of heavy lube oils.
CN1803998A discloses a dewaxing catalyst containing a composite molecular sieve, which contains a molecular sieve with a one-dimensional mesoporous structure and a molecular sieve with a macroporous structure, wherein the weight ratio of the molecular sieve with the one-dimensional mesoporous structure to the molecular sieve with the macroporous structure is 80-99: 1-20, the molecular sieve with the macroporous structure contains non-framework silicon, and the content of the silicon is 1-20 wt% calculated by oxide and based on the molecular sieve.
Disclosure of Invention
The invention aims to provide a combined hydroisomerization catalyst, which is characterized by comprising a first catalyst and a second catalyst, wherein the first catalyst comprises a carrier containing an ATS molecular sieve and an active metal component loaded on the carrier, and the second catalyst comprises a carrier containing a ten-membered ring silicon-aluminum molecular sieve and an active metal component loaded on the carrier.
The combined catalyst is applied to processing of hydrocarbon oil raw materials, particularly used for isomerization reactions of hydrocarbon oil raw materials rich in paraffin, such as cracking tail oil isomerization, biological aviation kerosene production, C5C6 isomerization, Fischer-Tropsch synthetic wax processing and the like, and the obtained target product has low pour point and high yield.
Specifically, the present invention includes the following: the invention provides a combined catalyst which comprises a first catalyst and a second catalyst, wherein the first catalyst comprises a carrier containing an ATS molecular sieve and an active metal component loaded on the carrier, and the second catalyst comprises a carrier containing a ten-membered ring silicon-aluminum molecular sieve and an active metal component loaded on the carrier. Preferably, the ATS molecular sieve is an ATS aluminum phosphate molecular sieve, and further preferably, the ATS type molecular sieve is selected from MAPO-36, SAPO-36 and AlPO4-36、CoSAPO-36、ZnAPO-36、AlPO4-36 and FAPO-36.
According to the combined catalyst, the carrier containing the ATS molecular sieve can also contain molecular sieves with other configurations and/or heat-resistant inorganic oxides except the molecular sieves, the molecular sieves with other configurations are one or more selected from ZSM-22 molecular sieves, ZSM-23 molecular sieves, ZSM-48 molecular sieves, ZSM-5 molecular sieves, SSZ-32 molecular sieves and Eu-1 molecular sieves, and the heat-resistant inorganic oxides except the molecular sieves are one or more selected from aluminum oxide, aluminum oxide-magnesium oxide, silicon oxide-aluminum oxide-titanium oxide, silicon oxide-aluminum oxide-magnesium oxide and silicon oxide-aluminum oxide-zirconium oxide. Preferably, the ATS molecular sieve content is 10-100 wt%, the molecular sieve content of other configurations is 0-90 wt%, and the refractory inorganic oxide content except the molecular sieve is 0-60 wt% based on the support containing the ATS molecular sieve.
According to the combined catalyst, the decatomic ring aluminosilicate molecular sieve in the second catalyst is preferably one or more selected from ZSM-22 molecular sieve, ZSM-23 molecular sieve, ZSM-48 molecular sieve, ZSM-5 molecular sieve, SSZ-32 molecular sieve and Eu-1 molecular sieve.
According to the combined catalyst of the present invention, the active metal in the first catalyst and the second catalyst is an active metal component commonly used in a hydroisomerization catalyst, and may be the same or different, and specifically, the active metal may be at least one of group VIII metal components, and is preferably at least one of group VIII noble metal components.
According to the combined catalyst, the active metal content and the carrier content in the first catalyst and the second catalyst can be the same or different, and can be the content of a conventional isomerization catalyst, for example, the content of the carrier is 99-99.9 wt% based on the catalyst, and the content of the active metal component in a reduced state is 0.1-1.0 wt%.
The combined catalyst according to the present invention, when applied to a specific device or reactor, may be such that the first catalyst is disposed upstream and the second catalyst is disposed downstream along the flow direction of the reactant stream; it is also possible that the second catalyst is arranged upstream and the first catalyst is arranged downstream. Preferably, the first catalyst is disposed upstream.
The ratio of the first catalyst to the second catalyst is not particularly limited in the present invention, and may be selected conventionally or specifically depending on the nature of the reaction material and the purpose of processing, and for example, the weight ratio of the first catalyst to the second catalyst may be 1:0.1 to 10, preferably 1:2 to 5.
The invention also provides a hydrocarbon oil raw material hydroisomerization method, which comprises the step of carrying out contact reaction on the hydrocarbon oil raw material and any one of the combined catalysts provided by the invention under the hydroisomerization condition.
The hydroisomerization conditions in the process of the invention are conventional conditions, such as: the temperature is 250 ℃ to 400 ℃, and the preference is that300 ℃ and 350 ℃; the pressure is 1-30MPa, preferably 5-20 MPa; the space velocity is 0.1-3h-1Preferably 0.5 to 2h-1(ii) a The volume ratio of the hydrogen to the oil is 50-1000, preferably 400-600.
According to the hydroisomerization method provided by the invention, the hydrocarbon oil raw material is preferably raw oil rich in paraffin, preferably one or more of self-cracking tail oil, biological aviation kerosene production raw material, C5C6 isomerization raw material and Fischer-Tropsch synthetic wax.
Drawings
FIG. 1 is an XRD spectrum of a sample of the molecular sieve synthesized in preparation 4; fig. 2 is an SEM photograph of a sample of the molecular sieve synthesized in preparation example 4.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The combined catalyst provided by the invention comprises a first catalyst and a second catalyst, wherein the first catalyst contains a carrier containing an ATS molecular sieve and an active metal component loaded on the carrier, and the second catalyst contains a carrier containing a ten-membered ring silicon-aluminum molecular sieve and an active metal component loaded on the carrier. Preferably, the ATS molecular sieve is an ATS aluminum phosphate molecular sieve, and further preferably, the ATS type molecular sieve is selected from MAPO-36, SAPO-36 and AlPO4-36、CoSAPO-36、ZnAPO-36、AlPO4-36 and FAPO-36.
The preparation method of the first catalyst and the second catalyst in the present invention is not particularly limited, and the supported catalyst can be prepared according to a conventional method for preparing a supported catalyst by using the carrier defined in the present invention. The supporting method of the present invention is not particularly limited as long as it is sufficient to support the active metal component on the support, and a preferable method is an impregnation method comprising preparing an impregnation solution of the metal-containing compound and thereafter impregnating the support with the solution. The impregnation method is a conventional method, and for example, the impregnation method can be excess liquid impregnation and pore saturation impregnation. The compound containing the active metal component is selected from one or more soluble compounds in the compound.
In the case of the first catalyst and the second catalyst, it is also possible to introduce a promoter component, such as a phosphorus component, which enhances the catalyst performance. When the catalyst further contains an additional component such as phosphorus, the additional component may be introduced by any method, for example, a compound containing the component such as phosphorus and a compound containing an active metal component may be formulated into a mixed solution, and then the carrier may be impregnated; or preparing a compound containing phosphorus and the like into a solution separately, impregnating the carrier and roasting. When the additive component such as phosphorus and the like and the active metal are introduced separately into the carrier, it is preferable that the carrier is first impregnated with a solution containing a compound of the additive component and calcined, and then impregnated with a solution containing a compound of the active metal component. Wherein, the roasting temperature is 400-600 ℃, preferably 420-500 ℃, and the roasting time is 2-6 hours, preferably 3-6 hours.
The ten-membered ring silicon aluminum molecular sieve and the ATS molecular sieve can be commercial agents and can also be prepared according to the existing method, and the method is not limited.
In the composite catalyst of the present invention, the ten-membered ring aluminosilicate molecular sieve is not particularly limited in type, and may be, for example, at least one of a ZSM-22 molecular sieve, a ZSM-23 molecular sieve, a ZSM-48 molecular sieve, a ZSM-5 molecular sieve, an SSZ-32 molecular sieve and an Eu-1 molecular sieve. Preferably, the ten-membered ring silicoaluminophosphate molecular sieve is a ZSM-22 molecular sieve and/or a ZSM-48 molecular sieve. Generally, the preparation of the ten-membered ring silicon-aluminum molecular sieve can be divided into steps of colloid formation, crystallization, post-treatment and the like, and the conditions of each step are the conventional conditions.
For the scheme of preparing the ATS molecular sieve according to the prior method, in a specific embodiment, taking the synthesis of the AlPO-36 molecular sieve as an example, phosphoric acid can be used as a phosphorus source, pseudo-boehmite can be used as an aluminum source, and tri-n-propylamine can be used(Pr3N) is taken as a template agent (marked as R), and then the AlPO-36 molecular sieve is synthesized by initial gelation, aging and hydrothermal treatment.
In another embodiment, taking the preparation of SAPO-36 as an example in a particular embodiment, one of three approaches can be used: the first method adopts phosphoric acid as a phosphorus source, polyaluminium chloride as an aluminum source, gas-phase silicon dioxide as a silicon source and tri-n-propylamine (Pr)3N) as template agent, adding partial MAPO-36 molecular sieve as crystal seed into the initial gel mixture during synthesis, and treating under hydrothermal condition for a period of time. The second method adopts phosphoric acid as a phosphorus source, pseudo-boehmite as an aluminum source, silica sol as a silicon source and tri-n-propylamine (Pr)3N) as a template, adding MAPO-36 molecular sieve as a seed crystal to the initial gel mixture, and treating for a period of time under hydrothermal conditions. And thirdly, adding a certain amount of MAPO-36 molecular sieve serving as seed crystal into the initial gel mixture by using phosphoric acid as a phosphorus source, pseudo-boehmite as an aluminum source, fumed silica as a silicon source and N, N-dimethylbenzylamine as a template agent (DMBA), and then treating for a period of time under a hydrothermal condition.
For the synthesis of other types of ATS molecular sieves, different sources of auxiliary and templating agents may be selected depending on the specific composition of the molecular sieve, e.g., ZnAPO-36 employs zinc acetate dihydrate (Zn (CH)3COO)2·2H2O) is a metal zinc source, and di-n-propylamine (di-n-propylamine) is used as a template agent; CoSAPO-36 can use cobalt sulfate as metal cobalt source, and tri-n-propylamine (Pr)3N) is a template agent; AlPO4-36 using tri-n-propylamine as a template; FAPO-36: adopting copperas (FeSO)4·7H2O) is used as an iron source, and tri-n-propylamine is used as a template agent.
In a preferred embodiment of the invention, 4-pyrrolidinylpyridine is used as a template agent to synthesize the ATS structure silicoaluminophosphate SAPO-36 molecular sieve, and the pure phase SAPO-36 molecular sieve can be synthesized in a wider synthesis range without adding any seed crystal. The SAPO-36 molecular sieve is synthesized by adopting a phosphor-aluminum dry glue solution phase inversion method or a hydrothermal method.
Specifically, the synthesis method comprises: providing an initial gel mixture, the initial gel mixture containing a templating agent; crystallizing the initial gel mixture; carrying out solid-liquid separation on the crystallized product, and washing, drying and optionally roasting the obtained solid phase; wherein the template agent is 4-pyrrolidinylpyridine.
When a phosphorus-aluminum dry glue solution phase inversion method is adopted, the initial gel mixture contains phosphorus-aluminum dry glue, a silicon source, a template agent 4-pyrrolidinyl pyridine and water; when the hydrothermal synthesis method is adopted, the initial gel mixture further contains a phosphorus source, an aluminum source, a silicon source, a template agent 4-pyrrolidinylpyridine and water.
The phase inversion method of the phosphor-aluminum dry glue solution comprises the following steps:
(1) providing a mixture A, wherein the mixture A contains a phosphorus source, an aluminum source and water; (2) aging the mixture A, and then drying to obtain the phosphorus-aluminum dry glue; (3) providing an initial gel mixture B, wherein the initial gel mixture B contains the phosphorus-aluminum dry glue prepared in the step (2), a silicon source, a template agent and water; (4) crystallizing the initial gel mixture B; (5) and (3) carrying out solid-liquid separation on the crystallized product, and washing, drying and optionally roasting the obtained solid phase.
When a hydrothermal process is employed, the hydrothermal process comprises the steps of:
(1) providing an initial gel mixture C, wherein the initial gel mixture C contains a phosphorus source, an aluminum source, a silicon source, a template agent and water; (2) crystallizing the initial gel mixture C; (3) and (3) carrying out solid-liquid separation on the crystallized product, and washing, drying and optionally roasting the obtained solid phase.
In the method for synthesizing the SAPO-36 molecular sieve by adopting a phosphorus-aluminum dry glue solution phase inversion method, when the mixture A is prepared, the mixture A contains a phosphorus source, an aluminum source and water, and the phosphorus source is P2O5The aluminum source is calculated as Al2O3The molar ratio of the phosphorus source to the aluminum source to the water is 0.6-1.2:1:30-70, preferably 0.8-1.2:1: 35-65. In preparing the mixture a, the water is the total amount of water, for example, including added water, and also including water in a phosphorus source and an aluminum source. In preparing the initial gel mixture B, the initial gel mixture B contains the gel mixture prepared in the step (2)The aluminum phosphate dry glue comprises Al, a silicon source, a template agent and water2O3The silicon source is SiO2The molar ratio of the phosphorus-aluminum dry glue to the silicon source to the template agent to the water is 1:0.1-1.2:1-10:10-200, preferably 1:0.15-1:1.5-5: 20-150. In preparing the initial gel mixture B, the water is the total amount of water, including, for example, the added water, as well as the amount of water in the phosphor-aluminum xerogel, the silicon source, and the templating agent.
In the method for synthesizing the SAPO-36 molecular sieve by adopting the dry aluminum phosphate gel liquid phase inversion method, the dry aluminum phosphate gel can be prepared by adopting a conventional method, and the dry aluminum phosphate gel, a silicon source, a template agent and water are mixed to obtain the initial gel mixture B. Specifically, an aluminum source is mixed with water, then a phosphorus source is added with stirring to obtain a mixture A, the mixture A is aged with stirring, the aging temperature can be 50-80 ℃, preferably 60-70 ℃, the aging time can be 6-20 hours, preferably 10-18 hours, then the aged mixture A is dried, the drying temperature can be 80-110 ℃, preferably 80-100 ℃, and the drying time can be 15-35 hours, preferably 20-30 hours, and the phosphorus aluminum dry glue is prepared. And sequentially adding and uniformly mixing the phosphorus-aluminum dry glue, the silicon source, the water and the template agent to obtain the initial gel mixture B.
In the method for synthesizing the SAPO-36 molecular sieve by a hydrothermal method, when an initial gel mixture C is prepared, the initial gel mixture C contains a phosphorus source, an aluminum source, a silicon source, a template agent and water, and the phosphorus source is P2O5The aluminum source is calculated as Al2O3The silicon source is SiO2The molar ratio of the phosphorus source, the silicon source, the aluminum source, the template agent R and the water is 0.6-1.2:0.1-1.2:1:1-10:10-200, preferably 0.8-1.2:0.15-1:1:1.5-5: 20-150. In preparing the initial gel mixture C, the water is the total amount of water, including, for example, the added water, and also including the amounts of water in the phosphorus source, silicon source, aluminum source, and templating agent.
In the method for synthesizing the SAPO-36 molecular sieve by a hydrothermal method, a phosphorus source, an aluminum source, a silicon source, a template agent and water can be mixed by a conventional method to obtain the initial gel mixture C. Specifically, an aluminum source, water, a phosphorus source, a silicon source, and a template agent may be sequentially added and uniformly mixed to obtain the initial gel mixture C.
The types of the phosphorus source, the silicon source, and the aluminum source are not particularly limited and may be conventionally selected.
Generally, the phosphorus source may be selected from at least one of orthophosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and an organic phosphide. Preferably, the organophosphate is at least one of trimethylphosphorus and triethylphosphorous.
The aluminum source may be at least one selected from the group consisting of aluminum salt, pseudoboehmite, aluminum isopropoxide, aluminum hydroxide dry gel and activated alumina. Preferably, the aluminum salt is at least one of aluminum chloride and aluminum sulfate.
The silicon source can be at least one selected from silica sol, active silica, solid silica gel, silicon-containing compound shown in formula I and white carbon black,
in the formula I, R, R2、R3And R4Each is C1-C4Such as methyl, ethyl, propyl and isomers thereof and butyl and isomers thereof.
Preferably, the silicon-containing compound is at least one of silica sol, active silica, solid silica gel, ethyl orthosilicate and white carbon black.
In addition, the hydrocarbon oil hydroisomerization method provided by the invention comprises the step of carrying out contact reaction on raw oil and the catalyst provided by the invention under the hydroisomerization condition, wherein the raw oil is preferably paraffin-rich raw oil, such as hydrocracking tail oil, a biological aviation fuel production raw material, a C5C6 isomerization raw material, Fischer-Tropsch synthetic wax and the like. The hydroisomerization conditions are conventional conditions, and as in the process of the present invention, the hydroisomerization conditions are not particularly limited as long as they are sufficient to cause a hydroisomerization reaction of the feedstock. Generally, the reaction conditions may include: the temperature is 200-500 ℃,preferably 250-400 ℃, more preferably 300-350 ℃; a pressure of 1 to 30MPa, preferably 2 to 20MPa, more preferably 5 to 20MPa, the pressure referred to herein being an absolute pressure; the space velocity is 0.1-5h-1Preferably 0.1 to 3h-1More preferably 0.5 to 2 hours-1(ii) a The volume ratio of the hydrogen to the oil is 50-3000, preferably 300-3000, more preferably 400-600.
In the combined catalyst of the present invention, the arrangement of the first catalyst and the second catalyst is not particularly limited. The first catalyst may be disposed upstream and the second catalyst downstream in the direction of flow of the reactant stream such that the reactant material first contacts the first catalyst and then contacts the second catalyst; alternatively, the second catalyst may be disposed upstream and the first catalyst disposed downstream such that the reaction mass first contacts the second catalyst for reaction and then contacts the first catalyst for reaction; or the first catalyst and the second catalyst are arranged in a staggered way, so that the reaction materials are sequentially and alternately in contact reaction with the first catalyst and the second catalyst.
In the present invention, in the reaction system, the same catalyst bed may include only one catalyst (e.g., the first catalyst or the second catalyst), or may include both the first catalyst and the second catalyst. When two catalysts are included in the same catalyst bed, the packing process of the catalyst bed is preferably as follows: one of the catalysts is loaded first, and the other catalyst is loaded.
In the combined catalyst of the present invention, the weight ratio of the first catalyst to the second catalyst is 1:0.1 to 10, preferably 1:2 to 5, more preferably 1: 1-2.5, more preferably 1: 1-2.
In the present invention, the weight ratio of the first catalyst to the second catalyst means the weight ratio of the first catalyst distributed in all catalyst beds to the second catalyst distributed in all catalyst beds.
In the catalyst of the present invention, the active metal component may be a group VIII metal component, preferably a group VIII noble metal component. The group VIII noble metal may be at least one of ruthenium, osmium, palladium, platinum, rhodium and iridium, preferably palladium and/or platinum, most preferably platinum.
In the present invention, the active metal component may be provided from an active metal component precursor. The active metal component precursor is selected from group VIII noble metal element-containing compounds. The group VIII noble metal element-containing compound may be selected from one or more of group VIII noble metal element-containing nitrates, chlorides, sulfates, formates, acetates, phosphates, citrates, oxalates, carbonates, hydroxycarbonates, hydroxides, phosphates, phosphides, sulfides, aluminates, molybdates, tungstates and water-soluble oxides.
The hydroisomerization method comprises the step of carrying out contact reaction on a hydrocarbon oil raw material and any one of the composite catalysts provided by the invention. The hydroisomerization conditions are conventional conditions, for example: the temperature is 250-400 ℃, preferably 300-350 ℃; the pressure is 1-30MPa, preferably 5-20 MPa; the space velocity is 0.1-3h-1Preferably 0.5 to 2h-1(ii) a The volume ratio of the hydrogen to the oil is 50-1000, preferably 400-600. The hydrocarbon oil raw material is preferably a raw material rich in paraffin, and can be one or more selected from cracking tail oil, biological aviation kerosene production raw material, C5C6 isomerization raw material and Fischer-Tropsch synthetic wax.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples, X-ray powder diffraction phase analysis (XRD) was performed using an Empyrean type diffractometer, parnaciaceae, netherlands, equipped with a PIXcel3D detector. And (3) testing conditions are as follows: cu target, Ka radiation, Ni filter, tube voltage 40kV, tube current 40mA, and scanning range 5-50 deg. Scanning electron microscope morphology analysis (SEM) adopted Japanese Hitachi S4800 type scanning electron microscope. And (3) testing conditions are as follows: after the sample was dried and ground, it was stuck on a conductive gel. The accelerating voltage of the analysis electron microscope is 5.0kV, and the magnification is 20-800000 times.
Preparation example 1
Phosphoric acid is used as a phosphorus source, pseudo-boehmite is used as an aluminum source, silica sol is used as a silicon source, andtri-n-propylamine (Pr)3N) as template agent, the synthetic process is according to 1.5Pr3N:1.0Al2O3:0.9P2O5:0.6SiO2:40H2The molar ratio of O is prepared into an initial gel mixture, 10 percent (based on the mass of the initial gel mixture) of MAPO-36 molecular sieve is added into the initial gel mixture as seed crystal, and then the crystallization is carried out for 72 hours at 150 ℃ under hydrothermal conditions. And (3) filtering or centrifugally separating, washing the obtained solid phase to be neutral by using deionized water, and drying at 110 ℃ for 12 hours to obtain the molecular sieve raw powder. And (3) carrying out X-ray diffraction analysis on the sample, and confirming the XRD spectrogram to be a pure-phase SAPO-36 molecular sieve.
Preparation example 2
AlPO-36 adopts phosphoric acid as a phosphorus source, pseudo-boehmite as an aluminum source and tri-n-propylamine (Pr)3N) as template agent, the synthetic process is according to 1.7Pr3N:1.0Al2O3:1.0P2O5:80H2And the molar ratio of O is that the initial gel mixture is aged for 120 hours at 120 ℃, then crystallized for 72 hours at 140 ℃ under the hydrothermal condition, and the AlPO-36 molecular sieve is synthesized. And (3) filtering or centrifugally separating, washing the obtained solid phase to be neutral by using deionized water, and drying at 110 ℃ for 12 hours to obtain the molecular sieve raw powder. The sample is subjected to X-ray diffraction analysis, and an XRD spectrogram proves that the sample is a pure-phase AlPO-36 molecular sieve.
Preparation example 3
CoSAPO-36, adopting phosphoric acid as phosphorus source, pseudo-boehmite as aluminum source, gas-phase silicon dioxide as silicon source, cobalt sulfate as metal cobalt source, tri-n-propylamine as template agent, and adopting 1.8Pr of synthesis process3N:0.95Al2O3:1.0P2O5:0.4SiO2:0.1CoO:60H2And (3) the molar ratio of O, stirring for 8 hours to be uniform when the raw materials are mixed, crystallizing for 100 hours at 150 ℃ under a hydrothermal condition, taking out a crystallized product when the temperature of the high-pressure kettle is reduced to room temperature after crystallization is finished, filtering or centrifugally separating, washing the obtained solid phase to be neutral by using deionized water, and drying for 12 hours at 110 ℃ to obtain the molecular sieve raw powder. And (3) carrying out X-ray diffraction analysis on the sample, and confirming the XRD spectrogram to be a pure-phase CoSAPO-36 molecular sieve.
Preparation example 4
4.91 g of pseudo-boehmite (Al)2O383 percent of mass fraction) and 33.81 g of deionized water are stirred and mixed until uniform, and 9.22 g of orthophosphoric acid (H) is slowly added in a trickle manner under the stirring state3PO485% by mass), stirring thoroughly at 70 ℃ and aging for 12 hours to obtain a mixture A. And pouring the mixture A into a tray, and drying at 80 ℃ for 24 hours to obtain the phosphorus-aluminum dry glue.
6.07 g of the prepared dry aluminum phosphate gel (solid content: 80.32%) was added to the polytetrafluoroethylene lining, followed by 0.39 g of solid silica gel (SiO)293% by mass), 5.80 g of deionized water, 6.11 g of 4-pyrrolidinylpyridine (C)9H12N297 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝1.0、SiO2/Al2O3＝0.3、R/Al2O3＝2.0、H2O/Al2O3＝20。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing first-stage crystallization under the autogenous pressure: crystallizing at 150 ℃ for 36 hours, heating to 180 ℃ again, and carrying out second-stage crystallization: crystallizing at 180 deg.C for 45 hr, cooling the autoclave to room temperature, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
The obtained molecular sieve is subjected to X-ray diffraction analysis, and an XRD spectrogram is shown in figure 1, and the molecular sieve is proved to be the pure-phase ATS structure silicoaluminophosphate SAPO-36 molecular sieve. The appearance of the molecular sieve is observed by adopting SEM, and an SEM picture is shown in figure 2 and is in an ellipsoid shape.
Preparation example 5
5.44 g of aluminum hydroxide dry glue (Al2O3 mass fraction of 75%) and 25.87 g of deionized water are stirred and mixed until uniform, and 10.61 g of orthophosphoric acid (H) is slowly added in a trickle manner under stirring3PO485% by mass), stirring thoroughly at 70 ℃ and aging for 10 hours to obtain a mixture A.And pouring the mixture A into a tray, and drying at 80 ℃ for 28 hours to obtain the phosphorus-aluminum dry glue.
6.50 g of the prepared phosphorus-aluminum dry glue (solid content 81.58%) was added to a polytetrafluoroethylene lining, and 0.60 g of silica Sol (SiO) was added in sequence 230% by mass of deionized water, 16.12 g of deionized water, 9.17 g of 4-pyrrolidinylpyridine (C)9H12N297 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝1.15、SiO2/Al2O3＝0.15、R/Al2O3＝3.0、H2O/Al2O3＝50。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing first-stage crystallization under the autogenous pressure: crystallizing at 160 ℃ for 35 hours, heating to 180 ℃ again, and carrying out second-stage crystallization: crystallizing at 180 deg.C for 50 hr, cooling the autoclave to room temperature, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
And (3) carrying out X-ray diffraction analysis on the obtained molecular sieve, and confirming that the molecular sieve is a pure-phase SAPO-36 molecular sieve by an XRD spectrogram. And observing the morphology of the molecular sieve by adopting SEM to show a sword-shaped morphology.
Preparation example 6
16.67 g of aluminum isopropoxide (C)9H21AlO398 percent of mass fraction) and 41.38 g of deionized water are stirred and mixed until uniform, and 10.15 g of orthophosphoric acid (H) is slowly added in a trickle manner under the stirring state3PO485% by mass), stirring thoroughly at 65 ℃ and aging for 15 hours to obtain a mixture A. And pouring the mixture A into a tray, and drying at 85 ℃ for 25 hours to obtain the phosphorus-aluminum dry glue.
6.19 g of the dry aluminum phosphate gel (83.34% solids) are added to a polytetrafluoroethylene liner, followed by 0.65 g of solid silica gel (SiO)293% by mass), 20.36 g of deionized water, 6.11 g of 4-pyrrolidinyl groupPyridine (C)9H12N297 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝1.1、SiO2/Al2O3＝0.5、R/Al2O3＝2.0、H2O/Al2O3＝60。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing first-stage crystallization under the autogenous pressure: crystallizing at 155 ℃ for 40 hours, heating to 190 ℃, and carrying out second-stage crystallization: crystallizing at 190 deg.C for 40 hr, cooling the autoclave to room temperature, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
And (3) carrying out X-ray diffraction analysis on the obtained molecular sieve, and confirming that the molecular sieve is a pure-phase SAPO-36 molecular sieve by an XRD spectrogram. And observing the morphology of the molecular sieve by adopting SEM, wherein the molecular sieve is in a regular ellipsoid shape.
Preparation example 7
Mixing 4.91 pseudo-boehmite (Al)2O383 percent of mass fraction) and 30.28 g of deionized water are stirred and mixed until uniform, and 8.76 g of orthophosphoric acid (H) is slowly added in a trickle manner under the stirring state3PO485% by mass), stirring thoroughly at 65 ℃ and aging for 18 hours to give a mixture A. And pouring the mixture A into a tray, and drying at 90 ℃ for 20 hours to obtain the phosphorus-aluminum dry glue.
5.53 g of the prepared dry aluminum phosphate gel (85.62% solids) were added to a polytetrafluoroethylene liner, followed by 1.20 g of silica Sol (SiO)230% by mass of deionized water, 12.50 g of deionized water, 9.17 g of 4-pyrrolidinylpyridine (C)9H12N297 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝0.95、SiO2/Al2O3＝0.3、R/Al2O3＝3.0、H2O/Al2O3＝40。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing first-stage crystallization under the autogenous pressure: crystallizing at 170 ℃ for 30 hours, heating to 190 ℃, and performing second-stage crystallization: crystallizing at 190 deg.C for 40 hr, cooling the autoclave to room temperature, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
And (3) carrying out X-ray diffraction analysis on the obtained molecular sieve and observing the morphology of the molecular sieve by adopting SEM (scanning Electron microscope), wherein the characterization result shows that the sample is a pure-phase SAPO-36 molecular sieve and the morphology of the sample is an ellipsoid morphology.
Preparation example 8
4.91 g of pseudo-boehmite (Al)2O383 percent of mass fraction) and 20.59 g of deionized water are stirred and mixed until uniform, and 9.70 g of ammonium hydrogen phosphate ((NH) is slowly added under stirring4)2HPO498% by mass), stirring thoroughly at 60 ℃ and aging for 18 hours to obtain a mixture A. And pouring the mixture A into a tray, and drying at 100 ℃ for 18 hours to obtain the phosphorus-aluminum dry glue.
5.51 g of the dry aluminum phosphate gel (83.35% solids) are added to a polytetrafluoroethylene liner, followed by 1.03 g of solid silica gel (SiO)293% by mass), 13.29 g of deionized water, 4.58 g of 4-pyrrolidinylpyridine (C)9H12N297 percent of mass fraction), and stirring uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝0.9、SiO2/Al2O3＝0.8、R/Al2O3＝1.5、H2O/Al2O3＝40。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing first-stage crystallization under the autogenous pressure: crystallizing at 135 deg.C for 40 hr, heating to 170 deg.C, and performing second-stage crystallization: crystallizing at 170 deg.C for 45 hr, cooling the autoclave to room temperature, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
And (3) carrying out X-ray diffraction analysis on the obtained molecular sieve, and confirming that the molecular sieve is a pure-phase SAPO-36 molecular sieve by an XRD spectrogram. And observing the morphology of the molecular sieve by adopting an SEM, wherein the SEM picture is in a regular ellipsoid shape.
Preparation example 9
2.46 g of pseudo-boehmite (Al)2O383% by mass), 5.89 g of deionized water, and 4.61 g of orthophosphoric acid (H)3PO485% by mass), 0.39 g of solid silica gel (SiO)293% by mass), 6.11 g of 4-pyrrolidinylpyridine (C)9H12N297 percent of mass fraction) are added into the polytetrafluoroethylene lining in sequence and are stirred uniformly, wherein the adding molar ratio of each component is as follows: p2O5/Al2O3＝1.0、SiO2/Al2O3＝0.3、R/Al2O3＝2.0、H2O/Al2O3＝20。
Covering the polytetrafluoroethylene lining filled with the reaction mixture, placing the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, placing the autoclave into a rotary convection oven, setting the rotating speed at 20r/min, and performing first-stage crystallization under the autogenous pressure: crystallizing at 150 ℃ for 36 hours, heating to 180 ℃ again, and carrying out second-stage crystallization: crystallizing at 180 deg.C for 45 hr, cooling the autoclave to room temperature, taking out crystallized product, filtering or centrifuging, washing the obtained solid phase with deionized water to neutrality, and drying at 110 deg.C for 12 hr to obtain molecular sieve powder.
And (3) carrying out X-ray diffraction analysis on the obtained molecular sieve, and confirming that the molecular sieve is a pure-phase SAPO-36 molecular sieve by an XRD spectrogram. And observing the morphology of the molecular sieve by adopting the SEM, wherein the SEM picture is in an ellipsoid shape.
Preparation example 10
36.3 g of a 40% by weight SiO solution were taken21.77 g of analytically pure Al2(SO4)3·18H2O, 3.94 g of analytically pure KOH and 8.44 g of hexamethylenediamine are used. Mixing hexamethylenediamine with silica sol, adding KOH and Al2(SO4)3·18H2O and 89.4 g of deionized water, then mixing the two solutions, stirring for 1 hour, transferring the mixture into a reaction kettle, and crystallizing for 72 hours at 160 ℃. The synthesized molecular sieve is a ZSM-22 molecular sieve.
Catalyst preparation
60 g of the molecular sieve obtained in the above preparation examples 1 to 10 was mixed with 20 g of alumina, and mixed with 80 g of a 2% nitric acid solution. And forming on a strip extruding machine. The shaped support was calcined at 600 ℃ for 4 hours. 0.5% of Pt was supported on the carrier, and then calcined in air and reduced in hydrogen gas at 400 ℃ for 4 hours, respectively. Are respectively named as C1-C10.
Examples 1 to 9
The obtained catalyst and a commercial catalyst RIW-2 are loaded in a first reactor and a second reactor of a high-pressure hydrogenation reactor according to the scheme in the table 1 to obtain the catalyst composition. The cracking tail oil raw material is injected into a reactor from top to bottom for reaction. And after the reaction is finished, distilling the product to cut off light components with the temperature of less than 370 ℃, and analyzing the components with the temperature of more than 370 ℃ and calculating the yield.
TABLE 1 filling scheme
| First reactor | Second reactor | |
| Example 1 | C1，80 | C10，100 |
| Example 2 | C2，100g | C10，100g |
| Example 3 | C3，100 | C10，80 |
| Example 4 | C4，100g | C10，100g |
| Example 5 | C5，200g | C10，80g |
| Example 6 | C6，80g | C10，120g |
| Example 7 | C7，100g | C10，100g |
| Example 8 | C8，100g | RIW-2，100g |
| Example 9 | C9，100g | RIW-2，100g |
TABLE 2 cracked tail oil Properties
TABLE 3 reaction conditions
TABLE 4
As can be seen from the data in Table 4 above, the Fischer-Tropsch wax modification method for producing lube base oil according to the present invention can achieve good pour point depressing effect, and the lube base oil has high yield and high viscosity index.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A combined catalyst, which is characterized by comprising a first catalyst and a second catalyst, wherein the first catalyst comprises a carrier containing an ATS molecular sieve and an active metal component loaded on the carrier, and the second catalyst comprises a carrier containing a ten-membered ring silicon aluminum molecular sieve and an active metal component loaded on the carrier.
2. The combined catalyst of claim 1, wherein the ATS molecular sieve is an ATS aluminum phosphate molecular sieve.
3. The combined catalyst of claim 1, wherein the ATS-type molecular sieve is selected from MAPO-36, SAPO-36, AlPO4-36、CoSAPO-36、ZnAPO-36、AlPO4-36 and FAPO-36.
4. The combined catalyst of claim 1, wherein the ten-membered ring silicoaluminophosphate molecular sieve is selected from one or more of a ZSM-22 molecular sieve, a ZSM-23 molecular sieve, a ZSM-48 molecular sieve, a ZSM-5 molecular sieve, an SSZ-32 molecular sieve and an Eu-1 molecular sieve.
5. The combined catalyst according to claim 1, wherein the support containing the ATS molecular sieve further contains a molecular sieve with other configuration and/or a heat-resistant inorganic oxide except the molecular sieve, the molecular sieve with other configuration is one or more selected from ZSM-22 molecular sieve, ZSM-23 molecular sieve, ZSM-48 molecular sieve, ZSM-5 molecular sieve, SSZ-32 molecular sieve and Eu-1 molecular sieve, and the heat-resistant inorganic oxide except the molecular sieve is one or more selected from alumina, alumina-magnesia, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
6. The combined catalyst according to claim 5, wherein the ATS molecular sieve content is 10-100 wt%, the molecular sieve content of other configurations is 0-90 wt%, and the refractory inorganic oxide other than molecular sieve is 0-60 wt% based on the ATS molecular sieve-containing support.
7. The combined catalyst of claim 1, wherein the active metal components in the first and second catalysts are independently selected from at least one of group VIII metal components; preferably, the active metal components in the first and second catalysts are independently selected from at least one of the group VIII noble metal components.
8. The combined catalyst according to claim 1, wherein the first catalyst has a content of the carrier of 99 to 99.9 wt% and an active metal component content in a reduced state of 0.1 to 1.0 wt%, based on the first catalyst; in the second catalyst, the content of the carrier is 99-99.9 wt% based on the second catalyst, and the content of the active metal component in a reduced state is 0.1-1.0 wt%.
9. The combined catalyst of any of claims 1-8, wherein the first catalyst is disposed upstream and the second catalyst is disposed downstream in a flow direction of the reactant stream; or the second catalyst is disposed upstream and the first catalyst is disposed downstream.
10. The combined catalyst according to any of claims 1-9, wherein the weight ratio of the first catalyst to the second catalyst is 1:0.1-10, preferably 1: 2-5.
11. A hydroisomerization process comprising contacting a hydrocarbon oil feedstock with a combined catalyst according to any one of claims 1 to 10 under hydroisomerization conditions.
12. The process of claim 11, wherein the hydroisomerization conditions comprise: the temperature is 250-400 ℃, preferably 300-350 ℃; the pressure is 1-30MPa, preferably 5-20 MPa; the space velocity is 0.1-3h-1Preferably 0.5 to 2h-1(ii) a The volume ratio of the hydrogen to the oil is 50-1000, preferably 400-600.
13. The method of claim 11, wherein the hydrocarbon oil feedstock is selected from one or more of cracked tail oil, bio-aviation kerosene production feedstock, C5C6 isomerization feedstock, Fischer-Tropsch wax.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112047356A (en) * | 2019-06-05 | 2020-12-08 | 中国石油化工股份有限公司 | Silicon-phosphorus-aluminum SAPO-36 molecular sieve with ATS structure and synthesis method thereof |
| WO2022257241A1 (en) * | 2021-06-08 | 2022-12-15 | 深圳技术大学 | Zinc-doped alpo-36 molecular sieve single crystal and preparation method therefor |
| CN116037199A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Hydroisomerization catalyst combination reaction system and hydroisomerization process |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040163997A1 (en) * | 2003-02-25 | 2004-08-26 | Theo Maesen | Process for producing high RON gasoline using ATS zeolite |
| JP2007181796A (en) * | 2006-01-10 | 2007-07-19 | Tosoh Corp | Aluminophosphate-based zeolite adsorbent consisting of oxygen-containing six-membered ring, manufacturing method and use thereof |
| CN107286980A (en) * | 2016-04-05 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of preparation method of lube base oil |
| CN107286979A (en) * | 2016-04-05 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of preparation method of lube base oil |
| CN107286981A (en) * | 2016-04-05 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of preparation method of lube base oil |
| CN107286978A (en) * | 2016-04-05 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of preparation method of lube base oil |
| CN109701590A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of method of combination catalyst and Fischer-Tropsch wax modification production lube base oil |
| CN109701612A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The method of hydroisomerisation catalysts and preparation method thereof and Fischer Tropsch waxes modification production lube base oil |
-
2019
- 2019-09-25 CN CN201910909990.3A patent/CN112547118B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040163997A1 (en) * | 2003-02-25 | 2004-08-26 | Theo Maesen | Process for producing high RON gasoline using ATS zeolite |
| JP2007181796A (en) * | 2006-01-10 | 2007-07-19 | Tosoh Corp | Aluminophosphate-based zeolite adsorbent consisting of oxygen-containing six-membered ring, manufacturing method and use thereof |
| CN107286980A (en) * | 2016-04-05 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of preparation method of lube base oil |
| CN107286979A (en) * | 2016-04-05 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of preparation method of lube base oil |
| CN107286981A (en) * | 2016-04-05 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of preparation method of lube base oil |
| CN107286978A (en) * | 2016-04-05 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of preparation method of lube base oil |
| CN109701590A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of method of combination catalyst and Fischer-Tropsch wax modification production lube base oil |
| CN109701612A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The method of hydroisomerisation catalysts and preparation method thereof and Fischer Tropsch waxes modification production lube base oil |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112047356A (en) * | 2019-06-05 | 2020-12-08 | 中国石油化工股份有限公司 | Silicon-phosphorus-aluminum SAPO-36 molecular sieve with ATS structure and synthesis method thereof |
| WO2022257241A1 (en) * | 2021-06-08 | 2022-12-15 | 深圳技术大学 | Zinc-doped alpo-36 molecular sieve single crystal and preparation method therefor |
| CN116037199A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Hydroisomerization catalyst combination reaction system and hydroisomerization process |
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