CN112547118B - Isomerization combined catalyst and hydroisomerization method - Google Patents
Isomerization combined catalyst and hydroisomerization method Download PDFInfo
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- CN112547118B CN112547118B CN201910909990.3A CN201910909990A CN112547118B CN 112547118 B CN112547118 B CN 112547118B CN 201910909990 A CN201910909990 A CN 201910909990A CN 112547118 B CN112547118 B CN 112547118B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 138
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000006317 isomerization reaction Methods 0.000 title claims description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 139
- 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 139
- 239000000203 mixture Substances 0.000 claims description 54
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 238000002425 crystallisation Methods 0.000 claims description 22
- 230000008025 crystallization Effects 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 15
- 239000007790 solid phase Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 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
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical group C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 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 description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002199 base oil Substances 0.000 abstract description 5
- 239000010687 lubricating oil Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000000881 depressing effect Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 49
- 239000000499 gel Substances 0.000 description 45
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 31
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 28
- 229910052698 phosphorus Inorganic materials 0.000 description 28
- 239000011574 phosphorus Substances 0.000 description 28
- 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
- 229910052710 silicon Inorganic materials 0.000 description 25
- 239000010703 silicon Substances 0.000 description 25
- 239000003921 oil Substances 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 24
- 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 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- -1 hydroxycarbonates Chemical class 0.000 description 21
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 18
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 13
- 235000011007 phosphoric acid Nutrition 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 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
- 239000012071 phase Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000003292 glue Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001027 hydrothermal synthesis 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
- 238000005470 impregnation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000614 phase inversion technique Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 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
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive 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
- 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
- 238000005336 cracking Methods 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
- 239000002149 hierarchical pore Substances 0.000 description 2
- 238000011068 loading method Methods 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
- 239000002243 precursor Substances 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
- 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
- 241001675646 Panaceae Species 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
- 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 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 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
- 239000012752 auxiliary agent Substances 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 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
- 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
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 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
- 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
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-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
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 an AST configuration molecular sieve. The composite catalyst of the invention is used for Fischer-Tropsch wax modification to produce lubricating oil base oil, so that good pour point depressing effect can be obtained, and the lubricating oil base oil has high yield and high viscosity index.
Description
Technical Field
The present invention relates to a combination catalyst and its use in the isomerisation of hydrocarbon oil feedstocks, more particularly to an isomerisation catalyst composition and a process for hydroisomerisation of hydrocarbon oil feedstocks.
Background
The molecular sieve material has high acidity and high specific surface area, has strong chemical stability and hydrothermal stability, is difficult to be destroyed by corrosion and dissolution of reactants, and is an excellent acidic catalyst. Compared with the commonly used homogeneous catalyst, the molecular sieve material catalyst can be directly recycled without separation, and meanwhile, the environment and the products cannot be polluted, so that the preparation of the molecular sieve with special performance is an important research direction in the chemical industry field.
CN104353484a discloses a preparation method of low-cost strong-acid hierarchical pore Beta zeolite, and relates to a preparation method of hierarchical pore Beta zeolite. CN103964458A discloses a Beta zeolite with high silica-alumina ratio and multiple pore channels and a preparation method thereof. CN103073020a discloses a zeolite molecular sieve with multilevel pore canal, its preparation method and application. CN104891526a discloses a preparation method of mesoporous molecular sieve with high hydrothermal stability. CN1703490a discloses a catalyst combination process for producing lubricating base oils. The invention relates to a process for converting a wax containing heavy components into a high quality lubricating oil basestock 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 diameter and the minimum diameter is less than or equal to 0.05nm, followed by a molecular sieve zeolite beta 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, the catalyst containing a molecular sieve having a one-dimensional mesoporous structure, a molecular sieve having a macroporous structure, wherein the weight ratio of the molecular sieve having a one-dimensional mesoporous structure to the molecular sieve having a macroporous structure is 80-99:1-20, the molecular sieve having a macroporous structure contains non-framework silicon, and the silicon content is 1-20 wt% based on oxide and based on the molecular sieve.
Disclosure of Invention
The invention aims at providing a hydroisomerization combined catalyst, which is characterized by comprising a first catalyst and a second catalyst, wherein the first catalyst contains a carrier containing an ATS molecular sieve and an active metal component supported on the carrier, and the second catalyst contains a carrier containing a ten-membered ring silicon-aluminum molecular sieve and an active metal component supported on the carrier.
The combined catalyst is applied to the processing of hydrocarbon oil raw materials, particularly the isomerization reaction of hydrocarbon oil raw materials rich in paraffin, such as isomerization of cracked tail oil, production of biological aviation kerosene, C5C6 isomerization, processing of Fischer-Tropsch synthetic wax and the like, and the obtained target product has lower pour point and high yield.
In particular, the invention includes, for exampleThe following contents are: the invention provides a combined catalyst, which 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 supported on the carrier, and the second catalyst contains a carrier containing a ten-membered ring silicon-aluminum molecular sieve and an active metal component supported on the carrier. Preferably, the ATS molecular sieve is an ATS aluminum phosphate molecular sieve, and more preferably, the ATS type molecular sieve is selected from MAPO-36, SAPO-36 and AlPO 4 -36、CoSAPO-36、ZnAPO-36、AlPO 4 -one or more of 36, 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, wherein 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 alumina, alumina-magnesia, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia. Preferably, the ATS molecular sieve is present in an amount of 10 to 100wt%, the other configurations are present in an amount of 0 to 90wt% and the refractory inorganic oxide other than the molecular sieve is present in an amount of 0 to 60wt%, based on the ATS molecular sieve-containing support.
According to the combined catalyst of the invention, the ten-membered ring silica alumina 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 hydroisomerization catalysts, which may be the same or different, and specifically, the active metal may be at least one of the group VIII metal components, preferably at least one of the group VIII noble metal components.
According to the combined catalyst of the invention, the content of active metal and the content of carrier 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 99-99.9wt% 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 invention, when applied to a specific device or reactor, may have a first catalyst disposed upstream and a second catalyst disposed downstream along the flow of reactant streams; 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, and may be selected conventionally, or may be specifically selected according to the nature of the reaction materials and the purpose of processing, 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 hydroisomerization conditions.
The hydroisomerization conditions in the process of the present invention are conventional conditions, such as: the temperature is 250-400 ℃, preferably 300-350 ℃; the pressure is 1-30MPa, preferably 5-20MPa; space velocity of 0.1-3h -1 Preferably 0.5-2h -1 The method comprises the steps of carrying out a first treatment on the surface of the The hydrogen oil volume ratio is 50-1000, preferably 400-600.
According to the hydroisomerization method provided by the invention, the hydrocarbon oil raw material is preferably paraffin-rich raw material oil, 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 molecular sieve sample synthesized in preparation example 4; FIG. 2 is an SEM photograph of a molecular sieve sample synthesized in preparation example 4.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to 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 more preferably, the ATS type molecular sieve is selected from MAPO-36, SAPO-36 and AlPO 4 -36、CoSAPO-36、ZnAPO-36、AlPO 4 -one or more of 36, FAPO-36.
The preparation methods of the first catalyst and the second catalyst in the present invention are not particularly limited, and the first catalyst and the second catalyst may be prepared according to a conventional method for preparing a supported catalyst by using the carrier defined in the present invention. The present invention is not particularly limited as long as it is sufficient to support the active metal component on the support, and a preferred method is an impregnation method comprising preparing an impregnation solution of a compound containing the metal, and then impregnating the support with the solution. The impregnation method is a conventional method, and for example, may be an excess liquid impregnation method or a pore saturation method impregnation method. The active metal component-containing compound is selected from one or more of soluble compounds in the active metal component-containing compound.
For the first catalyst and the second catalyst, an auxiliary component, such as a phosphorus component, which improves the catalyst performance, may also be incorporated therein. When the catalyst further contains an additive component such as phosphorus, the method of introducing the additive component may be any method, for example, a method of impregnating the carrier after preparing a mixed solution of a compound containing the component such as phosphorus and a compound containing an active metal component; it is also possible to impregnate the support after separately preparing a solution of a compound containing a component such as phosphorus and bake the support. When an additive component such as phosphorus and an active metal are introduced into the support separately, it is preferable that the support is impregnated with a solution containing the additive component compound first and calcined, and then impregnated with a solution containing the active metal component compound. 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 silica-alumina molecular sieve and the ATS molecular sieve of the invention can be commercial agents or can be prepared according to the prior method, and are not limited.
In the combination catalyst of the present invention, the type of the ten-membered ring silica alumina molecular sieve is not particularly limited, and may be 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 a Eu-1 molecular sieve, for example. Preferably, the ten membered ring aluminosilicate 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 the steps of gel formation, crystallization, post-treatment and the like, and the conditions of all the steps are the conventional conditions.
For the preparation of ATS molecular sieves according to the prior art, in one embodiment, taking the synthesis of AlPO-36 molecular sieves as an example, phosphoric acid may be used as the phosphorus source, pseudo-boehmite as the aluminum source, tri-n-propylamine (Pr 3 N) is taken as a template agent (marked as R), and then the AlPO-36 molecular sieve is synthesized through initial gel, aging and hydro-thermal treatment.
In another specific embodiment, taking the synthetic SAPO-36 as an example, one of three ways can be used: in the first method, phosphoric acid is used as a phosphorus source, polyaluminum chloride is used as an aluminum source, fumed silica is used as a silicon source, and tri-n-propylamine (Pr 3 N) is used as a template agent, part of MAPO-36 molecular sieve is used as seed crystal to be added into the initial gel mixture in the synthesis process, and then the mixture is treated for a period of time under the hydrothermal condition. In the second method, phosphoric acid is used as a phosphorus source, pseudo-boehmite is used as an aluminum source, silica sol is used as a silicon source, and tri-n-propylamine (Pr 3 N) is taken as a template agent, MAPO-36 molecular sieve is taken as seed crystal to be addedTo an initial gel mixture, and then treated under hydrothermal conditions for a period of time. The third method is to add a certain amount of MAPO-36 molecular sieve as seed crystal into the initial gel mixture, and then treat the mixture for a period of time under hydrothermal conditions by taking 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).
For the synthesis of other types of ATS molecular sieves, different sources of auxiliary agents and templates may be selected depending on the specific composition of the molecular sieve, for example ZnAPO-36 using zinc acetate dihydrate (Zn (CH) 3 COO) 2 ·2H 2 O) is a metal zinc source, and di-n-propylamine is used as a template agent; coSAPO-36 may use cobalt sulfate as a source of cobalt metal, and tri-n-propylamine (Pr 3 N) is a templating agent; alPO (AlPO) 4 -36 using tri-n-propylamine as template agent; FAPO-36: adopts copperas (FeSO) 4 ·7H 2 O) is 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 within a wider synthesis range without adding any seed crystal. The SAPO-36 molecular sieve is synthesized by adopting a phosphorus-aluminum dry glue solution phase inversion method or a hydrothermal method.
Specifically, the synthesis method comprises the following steps: 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, washing, drying and optionally roasting the obtained solid phase; wherein the template agent is 4-pyrrolidinyl pyridine.
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 a 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 aluminum phosphate dry glue solution comprises the following steps:
(1) Providing a mixture a, said mixture a comprising a phosphorus source, an aluminum source and water; (2) Aging the mixture A, and then drying to obtain phosphorus aluminum dry glue; (3) Providing an initial gel mixture B, wherein the initial gel mixture B contains the phosphorus aluminum dry gel 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, 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 containing a phosphorus source, an aluminum source, a silicon source, a templating agent, and water; (2) crystallizing the initial gel mixture C; (3) And (3) carrying out solid-liquid separation on the crystallized product, 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, wherein the phosphorus source is P 2 O 5 The aluminum source is calculated as Al 2 O 3 The molar ratio of phosphorus source, aluminum source and 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, including, for example, added water, as well as water from the phosphorus source and the aluminum source. In the preparation of an initial gel mixture B, the initial gel mixture B contains the phosphorus-aluminum dry gel prepared in the step (2), a silicon source, a template agent and water, wherein the phosphorus-aluminum dry gel is prepared by using Al 2 O 3 The silicon source is represented by SiO 2 The molar ratio of the phosphorus-aluminum dry gel 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 amount of water added, as well as the amount of water in the aluminum phosphate xerogel, the silicon source, and the templating agent.
In the method for synthesizing the SAPO-36 molecular sieve by adopting the phosphorus-aluminum dry glue solution phase inversion method, the phosphorus-aluminum dry glue can be prepared by adopting a conventional method, and the phosphorus-aluminum dry glue, a silicon source, a template agent and water are mixed to obtain the initial gel mixture B. Specifically, an aluminum source and water are mixed, then a phosphorus source is added with stirring to obtain a mixture A, the mixture A is aged under stirring at 50-80 ℃, preferably 60-70 ℃ for 6-20 hours, preferably 10-18 hours, and then the aged mixture A is dried at 80-110 ℃, preferably 80-100 ℃ for 15-35 hours, preferably 20-30 hours to obtain the aluminum phosphate dry adhesive. Sequentially adding and uniformly mixing the phosphorus aluminum dry gel, the silicon source, the water and the template agent, thereby obtaining the initial gel mixture B.
In the method for synthesizing the SAPO-36 molecular sieve by adopting 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, wherein the phosphorus source is P 2 O 5 The aluminum source is calculated as Al 2 O 3 The silicon source is represented by SiO 2 The molar ratio of the phosphorus source, the silicon source, the aluminum source, the template agent R and the water is 0.6-1.2:0.1-1.2:1-10:10-200, preferably 0.8-1.2:0.15-1:1.5-5:20-150. In preparing the initial gel mixture C, the water is the total amount of water, including, for example, the amount of water added, and also including the amounts of water in the phosphorus source, the silicon source, the aluminum source, and the 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, so that the initial gel mixture C is obtained. Specifically, an aluminum source, water, a phosphorus source, a silicon source, and a template agent may be sequentially added and uniformly mixed, thereby obtaining the initial gel mixture C.
The kinds of the phosphorus source, the silicon source and the aluminum source are not particularly limited, and may be selected conventionally.
In general, the phosphorus source may be selected from at least one of orthophosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, and organic phosphorus compounds. Preferably, the organic phosphide is at least one of trimethylphosphorus and triethylphosphorus.
The aluminum source may be selected from at least one of aluminum salts, pseudo-boehmite, 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 formula I, R, R 2 、R 3 And R is 4 Each is C 1 -C 4 Such 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, tetraethoxysilane 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 hydroisomerization conditions, wherein the raw oil is preferably raw oil rich in alkane, such as hydrocracking tail oil, biological aviation kerosene production raw material, C5C6 isomerization raw material, fischer-Tropsch synthetic wax and the like. The hydroisomerization conditions are conventional conditions, as in the process of the present invention, and the hydroisomerization conditions are not particularly limited, as long as they are sufficient to cause hydroisomerization of the feed oil. In general, the reaction conditions may include: the temperature is 200-500 ℃, preferably 250-400 ℃, more preferably 300-350 ℃; the pressure is 1-30MPa, preferably 2-20MPa, more preferably 5-20MPa, and the pressure is absolute pressure; space velocity of 0.1-5h -1 Preferably 0.1-3h -1 More preferably 0.5-2h -1 The method comprises the steps of carrying out a first treatment on the surface of the The hydrogen oil volume ratio is 50-3000, preferably 300-3000, more preferably 400-600.
In the combination 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 disposed downstream along the flow of reactant stream such that reactant material is contact reacted with the first catalyst prior to contact reaction with the second catalyst; alternatively, the second catalyst may be disposed upstream and the first catalyst disposed downstream such that the reaction mass is first contact reacted with the second catalyst and then contact reacted with the first catalyst; or the first catalysts and the second catalysts are staggered, so that the reaction materials are in contact reaction with the first catalysts and the second catalysts alternately in sequence.
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 simultaneously included in the same catalyst bed, the loading process of the catalyst bed is preferably as follows: one of the catalysts is filled first and the other catalyst is filled again.
In the combined catalyst according to the invention, the weight ratio of the first catalyst to the second catalyst is 1:0.1-10, preferably 1:2-5, more preferably 1:1-2.5, further 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 compounds containing noble metal elements of group VIII. 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 combined catalysts provided by the invention. The hydroisomerization conditions are conventional conditions, such as: the temperature is 250-400 ℃, preferably 300-350 ℃; the pressure is 1-30MPa, preferably 5-20MPa; space velocity of 0.1-3h -1 Preferably 0.5-2h -1 The method comprises the steps of carrying out a first treatment on the surface of the The hydrogen oil volume ratio 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 cracked 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) employed an Empyrean type diffractometer of the family panaceae, netherlands, which was equipped with a PIXcel3D detector. Test conditions: cu target, K alpha radiation, ni filter, tube voltage 40kV, tube current 40mA, scanning range 5-50 deg. Scanning electron microscope morphology analysis (SEM) a japanese scanning electron microscope type S4800. Test conditions: after the sample is dried and ground, it is stuck on the conductive adhesive. 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, and tri-n-propylamine (Pr 3 N) is used as a template agent, and the synthesis process is carried out according to 1.5Pr 3 N:1.0Al 2 O 3 :0.9P 2 O 5 :0.6SiO 2 :40H 2 The molar ratio of O was formulated as an initial gel mixture to which 10% (based on the mass of the initial gel mixture) MAPO-36 molecular sieve was added as seed crystals and crystallized at 150℃for 72 hours under hydrothermal conditions. Filtering or centrifugally separating, 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 sample was subjected to X-ray diffraction analysis and XRD spectrum confirmed to be a pure phase SAPO-36 molecular sieve.
Preparation example 2
AlPO-36 is prepared from phosphoric acid as phosphorus source, pseudo-boehmite as aluminium source, and tri-n-propylAmine (Pr) 3 N) is used as a template agent, and the synthesis process is carried out according to 1.7Pr 3 N:1.0Al 2 O 3 :1.0P 2 O 5 :80H 2 O molar ratio, aging the initial gel mixture at 120 ℃ for 120 hours, crystallizing at 140 ℃ for 72 hours under hydrothermal condition, and synthesizing to obtain the AlPO-36 molecular sieve. Filtering or centrifugally separating, 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 sample was subjected to X-ray diffraction analysis, and the XRD spectrum confirmed to be a pure phase AlPO-36 molecular sieve.
Preparation example 3
CoSAPO-36 adopts phosphoric acid as a phosphorus source, pseudo-boehmite as an aluminum source, fumed silica as a silicon source, cobalt sulfate as a metallic cobalt source, tri-n-propylamine as a template agent, and the synthesis process is according to 1.8Pr 3 N:0.95Al 2 O 3 :1.0P 2 O 5 :0.4SiO 2 :0.1CoO:60H 2 And (3) mixing the raw materials according to the molar ratio of O, stirring for 8 hours until the raw materials are uniform, crystallizing at 150 ℃ for 100 hours under a hydrothermal condition for synthesis, taking out a crystallized product when the temperature of the autoclave is reduced to room temperature after the crystallization is completed, filtering or centrifugally separating, washing the obtained solid phase with deionized water to be neutral, and drying at 110 ℃ for 12 hours to obtain the molecular sieve raw powder. The sample was subjected to X-ray diffraction analysis and the XRD spectrum confirmed to be a pure phase CoSAPO-36 molecular sieve.
Preparation example 4
4.91 g of pseudo-boehmite (Al 2 O 3 83% by mass) and 33.81 g of deionized water are stirred and mixed until uniform, 9.22 g of orthophosphoric acid (H) is slowly added in a trickle under stirring 3 PO 4 85% by mass) and is fully stirred at 70 ℃ and aged for 12 hours to prepare a mixture A. The mixture A is poured into a tray and dried at 80 ℃ for 24 hours to prepare the aluminum phosphate dry gel.
6.07 g of the prepared aluminum phosphate dry gel (solid content 80.32%) was added to a polytetrafluoroethylene liner, followed by 0.39 g of solid silica gel (SiO 2 93% by mass), 5.80 g of deionized water, 6.11 g of 4-pyrrolidinylpyridine (C) 9 H 12 N 2 97% of mass percent) and uniformly stirring, wherein the adding mole ratio of each component is as follows：P 2 O 5 /Al 2 O 3 ＝1.0、SiO 2 /Al 2 O 3 ＝0.3、R/Al 2 O 3 ＝2.0、H 2 O/Al 2 O 3 ＝20。
Covering a polytetrafluoroethylene lining filled with the reaction mixture, putting the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, putting the autoclave into a rotary convection oven, setting the rotating speed to be 20r/min, and carrying out first-stage crystallization under autogenous pressure: crystallizing at 150 ℃ for 36 hours, heating to 180 ℃ and carrying out second-stage crystallization: crystallizing at 180 deg.c for 45 hr, filtering or centrifuging to separate the crystallized product after the temperature of the high pressure kettle is lowered to room temperature, washing the solid phase with deionized water to neutrality, and drying at 110 deg.c for 12 hr to obtain the molecular sieve powder.
The obtained molecular sieve is subjected to X-ray diffraction analysis, an XRD spectrum is shown in figure 1, and the pure-phase ATS structure silicon-phosphorus-aluminum SAPO-36 molecular sieve is proved. The morphology of the molecular sieve is observed by adopting an SEM, and the SEM picture is shown in figure 2 and is in an ellipsoidal morphology.
Preparation example 5
5.44 g of aluminum hydroxide dry gel (Al 2O3 mass percent 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 way under the stirring state 3 PO 4 85% by mass) and is fully stirred at 70 ℃ and aged for 10 hours to prepare a mixture A. The mixture A is poured into a tray and dried at 80 ℃ for 28 hours to prepare the aluminum phosphate dry gel.
6.50 g of the prepared aluminum phosphate dry gel (solid content 81.58%) was added to a polytetrafluoroethylene liner, followed by 0.60 g of silica Sol (SiO) 2 30% by mass), 16.12 g of deionized water, 9.17 g of 4-pyrrolidinylpyridine (C) 9 H 12 N 2 97% of the mass fraction), and uniformly stirring, wherein the adding molar ratio of each component is as follows: p (P) 2 O 5 /Al 2 O 3 ＝1.15、SiO 2 /Al 2 O 3 ＝0.15、R/Al 2 O 3 ＝3.0、H 2 O/Al 2 O 3 ＝50。
Covering a polytetrafluoroethylene lining filled with the reaction mixture, putting the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, putting the autoclave into a rotary convection oven, setting the rotating speed to be 20r/min, and carrying out first-stage crystallization under autogenous pressure: crystallizing at 160 ℃ for 35 hours, heating to 180 ℃ and carrying out second-stage crystallization: crystallizing at 180 deg.c for 50 hr, filtering or centrifuging to separate the crystallized product after the temperature of the high pressure kettle is lowered to room temperature, washing the solid phase with deionized water to neutrality, and drying at 110 deg.c for 12 hr to obtain the molecular sieve powder.
And carrying out X-ray diffraction analysis on the obtained molecular sieve, wherein the XRD spectrum is proved to be the pure-phase SAPO-36 molecular sieve. And observing the morphology of the molecular sieve by adopting SEM, and displaying the rapier morphology.
Preparation example 6
16.67 g of aluminum isopropoxide (C) 9 H 21 AlO 3 98% by mass) and 41.38 g of deionized water were stirred and mixed until uniform, and 10.15 g of orthophosphoric acid (H) was slowly added in a trickle while stirring 3 PO 4 85% by mass) was stirred well at 65℃and aged for 15 hours to give mixture A. The mixture A is poured into a tray and dried at 85 ℃ for 25 hours to prepare the aluminum phosphate dry gel.
6.19 g of the prepared aluminum phosphate dry gel (solid content 83.34%) is added into a polytetrafluoroethylene lining, and 0.65 g of solid silica gel (SiO 2 93% by mass), 20.36 g of deionized water, 6.11 g of 4-pyrrolidinylpyridine (C) 9 H 12 N 2 97% of the mass fraction), and uniformly stirring, wherein the adding molar ratio of each component is as follows: p (P) 2 O 5 /Al 2 O 3 ＝1.1、SiO 2 /Al 2 O 3 ＝0.5、R/Al 2 O 3 ＝2.0、H 2 O/Al 2 O 3 ＝60。
Covering a polytetrafluoroethylene lining filled with the reaction mixture, putting the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, putting the autoclave into a rotary convection oven, setting the rotating speed to be 20r/min, and carrying out first-stage crystallization under 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, filtering or centrifuging to separate the crystallized product after the temperature of the high pressure kettle is lowered to room temperature, washing the solid phase with deionized water to neutrality, and drying at 110 deg.c for 12 hr to obtain the molecular sieve powder.
And carrying out X-ray diffraction analysis on the obtained molecular sieve, wherein the XRD spectrum is proved to be the pure-phase SAPO-36 molecular sieve. And observing the morphology of the molecular sieve by adopting SEM, and obtaining a regular ellipsoidal morphology.
Preparation example 7
4.91 pseudo-boehmite (Al 2 O 3 83% by mass) and 30.28 g of deionized water were stirred and mixed until uniform, and 8.76 g of orthophosphoric acid (H) was added slowly in a trickle while stirring 3 PO 4 85% by mass) and the mixture A is prepared by fully stirring at 65 ℃ and aging for 18 hours. And pouring the mixture A into a tray, and drying at 90 ℃ for 20 hours to obtain the aluminum phosphate dry gel.
5.53 g of the prepared aluminum phosphate dry gel (solid content 85.62%) is added into a polytetrafluoroethylene lining, and 1.20 g of silica sol (SiO 2 30% by mass), 12.50 g of deionized water, 9.17 g of 4-pyrrolidinylpyridine (C) 9 H 12 N 2 97% of the mass fraction), and uniformly stirring, wherein the adding molar ratio of each component is as follows: p (P) 2 O 5 /Al 2 O 3 ＝0.95、SiO 2 /Al 2 O 3 ＝0.3、R/Al 2 O 3 ＝3.0、H 2 O/Al 2 O 3 ＝40。
Covering a polytetrafluoroethylene lining filled with the reaction mixture, putting the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, putting the autoclave into a rotary convection oven, setting the rotating speed to be 20r/min, and carrying out first-stage crystallization under autogenous pressure: crystallizing at 170 ℃ for 30 hours, heating to 190 ℃ and carrying out second-stage crystallization: crystallizing at 190 deg.c for 40 hr, filtering or centrifuging to separate the crystallized product after the temperature of the high pressure kettle is lowered to room temperature, washing the solid phase with deionized water to neutrality, and drying at 110 deg.c for 12 hr to obtain the molecular sieve powder.
And carrying out X-ray diffraction analysis on the obtained molecular sieve, observing the morphology of the molecular sieve by adopting SEM, and the characterization result shows that the sample is a pure-phase SAPO-36 molecular sieve, and the morphology of the sample is an ellipsoidal morphology.
Preparation example 8
4.91 g of pseudo-boehmite (Al 2 O 3 83% by mass) and 20.59 g of deionized water were stirred and mixed until uniform, and 9.70 g of ammonium hydrogen phosphate ((NH) was slowly added in a stirred state 4 ) 2 HPO 4 98% by mass) was stirred well at 60℃and aged for 18 hours to give mixture A. The mixture A is poured into a tray and is dried for 18 hours at 100 ℃ to prepare the aluminum phosphate dry gel.
5.51 g of the prepared aluminum phosphate dry gel (solid content 83.35%) is added into a polytetrafluoroethylene lining, and 1.03 g of solid silica gel (SiO 2 93% by mass), 13.29 g of deionized water, 4.58 g of 4-pyrrolidinylpyridine (C) 9 H 12 N 2 97% of the mass fraction), and uniformly stirring, wherein the adding molar ratio of each component is as follows: p (P) 2 O 5 /Al 2 O 3 ＝0.9、SiO 2 /Al 2 O 3 ＝0.8、R/Al 2 O 3 ＝1.5、H 2 O/Al 2 O 3 ＝40。
Covering a polytetrafluoroethylene lining filled with the reaction mixture, putting the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, putting the autoclave into a rotary convection oven, setting the rotating speed to be 20r/min, and carrying out first-stage crystallization under autogenous pressure: crystallizing at 135 ℃ for 40 hours, heating to 170 ℃ and carrying out second-stage crystallization: crystallizing at 170 deg.c for 45 hr, filtering or centrifuging to separate the crystallized product after the temperature of the high pressure kettle is lowered to room temperature, washing the solid phase with deionized water to neutrality, and drying at 110 deg.c for 12 hr to obtain the molecular sieve powder.
And carrying out X-ray diffraction analysis on the obtained molecular sieve, wherein the XRD spectrum is proved to be the pure-phase SAPO-36 molecular sieve. And observing the morphology of the molecular sieve by adopting an SEM, wherein the SEM picture shows regular ellipsoidal morphology.
Preparation example 9
2.46 g of pseudo-boehmite (Al 2 O 3 83% by mass), 5.89 g deionized water, 4.61 g orthophosphoric acid (H) 3 PO 4 85% by mass), 0.39 g of solid silica gel (SiO) 2 Mass fraction 93%), 6.11 g of 4-pyrrolidinylpyridine (C) 9 H 12 N 2 97% of the mass fraction) are sequentially added into the polytetrafluoroethylene lining, and the mixture is stirred uniformly, wherein the molar ratio of the components is as follows: p (P) 2 O 5 /Al 2 O 3 ＝1.0、SiO 2 /Al 2 O 3 ＝0.3、R/Al 2 O 3 ＝2.0、H 2 O/Al 2 O 3 ＝20。
Covering a polytetrafluoroethylene lining filled with the reaction mixture, putting the polytetrafluoroethylene lining into a stainless steel autoclave for sealing, putting the autoclave into a rotary convection oven, setting the rotating speed to be 20r/min, and carrying out first-stage crystallization under autogenous pressure: crystallizing at 150 ℃ for 36 hours, heating to 180 ℃ and carrying out second-stage crystallization: crystallizing at 180 deg.c for 45 hr, filtering or centrifuging to separate the crystallized product after the temperature of the high pressure kettle is lowered to room temperature, washing the solid phase with deionized water to neutrality, and drying at 110 deg.c for 12 hr to obtain the molecular sieve powder.
And carrying out X-ray diffraction analysis on the obtained molecular sieve, wherein the XRD spectrum is proved to be the pure-phase SAPO-36 molecular sieve. And observing the morphology of the molecular sieve by adopting an SEM, wherein an SEM picture shows an ellipsoidal morphology.
Preparation example 10
36.3 g of SiO containing 40% by weight are taken 2 1.77 g of analytically pure Al 2 (SO 4 ) 3 ·18H 2 O,3.94 g of analytically pure KOH and 8.44 g of hexamethylenediamine were used. Mixing hexamethylenediamine with silica sol, mixing KOH and Al 2 (SO 4 ) 3 ·18H 2 O and 89.4 g of deionized water were mixed, and then the two solutions were mixed, stirred for 1 hour, transferred into a reaction kettle, and crystallized at 160℃for 72 hours. The synthesized molecular sieve is 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 80 g of a nitric acid solution containing 2% was used. Molding on a strip extruder. The shaped support was calcined at 600 degrees for 4 hours. Pt was supported on the carrier at 0.5%, and then calcined in air and reduced in hydrogen at 400 degrees for 4 hours, respectively. Respectively designated as C1-C10.
Examples 1 to 9
The obtained catalyst and commercial catalyst RIW-2 were loaded into the first reactor and the second reactor of the high pressure hydrogenation reactor according to the schemes in Table 1 to obtain the catalyst composition of the present invention. And (3) injecting the cracked tail oil raw material into a reactor from top to bottom for reaction. After the reaction is completed, the product is distilled to cut off light components of less than 370 degrees, and components of more than 370 degrees are analyzed and yield calculated.
Table 1 loading 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 cracking tail oil quality
TABLE 3 reaction conditions
TABLE 4 Table 4
From the data in table 4, it can be seen that the method for producing the lubricating base oil by modifying the fischer-tropsch wax according to the present invention can obtain a better pour point depressing effect, and the lubricating base oil has a high yield and a high viscosity index.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. A combination catalyst comprising a first catalyst comprising a support comprising an ATS molecular sieve and an active metal component supported on the support, and a second catalyst comprising a support comprising a ten membered ring aluminosilicate molecular sieve and an active metal component supported on the support;
the ATS molecular sieve is an SAPO-36 molecular sieve, and the synthesis method of the SAPO-36 molecular sieve comprises the following steps: 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, washing, drying and optionally roasting the obtained solid phase; wherein the template agent is 4-pyrrolidinyl pyridine;
the crystallization is a two-stage crystallization process, which comprises the steps of carrying out the first-stage crystallization under autogenous pressure, wherein the crystallization temperature is 135-170 ℃ and the crystallization time is 30-40 hours; then the second stage crystallization is carried out, the crystallization temperature is 170-190 ℃, and the crystallization time is 40-50 hours.
2. The combination catalyst of claim 1, wherein the ten membered ring silica alumina 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, a SSZ-32 molecular sieve, and a Eu-1 molecular sieve.
3. The combination catalyst according to claim 1, wherein the support containing the ATS molecular sieve further contains thereon a molecular sieve of other configurations and/or a refractory inorganic oxide other than the molecular sieve, the molecular sieve of other configurations being one or more selected from the group consisting of 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, the refractory inorganic oxide other than the molecular sieve being one or more selected from the group consisting of alumina, alumina-magnesia, silica-alumina-titania, silica-alumina-magnesia, silica-alumina-zirconia.
4. A combination catalyst according to claim 3, wherein the ATS molecular sieve is present in an amount of 10-100wt%, the other configurations are present in an amount of 0-90wt% and the refractory inorganic oxide other than molecular sieve is present in an amount of 0-60wt%, based on the ATS molecular sieve-containing support.
5. The combination catalyst of claim 1, wherein the active metal component of the first and second catalysts is independently selected from at least one of the group VIII metal components.
6. The combination catalyst according to claim 5, wherein the active metal component in the first and second catalysts is independently selected from at least one of the group VIII noble metal components.
7. The combination catalyst according to claim 1, wherein the content of the carrier in the first catalyst is 99 to 99.9wt% based on the first catalyst, and the content of the active metal component in the reduced state is 0.1 to 1.0wt%; in the second catalyst, the content of the carrier is 99-99.9wt% based on the second catalyst, and the content of the active metal component in the reduced state is 0.1-1.0 wt%.
8. The combination catalyst of any one of claims 1-7, wherein the first catalyst is disposed upstream and the second catalyst is disposed downstream along the flow direction of the reactant stream; or the second catalyst is disposed upstream and the first catalyst is disposed downstream.
9. The combination catalyst of any one of claims 1-7, wherein the weight ratio of the first catalyst to the second catalyst is 1:0.1-10.
10. The combination catalyst of claim 9, wherein the weight ratio of the first catalyst to the second catalyst is 1:2-5.
11. A hydroisomerization process comprising contacting a hydrocarbon oil feedstock with the combined catalyst of any one of claims 1-10 under hydroisomerization conditions.
12. The process of claim 11, wherein the hydroisomerization conditions comprise: the temperature is 250-400 ℃; the pressure is 1-30MPa; space velocity of 0.1-3h -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume ratio of hydrogen to oil is 50-1000.
13. The process of claim 12, wherein the hydroisomerization conditions comprise: the temperature is 300-350 ℃; the pressure is 5-20MPa; space velocity of 0.5-2h -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume ratio of hydrogen to oil is 400-600.
14. The method of claim 11, wherein the hydrocarbon oil feedstock is selected from one or more of cracked tail oil, bioaviation kerosene production feedstock, C5C6 isomerisation feedstock, fischer-tropsch wax.
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