CN109926093A - A kind of hydrocracking catalyst and preparation method thereof - Google Patents
A kind of hydrocracking catalyst and preparation method thereof Download PDFInfo
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- CN109926093A CN109926093A CN201711353765.3A CN201711353765A CN109926093A CN 109926093 A CN109926093 A CN 109926093A CN 201711353765 A CN201711353765 A CN 201711353765A CN 109926093 A CN109926093 A CN 109926093A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 168
- 238000002360 preparation method Methods 0.000 title claims abstract description 69
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 41
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 40
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 150000007513 acids Chemical class 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims description 44
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 32
- 239000002283 diesel fuel Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 239000011964 heteropoly acid Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 19
- -1 molybdate compound Chemical class 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 15
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 12
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 150000001869 cobalt compounds Chemical class 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 3
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- BNCXNUWGWUZTCN-UHFFFAOYSA-N trichloro(dodecyl)silane Chemical compound CCCCCCCCCCCC[Si](Cl)(Cl)Cl BNCXNUWGWUZTCN-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 235000015165 citric acid Nutrition 0.000 claims 1
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 claims 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims 1
- 239000000571 coke Substances 0.000 claims 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 239000005078 molybdenum compound Substances 0.000 claims 1
- 150000002752 molybdenum compounds Chemical class 0.000 claims 1
- 239000006012 monoammonium phosphate Substances 0.000 claims 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims 1
- 239000005052 trichlorosilane Substances 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 abstract description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005336 cracking Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000000197 pyrolysis Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000037396 body weight Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 229910020628 SiW12O40 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYPYGDUZKOPBEL-UHFFFAOYSA-N trichloro(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl RYPYGDUZKOPBEL-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a kind of hydrocracking catalysts and preparation method thereof, the hydrocracking catalyst includes acidic components, hydrogenation metal component, auxiliary agent and carrier, acidic components are ammonium heteropoly acids, hydrogenation metal component is one or more of vib metals and/or group VIII metal, P is auxiliary agent, and carrier is aluminium oxide and silica complex carrier.A kind of preparation method of above-mentioned hydrocracking catalyst is also provided.The catalyst that the method for the present invention obtains shows higher reactivity and liquid hydrocarbon-selective in the hydrocracking reaction for long chain alkane.
Description
Technical field
The invention belongs to refining arts, are related to a kind of catalysis material preparation method, more particularly, to a kind of hydrogenation catalyst
Agent and preparation method thereof.
Background technique
In petroleum refining industry, it is that feedstock oil exists that being hydrocracked, which is by the important process of mink cell focus production high-quality light-weight oil product,
High temperature, high pressure carry out adding hydrogen, desulfurization, denitrogenation, molecular skeleton rearrangement and cracking etc. chemical under the conditions of facing existing for hydrogen and catalyst
A kind of conversion process of reaction.Hydrocracking process can not only produce high grade light-end products, and liquid-phase product high income, skill
Art core is catalyst.Hydrocracking catalyst is a kind of bifunctional catalyst, has both acid function and hydrogenating function.US5,
536,687, the acid function of hydrocracking catalyst involved in US5,447,623 and EP0028938A1 is mainly by dividing
Son sieve provides, and hydrogenation component selects Mo-Ni or W-Ni.Catalyst zeolite containing Y 20%~40% involved by CN1389545A,
Phosphorus heteropoly tungstic acid or silicotungstic heteropolyacid 5%~20%, nickel oxide 5%~10%, aluminium oxide 40%~60%.Above-mentioned is adding containing molecular sieve
Hydrogen Cracking catalyst has acid strong, a big advantage of specific surface, but the disadvantage is that molecular sieve bore diameter is small, so as to cause reactant with
Product diffusional resistance increases, and the probability of second pyrolysis reaction increases.
CN1927461A discloses a kind of hydrocracking catalyst containing heteropoly acid, and heteropoly acid can be phosphotungstic acid or silicon tungsten
Acid, content are 40%~60%, and hydrogenation component (in terms of simple substance) preferably 5%~10%, surplus is carrier.Nothing is selected when preparation according to the ratio
Machine heat proof material particulate vector prepares the aqueous metal salt of hydrogenation component, impregnated carrier as catalyst carrier；Liquid is consolidated point
Solids drying from after, roasting；Heteropoly acid aqueous solution is prepared, solids obtained is impregnated, stands, dry, roasting.This contains miscellaneous
The hydrocracking catalyst of polyacid have the advantages that it is acid by force and aperture is big, but the disadvantage is that phosphotungstic acid high water solubility, use
A possibility that being relatively easy to run off in the process, and since the catalyst has highly acid, increasing second pyrolysis reaction.
CN201110350796.X discloses hydrocracking catalyst and preparation method thereof.The catalyst includes acid group
Point, hydrogenation component and carrier, acidic components are heteropoly acid alkali metal salt, and hydrogenation component is nickel, and carrier is silica；Catalyst is each
Content is acidic components 10%~20% to component by mass percentage, and hydrogenation component 3%~8%, surplus is carrier.This method is
Catalyst carrier is prepared using sol-gal process, and introduces hydrogenation metal component and alkali metal salt in carrier preparation process, it will
Carrier immerses heteropoly acid solution, up to catalyst after drying.The invention catalyst, heteropolyacid salt is evenly dispersed in the carrier, by
Acid weaker in it, content is lower, shows high liquid hydrocarbon-selective, but activity is relatively low.
CN201110350795.5 discloses a kind of hydrocracking catalyst and preparation method thereof.It is acid in the catalyst
Group is divided into silicotungstate, and hydrogenation metal component is nickel, and carrier is silica.This method is the introducing silicon tungsten in carrier preparation process
Hydrochlorate, silicotungstate is evenly dispersed in the carrier, and catalyst has preferable catalytic performance.But loaded in catalyst duct
Silicotungstate can make a part of product that second pyrolysis reaction occur, and reduce the selectivity of catalyst, influence target product yield.
Summary of the invention
It is in the prior art there are aiming at the problem that, it is an object of the present invention to provide a kind of hydrocracking catalyst and its systems
Preparation Method.Catalyst made from the method for the present invention shows higher reaction in the hydrocracking reaction for long chain alkane
Activity and liquid hydrocarbon-selective.
First aspect present invention provides a kind of hydrocracking catalyst, the hydrocracking catalyst include acidic components,
Hydrogenation metal component, auxiliary agent and carrier, acidic components are ammonium heteropoly acids, and hydrogenation metal component is vib metals and/or the
One or more of group VIII metal, P are auxiliary agent, and carrier is aluminium oxide and silica complex carrier；With the weight of catalyst
On the basis of amount, the content of acidic components is 32%~40%, and the content of hydrogenation metal component is 6%~25%, and auxiliary agent content is 1.0%
~4.6%, the content of carrier is 30.4%~63.0%.
In hydrocracking catalyst of the present invention, vib metals are generally Mo and/or W, and group VIII metal is generally Ni
And/or Co.
In hydrocracking catalyst of the present invention, in aluminium oxide and silica complex carrier Silica-coated oxidation
Aluminium, the weight of silica account for the 3%~15% of alumina weight.
In hydrocracking catalyst of the present invention, the specific surface area of the hydrocracking catalyst is 120~200m2/ g, hole
Holding is 0.2~0.4mL/g, and average pore diameter is 5.0~10.0nm.
In hydrocracking catalyst of the present invention, ammonium heteropoly acids are distributed in containing in catalyst center to 3/4 radius
Amount is the 11.4wt%~45.0wt%, preferably 18.8wt%~37.5wt% of total content；3/4 radius is distributed in catalyst appearance
The content in face is the 55.0wt%~88.6wt%, preferably 62.5wt%~81.2wt% of total content.
In hydrocracking catalyst of the present invention, the catalyst acid content is in the heart to 3/4 radius in the catalyst
It is uniformly distributed, acid content obviously increases within the scope of 3/4 radius to catalyst external surface, and 3/4 radius is to catalyst external surface
The ratio that the odds ratio catalyst center that acid content accounts for total acid content in range accounts for total acid content to the acid content in 3/4 radius is high
8.0wt%~75.0wt%, preferably 23.0~60.0wt%.
In hydrocracking catalyst of the present invention, the hydrogenation metal component is preferably Mo and Co, is with the weight of catalyst
Benchmark, MoO3Content is 5%~20%, Co2O3Content be 1%~5%.
In hydrocracking catalyst of the present invention, the heteropolyacid salt molecular formula is Hm(NH4)nYX12O40, wherein X represent W or
Mo, Y represent Si or P；When Y represents Si, m+n=4, n value is 0.1~1.0；When Y represents P, m+n=3, n value be 0.1~
1.0。
Second aspect of the present invention provides a kind of preparation method of above-mentioned hydrocracking catalyst, and the preparation method includes such as
Lower content:
(1) it is prepared with compound, phosphorus-containing compound and water containing hydrogenation metal component water-soluble containing hydrogenation metal component and auxiliary agent P
Liquid；
(2) alumina support is added in aqueous solutions of organic acids, is dried after mixing；
(3) material that step (2) obtains is added in the alkaline solution containing ammonium, impregnates 5min~10min, is then filtered
And drying；
(4) aqueous solution and heteropoly acid the aqueous solution mixing obtained step (1), is added in the material that step (3) obtains, mixes
Through dry obtained catalyst precarsor A after uniformly；
(5) it is handled using the catalyst precarsor A that auxiliary agent A obtains step (4), obtains catalyst precarsor B；
(6) the catalyst precarsor B that step (5) obtains is added in auxiliary agent B, is separated by solid-liquid separation after mixing, will obtained
Solid phase stood at -50 DEG C~0 DEG C, preferably -30~0 DEG C；
(7) aqueous solutions of organic acids is mixed with the material that step (6) obtains, is separated by solid-liquid separation after mixing；
(8) alkaline solution containing ammonium is mixed with the solid-phase material that step (7) obtains, is separated by solid-liquid separation after mixing；
(9) heteropoly acid aqueous solution is mixed with the solid-phase material that step (8) obtains, is separated by solid-liquid separation after mixing, separated
Obtained solid phase obtains catalyst after drying, roasting.
In preparation method of the present invention, the compound containing hydrogenation metal component described in step (1) is containing vib metals
And/or the compound of group VIII metal, the compound containing vib metals can be molybdate compound, tungstenic chemical combination
One or more of object, the compound of the metal containing group VIII are cobalt compound, nickel compound containing, iron containing compounds
One or more of.The molybdate compound can be molybdenum oxide and/or ammonium heptamolybdate；The cobalt compound is alkali formula carbon
Sour cobalt and/or cobalt nitrate.
In preparation method of the present invention, the compound containing hydrogenation metal component described in step (1) is preferably molybdate compound
And cobalt compound.The molybdate compound can be molybdenum oxide and/or ammonium heptamolybdate；The cobalt compound is basic carbonate
Cobalt and/or cobalt nitrate.
In preparation method of the present invention, phosphorus-containing compound described in step (1) can be phosphoric acid, ammonium dihydrogen phosphate, phosphoric acid one
One or more of hydrogen ammonium.
In preparation method of the present invention, hydrogenation metal in the aqueous solution containing hydrogenation metal component and auxiliary agent P described in step (1)
The concentration of component is 0.03~0.3g/mL(in terms of hydrogenation metal oxide), the concentration of auxiliary agent P is 0.002~0.03 g/mL.
It can be prepared using the existing method in this field.
In preparation method of the present invention, alumina support described in step (2) generallys use cylinder bar shaped aluminium oxide, aluminium oxide
Carrier can be obtained by boehmite through molding, drying and roasting.The boehmite can be used conventional method and be made,
Such as Alchlor process, aluminum sulfate method, carbonizatin method.
In preparation method of the present invention, carrying alumina volume property described in step (2) is as follows: 0.6~0.9mL/g of Kong Rongwei,
Specific surface area is 160~320m2/ g, particle diameter 0.5mm~2.0mm.
In preparation method of the present invention, organic acid described in step (2) and step (7) is citric acid, in tartaric acid, malic acid
It is one or more；The mass ratio of the step (2) and the total organic acid and aluminium oxide of step (7) is 0.1~1.5, step (2)
Mass ratio with organic acid in step (7) is 4:1~1:4.
In preparation method of the present invention, drying temperature described in step (2) be 60~90 DEG C, drying time be 5.0~
10.0h。
In preparation method of the present invention, the alkaline solution containing ammonium described in step (3) and step (8) is ammonium hydroxide, ammonium carbonate
One of solution, ammonium bicarbonate soln are a variety of.The dosage of the alkaline solution containing ammonium is excessive.
In preparation method of the present invention, drying temperature described in step (3) be 60~90 DEG C, drying time be 5.0~
10.0h。
In preparation method of the present invention, heteropoly acid described in step (4) and step (9) is phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid
One of or it is a variety of.Wherein the molar ratio of heteropoly acid is introduced as 4:1~1:4 in step (4) and step (9).
In preparation method of the present invention, drying temperature described in step (4) be 60~120 DEG C, drying time be 3.0~
12.0h；The drying is carried out preferably by the way of Two stage dryer, and wherein first segment drying temperature is 60~90 DEG C, second segment
Drying temperature is 90~120 DEG C.
In preparation method of the present invention, modification process described in step (5) is as follows:
(5.1) auxiliary agent A is mixed with organic solvent, obtains solution I after mixing；
(5.2) alumina support is mixed with solution I, is reacted after mixing, then through being dried to obtain catalyst precarsor
B。
In step (5.1), the auxiliary agent A is octadecyl trimethoxysilane, hexadecyl trimethoxy silane, ten
One of dialkyl group trimethoxy silane, octadecyl trichlorosilane alkane, hexadecyl trichlorosilane, dodecyltrichlorosilane
Or it is several.
In step (5.1), the organic solvent be one or more of benzene, toluene, hexamethylene, wherein auxiliary agent A with
The mass ratio of organic solvent is 1:1~1:50.
In step (5.2), the reaction temperature is 40~60 DEG C, and the reaction time is 1.0~5.0h；The drying temperature
It is 70~90 DEG C, the time is 3.0~12.0h.
In preparation method of the present invention, auxiliary agent B described in step (6) is diesel oil, and the condensation point of the diesel oil is -40~20
DEG C, preferably -40~0 DEG C, further preferably -30~0 DEG C, the diesel oil can be straight-run diesel oil, hydrogenated diesel oil, coking bavin
Oil, one of catalytic diesel oil or a variety of, it is preferred to use hydrogenated diesel oil, specifically can use commercial goods diesel oil, as 5# diesel oil,
One of 0# diesel oil, -10# diesel oil, -20# diesel oil, -35# diesel oil are a variety of, and the volume ratio of the auxiliary agent B and aluminium oxide is 1
~4:1, preferably 1~2:1.
In preparation method of the present invention, drying described in step (9) carries out under vacuum, and relative degree of vacuum is -0.1MPa, does
Dry temperature be 90~120 DEG C, drying time be 3.0~12.0h, maturing temperature be 300~550 DEG C, calcining time be 2.0~
6.0h。
Compared with prior art, hydrocracking catalyst of the present invention and preparation method thereof has the advantages that
1, hydrocracking catalyst of the present invention has the advantages that outer surface acidity constituent content is high and utilization rate is high, described to add
Hydrogen Cracking catalyst improves catalyst external surface acidity while guaranteeing catalytic inner acidity, it is made to have high live
While property, selectivity with higher.
It 2,, not only can be with accelerating auxiliaries by introducing auxiliary agent A in the preparation method of hydrocracking catalyst of the present invention
Interaction between B and carrier, and realize the purpose being modified to alumina support simultaneously, in auxiliary agent A and auxiliary agent B
Under collective effect, it is possible to reduce a possibility that second pyrolysis occurred in catalyst duct reacts avoids generating excessively low
Carbon hydrocarbon.But also the ammonium heteropoly acids of subsequent load can be made to be distributed on the surface of the carrier, make major part heteropoly acid ammonium in this way
Salt is dispersed in carrier surface, and smaller portions ammonium heteropoly acids are dispersed in carrier duct, so that the catalyst acid content of preparation exists
It is evenly distributed in center to 3/4 radius, and acid content obviously increases within the scope of 3/4 radius to catalyst external surface,
Acid content accounts in the odds ratio catalyst center to 3/4 radius of total acid content out of 3/4 radius to catalyst external surface
Acid content account for the high 23.0wt%~60.0wt% of ratio of total acid content.
3, in the preparation method of hydrocracking catalyst of the present invention, modification of the auxiliary agent A to carrier makes alumina support
Outer surface coated silica can reduce the interaction between the ammonium heteropoly acids of generation and aluminium oxide, improve catalysis
The acid amount of agent.
4, catalyst made from the method for the present invention is shown high anti-in the hydrocracking reaction for long chain alkane
Answer activity and higher liquid hydrocarbon-selective.
Specific embodiment
Below by embodiment, the present invention is described further, and reaction hydrocarbon raw material used in embodiment is to contain 525
The n-decane solution of μ g/g thiophene and 170 μ g/g pyridines.In the present invention, wt% is mass fraction.
Specific surface area, Kong Rong are measured using low temperature liquid nitrogen physisorphtion in the present invention, specifically use Merck & Co., Inc, the U.S.
The nitrogen absorption under low temperature instrument of ASAP2420 model measures；Detailed process: a small amount of sample is taken to be vacuum-treated 3~4h at 300 DEG C, most
Product is placed under the conditions of liquid nitrogen cryogenics (- 200 DEG C) afterwards and carries out nitrogen suction-desorption test.Wherein surface area is obtained according to BET equation
It arrives, pore-size distribution is obtained according to BJH model.SEM(scanning electron microscope) specifically using the JSM- of JEOL company, Japan production
The SEM(scanning electron microscope of 7500F type), it is equipped with EDAX-EDS, acceleration voltage: 20Kv, operating distance: 8mm, resolution ratio:
1nm。
Hydrogenation cracking activity indicates by the conversion ratio of n-decane, selectivity by " in product containing 5 carbon atoms and 5 with
The alkane molal quantity of upper carbon atom is divided by product total mole number " it indicates, it is denoted as C5 +Selectivity.This is because in general plus hydrogen
In process, it is desirable to which a pyrolysis product is more and second pyrolysis product is few, when being reaction hydrocarbon raw material with n-decane, in product
Alkane containing 5 carbon atoms and 5 or more carbon atom is all a pyrolysis product, so C5 +Selectivity characterizes one in product
The relative quantity of secondary pyrolysis product.
Embodiment 1
(1) preparation of Mo-Co-P aqueous solution:
By 1.9g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80mL water, and 5.2g molybdenum trioxide and 1.9g alkali formula carbon is then added
Sour cobalt is warming up to 100 DEG C and is stirred at reflux 2.0h, and constant volume is 100mL to get Mo-Co-P aqueous solution after filtering.Wherein MoO3's
Concentration is 0.05g/mL, Co2O3Concentration be 0.01g/mL, the concentration of P is 0.005g/mL.
(2) preparation of catalyst:
By 45g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, cylinder bar shaped, diameter 0.8mm) it is added
In the aqueous solution for containing 18g citric acid to 100mL, the dry 8h at 70 DEG C；Obtained material is added to 100mL mass fraction
5min is impregnated in 30% sal volatile, dries 8h after filtering at 70 DEG C；100mL Mo-Co-P aqueous solution is contained with 100mL
There is the aqueous solution of 33.1g phosphotungstic acid to mix, is added in above-mentioned material, after mixing in 70 DEG C of dry 4h, then heats to
Catalyst precarsor A is made in 110 DEG C of dry 4h；It is then added to the ring that 150mL contains 35.8g dodecyltrimethoxysilane
In hexane solution, 3.0h is reacted at 50 DEG C, in 70 DEG C of dry 8h, obtains catalyst precarsor B；It is then added to 120mL5# bavin
It in oil, is filtered after impregnating 30min, obtained material is placed in 0 DEG C of low-temp reaction bath, and 100mL is then added and contains 4.5g lemon
The aqueous solution of lemon acid pours out solution after impregnating 30min, and the sal volatile that 100mL mass fraction is 30% is then added and soaks
Stain 5min, solution is poured out, and the aqueous solution that 100mL contains 8.3g phosphotungstic acid is then added, filters after impregnating 5min, by what is obtained
Solid is in the case where relative degree of vacuum is -0.1MPa, 110 DEG C of dry 8.0h, and then in 400 DEG C of roasting 3.0h, catalyst is made,
Middle MoO3Content is 5wt%, Co2O3Content is 1wt%, P content 0.5wt%, (NH4)0.7H2.3PW12O40Content is 40wt%, dioxy
The weight of SiClx accounts for the 15% of carrying alumina body weight.The physico-chemical property of catalyst is shown in Table 1.
(3) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(4) evaluating catalyst:
After 0.5g catalyst to be packed into the isothermal section among reaction tube, it is passed through hydrogen, reaction system steps up pressure extremely
2.0MPa is passed through the CS of % containing 2wt after inspection is air tight2N-heptane solution, reaction system is warming up to 320 DEG C of 3 h of vulcanization,
After cut the n-decane liquid containing 525 μ g/g thiophene and 170 μ g/g pyridines, reaction system is then warming up to 400
DEG C, in hydrogen volume air speed 1500h-1Under, mass space velocity is 3.0 h-1, start to acquire sample, detection catalysis after reacting 1 h
Agent hydrogenation cracking activity at reaction conditions and selectivity, the results are shown in Table 3.
Embodiment 2
(1) preparation of Mo-Co-P aqueous solution:
By 3.8g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80mL water, and 10.4g molybdenum trioxide and 4.8g alkali formula carbon is then added
Sour cobalt is warming up to 100 DEG C and is stirred at reflux 2.0h, and constant volume is 100mL to get Mo-Co-P aqueous solution after filtering.Wherein MoO3's
Concentration is 0.1g/mL, Co2O3Concentration be 0.025g/mL, the concentration of P is 0.01g/mL.
(2) preparation of catalyst:
By 46.2g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, cylinder bar shaped, diameter 0.8mm) plus
Enter in the aqueous solution for containing 23.1g citric acid to 100mL, the dry 8h at 70 DEG C；Obtained material is added to 100mL mass point
5min is impregnated in several sal volatiles for 30%, dries 8h after filtering at 70 DEG C；By 100mL Mo-Co-P aqueous solution with
50mL contains the aqueous solution mixing of 18.1g phosphotungstic acid, is added in above-mentioned material, after mixing in 70 DEG C of dry 4h, then
110 DEG C of dry 4h are warming up to, catalyst precarsor A is made；It is then added to 150mL and contains 21.7g hexadecyl trimethoxy silicon
In the cyclohexane solution of alkane, 3.0h is reacted at 50 DEG C, in 70 DEG C of dry 8h, obtains catalyst precarsor B；It is then added to
It in 120mL0# diesel oil, is filtered after impregnating 30min, obtained material is placed in -10 DEG C of low-temp reaction bath, and 100mL is then added
Aqueous solution containing 23.1g citric acid pours out solution after impregnating 30min, and the carbon that 100mL mass fraction is 30% is then added
Acid ammonium solution impregnates 5min, and solution is poured out, and the aqueous solution that 100mL contains 18.1g phosphotungstic acid is then added, impregnates mistake after 5min
Filter, by obtained solid in the case where relative degree of vacuum is -0.1MPa, 110 DEG C of dry 8.0h, then in 470 DEG C of roasting 3.0h, system
Catalyst is obtained, wherein MoO3Content is 10wt%, Co2O3Content is 2.5wt%, P content 1wt%, (NH4)0.5H2.5PW12O40Content
For 35 wt%, the weight of silica accounts for the 8% of carrying alumina body weight.The physico-chemical property of catalyst is shown in Table 1.
(3) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(4) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 3.
Embodiment 3
(1) preparation of Mo-Co-P aqueous solution:
By 7.6g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80mL water, and 20.8g molybdenum trioxide and 9.6g alkali formula carbon is then added
Sour cobalt is warming up to 100 DEG C and is stirred at reflux 2.0h, and constant volume is 100mL to get Mo-Co-P aqueous solution after filtering.Wherein MoO3's
Concentration is 0.2g/mL, Co2O3Concentration be 0.05g/mL, the concentration of P is 0.02g/mL.
(2) preparation of catalyst:
By 37.2g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, cylinder bar shaped, diameter 0.8mm) plus
Enter in the aqueous solution for containing 11.2g citric acid to 100mL, the dry 8h at 70 DEG C；Obtained material is added to 100mL mass point
5min is impregnated in several sal volatiles for 30%, dries 8h after filtering at 70 DEG C；By 100mL Mo-Co-P aqueous solution with
50mL contains the aqueous solution mixing of 6.7g phosphotungstic acid, is added in above-mentioned material, after mixing in 70 DEG C of dry 4h, then rises
Catalyst precarsor A is made to 110 DEG C of dry 4h in temperature；It is then added to 150mL and contains 7.0g octadecyl trimethoxysilane
In cyclohexane solution, 3.0h is reacted at 50 DEG C, in 70 DEG C of dry 8h, obtains catalyst precarsor B；It is then added to 120mL-
It in 10# diesel oil, is filtered after impregnating 30min, obtained material is placed in -20 DEG C of low-temp reaction bath, and 100mL is then added and contains
The aqueous solution of 44.6g citric acid pours out solution after impregnating 30min, and the ammonium carbonate that 100mL mass fraction is 30% is then added
Solution impregnates 5min, and solution is poured out, and the aqueous solution that 100mL contains 26.5g phosphotungstic acid is then added, filters after impregnating 5min,
By obtained solid in the case where relative degree of vacuum is -0.1MPa, 110 DEG C of dry 8.0h are made and urge then in 500 DEG C of roasting 3.0h
Agent, wherein MoO3Content is 20wt%, Co2O3Content is 5.0wt%, P content 2.0wt%, (NH4)0.1H2.9PW12O40Content is
32wt%, the weight of silica account for the 3% of carrying alumina body weight.The physico-chemical property of catalyst is shown in Table 1.
(3) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(4) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 3.
Embodiment 4
(1) preparation of catalyst:
In embodiment 3, phosphotungstic acid is changed to silico-tungstic acid, it is 20% that the sal volatile that mass fraction is 30%, which is changed to mass fraction,
Ammonium hydroxide, catalyst is made, wherein MoO with embodiment 3 in remaining3Content is 20wt%, Co2O3Content is 5.0wt%, and P content is
2.0wt%, (NH4)0.1H3.9SiW12O40Content is 32wt%, and the weight of silica accounts for the 3% of carrying alumina body weight.Catalyst
Physico-chemical property be shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(3) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 3.
Embodiment 5
In embodiment 3, n-decane solution is changed to hexadecane solution, remaining evaluation is with embodiment 3, and catalyst is in reaction item
Hydrogenation cracking activity and selectivity under part, the results are shown in Table 3.
Comparative example 1
(1) preparation of catalyst:
In embodiment 3, by 38.4g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, cylinder bar shaped,
Diameter 0.8mm) it is added to 150mL and contains in the aqueous solution of 57.6g citric acid, the dry 8h at 70 DEG C；Obtained material is added
5min is impregnated in the sal volatile for being 30% to 100mL mass fraction, dries 8h after filtering at 70 DEG C；By 100mL Mo-
Co-P aqueous solution is mixed with the 100mL aqueous solution for containing 33.2g phosphotungstic acid, is added in above-mentioned material, after mixing 70
DEG C dry 4h, in the case where relative degree of vacuum is -0.1MPa, 110 DEG C of dry 8.0h are obtained to be catalyzed then in 500 DEG C of roasting 3.0h
Agent, wherein MoO3Content is 20wt%, Co2O3Content is 5.0wt%, P content 2.0wt%, (NH4)0.1H2.9PW12O40Content is
32wt%.The physico-chemical property of catalyst is shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(3) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 3.
Comparative example 2
It is substantially the same manner as Example 3, the difference is that auxiliary agent A is not used to be modified catalyst precarsor A.
(1) preparation of catalyst:
In embodiment 3, by 38.4g alumina support (Kong Rongwei 0.70mL/g, specific surface area 300m2/ g, cylinder bar shaped,
Diameter 0.8mm) it is added to 100mL and contains in the aqueous solution of 11.6g citric acid, the dry 8h at 70 DEG C；Obtained material is added
5min is impregnated in the sal volatile for being 30% to 100mL mass fraction, dries 8h after filtering at 70 DEG C；By 100mL Mo-
Co-P aqueous solution is mixed with the 50mL aqueous solution for containing 6.7g phosphotungstic acid, is added in above-mentioned material, after mixing at 70 DEG C
Dry 4h, then heats to 110 DEG C of dry 4h, and catalyst precarsor A is made；By catalyst precarsor A, it is added to 120mL-10# bavin
It in oil, is filtered after impregnating 30min, obtained material is placed in -20 DEG C of low-temp reaction bath, and 100mL is then added and contains 46.0g
The aqueous solution of citric acid pours out solution after impregnating 30min, and the sal volatile that 100mL mass fraction is 30% is then added
5min is impregnated, solution is poured out, the aqueous solution that 100mL contains 26.5g phosphotungstic acid is then added, is filtered after impregnating 5min, will
The solid arrived is in the case where relative degree of vacuum is -0.1MPa, 110 DEG C of dry 8.0h, and then in 500 DEG C of roasting 3.0h, catalysis is made
Agent, wherein MoO3Content is 20wt%, Co2O3Content is 5.0wt%, P content 2.0wt%, (NH4)0.1H2.9PW12O40Content is
32wt%.The physico-chemical property of catalyst is shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(3) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 3.
Modification of the auxiliary agent A to catalyst, on the one hand can weaken the acidity of carrier itself, on the other hand can weaken carrier
Interaction between phosphotungstic acid amine salt reduces the salt acidic loss of heteropoly acid ammonium, so the modification of auxiliary agent A plays weakening
It is acid in catalyst duct, improve the effect of catalyst external surface acidity.Compared with Example 3,2 catalyst of comparative example does not use
Auxiliary agent A is modified, acid in catalyst duct not to be weakened, and outer surface acidity, because ammonium heteropoly acids and carrier interact
Weakened.Therefore, the conversion ratio of catalyst and selectivity all decrease.
Comparative example 3
It is substantially the same manner as Example 3, the difference is that auxiliary agent B is not used to be modified catalyst precarsor B.
(1) preparation of catalyst:
Catalyst precarsor B is added to the aqueous solution that 100mL contains 44.6g citric acid, it is dry at 70 DEG C after impregnating 30min
8h；Then the sal volatile that 100mL mass fraction is 30% is added and impregnates 5min, after filtering at 70 DEG C dry 8h, then plus
Enter the aqueous solution that 100mL contains 26.5g phosphotungstic acid, is filtered after impregnating 5min, be in relative degree of vacuum by obtained solid-
Under 0.1MPa, then in 500 DEG C of 3.0 h of roasting catalyst is made, wherein MoO in 110 DEG C of dry 8.0h3Content is 20wt%,
Co2O3Content is 5.0wt%, P content 2.0wt%, (NH4)0.1H2.9PW12O40Content is 32wt%, and the weight of silica accounts for oxygen
Change the 3% of alumina supporter weight.The physico-chemical property of catalyst is shown in Table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(3) evaluating catalyst:
For evaluating catalyst with embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 3.
The physico-chemical property of 1 each catalyst of table
| Embodiment | Specific surface area, m2/g | Kong Rong, ml/g | Average pore diameter, nm |
| Embodiment 1 | 182 | 0.32 | 7.0 |
| Embodiment 2 | 171 | 0.30 | 6.9 |
| Embodiment 3 | 165 | 0.28 | 6.8 |
| Embodiment 4 | 168 | 0.29 | 6.9 |
| Comparative example 1 | 162 | 0.29 | 7.1 |
| Comparative example 2 | 163 | 0.29 | 7.1 |
| Comparative example 3 | 167 | 0.28 | 6.7 |
2 catalyst different location heteropoly acid ammonium salt content of table accounts for the percentage (wt%) of total content
| Catalyst | Center is to 1/4 radius | 1/4 radius to 2/4 radius | 2/4 radius to 3/4 radius | 3/4 radius is to outer surface |
| Embodiment 1 | 5.0 | 15.0 | 25.0 | 55.0 |
| Embodiment 2 | 3.1 | 9.4 | 15.6 | 71.9 |
| Embodiment 3 | 1.3 | 3.8 | 6.3 | 88.6 |
| Embodiment 4 | 1.3 | 3.8 | 6.4 | 88.5 |
| Comparative example 1 | 6.3 | 18.8 | 31.3 | 43.6 |
| Comparative example 2 | 1.3 | 3.8 | 6.5 | 88.4 |
| Comparative example 3 | 6.3 | 18.8 | 31.4 | 43.5 |
The hydrogenation cracking activity and selectivity of 3 each catalyst of table
| Embodiment | N-decane conversion ratio, wt% | C5 +Selectivity, wt% |
| Embodiment 1 | 78.2 | 84.6 |
| Embodiment 2 | 85.3 | 89.4 |
| Embodiment 3 | 84.0 | 90.6 |
| Embodiment 4 | 83.6 | 90.8 |
| Embodiment 5 | 83.8 | 90.9 |
| Comparative example 1 | 71.0 | 80.5 |
| Comparative example 2 | 80.1 | 87.3 |
| Comparative example 3 | 74.5 | 78.4 |
Claims (32)
1. a kind of hydrocracking catalyst, the hydrocracking catalyst includes acidic components, hydrogenation metal component, auxiliary agent and load
Body, acidic components are ammonium heteropoly acids, hydrogenation metal component be one of vib metals and/or group VIII metal or
Several, P is auxiliary agent, and carrier is aluminium oxide and silica complex carrier；On the basis of the weight of catalyst, acidic components contain
Amount is 32%~40%, and the content of hydrogenation metal component is 6%~25%, and auxiliary agent content is 1.0%~4.6%, and the content of carrier is
30.4%~63.0%；The catalyst acid content is evenly distributed in the heart to 3/4 radius in the catalyst, and 3/4 radius
The odds ratio catalyst center that acid content accounts for total acid content within the scope of to catalyst external surface is accounted for the acid content in 3/4 radius
The ratio of total acid content high 8.0wt%~75.0wt%, preferably 23.0~60.0wt%.
2. hydrocracking catalyst described in accordance with the claim 1, it is characterised in that: in aluminium oxide and silica complex carrier
Silica-coated aluminium oxide, the weight of silica account for the 3%~15% of alumina weight.
3. hydrocracking catalyst described in accordance with the claim 1, it is characterised in that: ammonium heteropoly acids are distributed in catalyst center
It is the 11.4wt%~45.0wt%, preferably 18.8wt%~37.5wt% of total content to the content in 3/4 radius；It is distributed in
The content of 3/4 radius to catalyst external surface is the 55.0wt%~88.6wt%, preferably 62.5wt%~81.2wt% of total content.
4. hydrocracking catalyst described in accordance with the claim 1, it is characterised in that: the specific surface area of hydrocracking catalyst is
120~200m20.2~0.4mL/g of/g, Kong Rongwei, average pore diameter are 5.0~10.0nm.
5. hydrocracking catalyst described in accordance with the claim 1, it is characterised in that: vib metals are Mo and/or W, the
Group VIII metal is Ni and/or Co.
6. hydrocracking catalyst described in accordance with the claim 1, it is characterised in that: the hydrogenation metal component is Mo and Co,
On the basis of the weight of catalyst, MoO3Content is 5%~20%, Co2O3Content be 1%~5%.
7. hydrocracking catalyst described in accordance with the claim 1, it is characterised in that: the heteropolyacid salt molecular formula is Hm
(NH4)nYX12O40, wherein X represents W or Mo, and Y represents Si or P；When Y represents Si, m+n=4, n value is 0.1~1.0；Work as Y
When representing P, m+n=3, n value is 0.1~1.0.
8. the preparation method of hydrocracking catalyst described in any claim in claim 1-7, it is characterised in that: the system
Preparation Method includes following content:
(1) it is prepared with compound, phosphorus-containing compound and water containing hydrogenation metal component water-soluble containing hydrogenation metal component and auxiliary agent P
Liquid；
(2) alumina support is added in aqueous solutions of organic acids, is dried after mixing；
(3) material that step (2) obtains is added in the alkaline solution containing ammonium, impregnates 5min~10min, is then filtered
And drying；
(4) aqueous solution and heteropoly acid the aqueous solution mixing obtained step (1), is added in the material that step (3) obtains, mixes
Through dry obtained catalyst precarsor A after uniformly；
(5) it is handled using the catalyst precarsor A that auxiliary agent A obtains step (4), obtains catalyst precarsor B；
(6) the catalyst precarsor B that step (5) obtains is added in auxiliary agent B, is separated by solid-liquid separation after mixing, will obtained
Solid phase stood at -50 DEG C~0 DEG C, preferably -30~0 DEG C；
(7) aqueous solutions of organic acids is mixed with the material that step (6) obtains, is separated by solid-liquid separation after mixing；
(8) alkaline solution containing ammonium is mixed with the solid-phase material that step (7) obtains, is separated by solid-liquid separation after mixing；
(9) heteropoly acid aqueous solution is mixed with the solid-phase material that step (8) obtains, is separated by solid-liquid separation after mixing, separated
Obtained solid phase obtains catalyst after drying, roasting.
9. preparation method according to claim 8, it is characterised in that: the change containing hydrogenation metal component described in step (1)
Conjunction object is the compound containing vib metals and/or group VIII metal.
10. preparation method according to claim 9, it is characterised in that: the compound containing vib metals is containing molybdenum
One or more of compound, Tungstenic compound, the compound of the metal containing group VIII are cobalt compound, nickeliferousization
Close one or more of object, iron containing compounds.
11. preparation method according to claim 8, it is characterised in that: the compound containing hydrogenation metal component be containing
Molybdenum compound and cobalt compound.
12. according to preparation method described in claim 10 or 11, it is characterised in that: the molybdate compound be molybdenum oxide and/
Or ammonium heptamolybdate；The cobalt compound is basic cobaltous carbonate and/or cobalt nitrate.
13. preparation method according to claim 8, it is characterised in that: the phosphorus-containing compound is phosphoric acid, biphosphate
One or more of ammonium, monoammonium phosphate.
14. preparation method according to claim 8, it is characterised in that: contain hydrogenation metal component described in step (1) and help
The concentration of hydrogenation metal component is 0.03~0.3g/mL in the aqueous solution of agent P, and the concentration of auxiliary agent P is 0.002~0.03 g/mL.
15. preparation method according to claim 8, it is characterised in that: organic acid described in step (2) and step (7) is
One of citric acid, tartaric acid, malic acid are a variety of.
16. preparation method according to claim 8, it is characterised in that: the step (2) and the total organic acid of step (7)
Mass ratio with aluminium oxide is 0.1~1.5, and the mass ratio of organic acid is 4:1~1:4 in step (2) and step (7).
17. preparation method according to claim 8, it is characterised in that: drying temperature described in step (2) is 60~90
DEG C, drying time is 5.0~10.0h.
18. preparation method according to claim 8, it is characterised in that: the alkali containing ammonium described in step (3) and step (8)
Property solution be one of ammonium hydroxide, sal volatile, ammonium bicarbonate soln or a variety of.
19. preparation method according to claim 8, it is characterised in that: drying temperature described in step (3) is 60~90
DEG C, drying time is 5.0~10.0h.
20. preparation method according to claim 8, it is characterised in that: heteropoly acid described in step (4) and step (9)
For one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or a variety of.
21. preparation method according to claim 8, it is characterised in that: introduce heteropoly acid in step (4) and step (9)
Molar ratio is 4:1~1:4.
22. preparation method according to claim 8, it is characterised in that: drying temperature described in step (4) is 60~120
DEG C, drying time is 3.0~12.0h；The drying is carried out preferably by the way of Two stage dryer, wherein first segment drying temperature
It is 60~90 DEG C, second segment drying temperature is 90~120 DEG C.
23. preparation method according to claim 8, it is characterised in that: modification process described in step (5) is such as
Under:
(5.1) auxiliary agent A is mixed with organic solvent, obtains solution I after mixing；
(5.2) alumina support is mixed with solution I, is reacted after mixing, then through being dried to obtain catalyst precarsor
B。
24. according to the preparation method described in claim 23, it is characterised in that: the auxiliary agent A in step (5.1) is octadecyl three
Methoxy silane, hexadecyl trimethoxy silane, dodecyltrimethoxysilane, octadecyl trichlorosilane alkane, hexadecane
One or more of base trichlorosilane, dodecyltrichlorosilane.
25. according to the preparation method described in claim 23, it is characterised in that: the organic solvent in step (5.1) is benzene, first
One or more of benzene, hexamethylene.
26. according to the preparation method described in claim 23, it is characterised in that: the mass ratio of auxiliary agent A and organic solvent be 1:1~
1:50。
27. according to the preparation method described in claim 23, it is characterised in that: reaction temperature is 40~60 DEG C in step (5.2),
Reaction time is 1.0~5.0h；Drying temperature is 70~90 DEG C, and the time is 3.0~12.0h.
28. preparation method according to claim 8, it is characterised in that: auxiliary agent B described in step (6) is diesel oil, described
The condensation point of diesel oil is -40~20 DEG C, preferably -40~0 DEG C, further preferably -30~0 DEG C.
29. according to the preparation method described in claim 28, it is characterised in that: the diesel oil is straight-run diesel oil, hydrogenated diesel oil, coke
Change diesel oil, one of catalytic diesel oil or a variety of, it is preferred to use hydrogenated diesel oil.
30. according to the preparation method described in claim 28, it is characterised in that: the diesel oil uses commercial goods diesel oil, 5# bavin
One of oil, 0# diesel oil, -10# diesel oil, -20# diesel oil, -35# diesel oil are a variety of.
31. preparation method according to claim 8, it is characterised in that: auxiliary agent B and the volume ratio of aluminium oxide are 1~4:1,
Preferably 1~2:1.
32. preparation method according to claim 8, it is characterised in that: drying described in step (9) carries out under vacuum,
Relative degree of vacuum be -0.1MPa, drying temperature be 90~120 DEG C, drying time be 3.0~12.0h, maturing temperature be 300~
550 DEG C, calcining time is 2.0~6.0h.
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