CN1690173A - Hydrocracking catalyst containing silicon oxide-alumina - Google Patents
Hydrocracking catalyst containing silicon oxide-alumina Download PDFInfo
- Publication number
- CN1690173A CN1690173A CN 200410037668 CN200410037668A CN1690173A CN 1690173 A CN1690173 A CN 1690173A CN 200410037668 CN200410037668 CN 200410037668 CN 200410037668 A CN200410037668 A CN 200410037668A CN 1690173 A CN1690173 A CN 1690173A
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- Prior art keywords
- alumina
- silica
- weight
- content
- catalyzer
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 88
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title description 2
- 229910052710 silicon Inorganic materials 0.000 title description 2
- 239000010703 silicon Substances 0.000 title description 2
- 239000010457 zeolite Substances 0.000 claims abstract description 53
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 45
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 62
- 239000002808 molecular sieve Substances 0.000 claims description 36
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 36
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 238000002441 X-ray diffraction Methods 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 150000004682 monohydrates Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000005755 formation reaction Methods 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000003921 oil Substances 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 15
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004615 ingredient Substances 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 22
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- 239000002243 precursor Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 229910000480 nickel oxide Inorganic materials 0.000 description 10
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 10
- 229910001930 tungsten oxide Inorganic materials 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 238000005336 cracking Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 241000640882 Condea Species 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910001648 diaspore Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- -1 Fluoride Anions Chemical group 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000003079 shale oil Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- ZNEMGFATAVGQSF-UHFFFAOYSA-N 1-(2-amino-6,7-dihydro-4H-[1,3]thiazolo[4,5-c]pyridin-5-yl)-2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound NC=1SC2=C(CN(CC2)C(CC=2OC(=NN=2)C=2C=NC(=NC=2)NC2CC3=CC=CC=C3C2)=O)N=1 ZNEMGFATAVGQSF-UHFFFAOYSA-N 0.000 description 1
- SBMYBOVJMOVVQW-UHFFFAOYSA-N 2-[3-[[4-(2,2-difluoroethyl)piperazin-1-yl]methyl]-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCN(CC1)CC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SBMYBOVJMOVVQW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- FVIGODVHAVLZOO-UHFFFAOYSA-N Dixanthogen Chemical compound CCOC(=S)SSC(=S)OCC FVIGODVHAVLZOO-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004645 aluminates Chemical class 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000001845 vibrational spectrum Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
A silicon oxide - aluminum oxide contained hydrocracking catalyst contains a silicon oxide - aluminum oxide, a beta zeolite, metallic component containing at least a ferrum, cobalt or nickel from the VIII group and containing at least a molybdenum or wolfram from the VIB group, and the K value of said silicon oxide - aluminum oxide being from 0.4 to 15 A.(cm2.g)-1, catalyst as the datum, the weigh ratio of silicon oxide - aluminum oxide being from 10 to 99 percent, beta zeolite being from 1 to 50 percent, counted as oxidate, the weigh content ratio of metallic ingredient of the VIII group being from 1 to 10 percent, and the weigh content ratio of metallic ingredient of the VIB group being from 5 to 40 percent. The catalyst has a high hydrocracking activity, and a good selectivity to intermediate fraction oil.
Description
Technical field
The invention relates to a kind of hydrocracking catalyst, more specifically say so about a kind of monox-alumina containning hydrocracking catalyst.
Background technology
In recent years, crude oil heavy and poor qualityization tendency are obvious day by day in the world wide, meanwhile, demand to middle distillate and reformation, steam crack material but constantly increases, this impels the hydrocracking technology that turns to purpose with the high-quality of heavy distillate and lightweight to be developed rapidly, and hydrocracking catalyst is wherein important and one of The key factor.
Hydrocracking catalyst is a kind of dual-function catalyst, and it has lytic activity and hydrogenation activity simultaneously, promptly contains acidic components and hydrogenation activity component simultaneously, and its acidity is mainly provided by heat-resistant inorganic oxide that constitutes carrier and/or various zeolite; The hydrogenation activity component generally is selected from metal, metal oxide and/or the metallic sulfide of group vib and VIII family in the periodic table of elements.For reaching different requirements, need carry out adaptive modulation to acidic components in the catalyzer and hydrogenation activity component to the hydrocracking product.
For example, molecular sieve is the main acidic components in the hydrocracking catalyst, by to the selection of molecular sieve type and the control of consumption, can reconcile and improve the distribution and the character of hydrocracking product.But the heat-resistant inorganic oxide that constitutes carrier also directly influences the character of catalyzer.In the hydrocracking catalyst of forming by molecular sieve and alumina host, introduce silica-alumina, can remedy the active low defective of alumina host acid catalysis, activity of such catalysts and selectivity are improved.
CN1315883 discloses a kind of hydrocracking catalyst that contains modification Beta zeolite, is benchmark with the weight percent of catalyzer, comprising: (a) Beta zeolite 5%-40%; (b) large pore volume refractory oxide 10%-70%; (c) aperture aluminum oxide 0%-30%; (d) group vib metal oxide 10%-40%; (e) VIII metal oxide 1%-10%; Described Beta zeolite SiO2/Al2O3 mol ratio is 20-150, and the secondary pore pore volume of＞2nm accounts for more than 40% of total pore volume, specific surface 500-750m2/g, infrared acidity 0.05-0.5mmol/g, Na
2O weight content＜0.2%, at 25 ℃, P/Po is 0.1 o'clock, and water adsorption amount is less than 5 heavy %, and propyl carbinol adsorption experiment residual value is less than 0.4, loading capacity＜0.07.Said large pore volume refractory oxide is selected from the mixture of aluminum oxide, sial or aluminum oxide and silicon oxide.Adopt this catalyzer to carry out hydrocracking, the diesel oil zero pour in the product is lower, can produce the wide fraction low freezing point diesel fuel.
Though the monox-alumina containning hydrocracking catalyst that prior art provides can satisfy the requirement of some hydrocracking reactions, its hydrogenation cracking activity is still lower.
Summary of the invention
The objective of the invention is provides higher hydrocracking catalyst of a kind of activity and preparation method thereof at the existing lower shortcoming of catalyst hydrogenation cracking activity.
The present inventor finds that the protonic acid amount of contained silica-alumina is lower in the monox-alumina containning hydrocracking catalyst that prior art provides, and its k value is less than 0.4A (cm
2G)
-1This is to cause the low major reason of this class catalyst hydrogenation cracking activity.
Catalyzer provided by the invention contains a kind of silica-alumina, a kind of beta-zeolite, at least a iron, cobalt or nickel and at least a molybdenum or the tungsten metal component that is selected from group vib that is selected from group VIII, and the k value of wherein said silica-alumina is 0.4-15A (cm
2G)
-1, be benchmark with the catalyzer, the content of silica-alumina is 10-90 weight %, and the content of beta-zeolite is 1-50 weight %, and in oxide compound, the content of group VIII metal component is that the content of 1-10 weight %, group vib metal component is 5-40 weight %; Described k=B/M
SiO2, B is the protonic acid amount of silica-alumina, M
SiO2Molar fraction for silicon oxide in the silica-alumina.
The invention provides the Preparation of catalysts method comprises, a kind of silica-alumina and a kind of beta-zeolite are mixed iron, cobalt or nickel and at least a molybdenum or the tungsten metal component that is selected from group vib that is incorporated at least a group VIII of introducing in this mixture, and the k value of wherein said silica-alumina is 0.4-15A (cm
2G)
-1Said k=B/M
SiO2, B is the protonic acid amount of silica-alumina, M
SiO2Molar fraction for silicon oxide in the silica-alumina.
Catalyzer provided by the invention is compared with existing catalyzer owing to adopted the high silica-alumina of protonic acid content, and its hydrogenation cracking activity improves.In addition, catalyzer provided by the invention also has the selectivity of intermediate oil preferably.
For example, catalyzer CH-2 provided by the invention is identical with Beta molecular sieve, Tungsten oxide 99.999, nickel oxide content among the comparative catalyst X, and the k value of different the is contained silica-alumina of catalyzer CH-2 is 2.1, and the k value of catalyzer X is 0.36.Adopt same materials oil two kinds of different catalysts to be estimated, relatively give birth to olefiant products distribution, the invention provides 370 ℃ of catalyzer with identical reaction conditions
+The comparison of distillate yield is than catalyzer low 4.8%, illustrate that catalyzer provided by the invention has higher hydrogenation cracking activity, the yield comparison of 65-370 ℃ of lightweight oil that the invention provides catalyzer is higher by 2.3% than catalyzer, illustrates that catalyzer provided by the invention has better intermediate oil selectivity.
Description of drawings
Fig. 1 is the contained silica-alumina of catalyzer provided by the invention, the existing contained silica-alumina of hydrocracking catalyst and γ-Al
2O
3X-ray diffraction spectra.
Embodiment
According to catalyzer provided by the invention, wherein said silica-alumina is that the k value is 0.4-15A (cm
2G)
-1Silica-alumina, k=B/M wherein
SiO2, B is the protonic acid amount of silica-alumina, M
SiO2Molar fraction for silicon oxide in the silica-alumina.B adopts Bio-Rad IFS-3000 type determination of infrared spectroscopy.Concrete grammar is: be pressed into about 10mg/cm behind sample self porphyrize
2The self-supporting sheet, place the original position pond of infrared spectrometer, in 350 ℃, 10-3Pa vacuum tightness lower surface purifying treatment 2 hours, reduce to room temperature and introduce the pyridine saturated vapo(u)r, after the adsorption equilibrium 15 minutes, under 200 ℃, vacuumized desorption 30 minutes, reduce to room temperature survey absorption and decide the pyridine vibrational spectrum.Sweep limit is 1400cm
-1-1700cm
-1, with 1540 ± 5cm
-1[the infrared Absorption value of unit surface, unit mass sample is expressed as its protonic acid amount of ratio value defined of the infrared Absorption value of bands of a spectrum and sample strip weight and area: A (cm
2G)
-1].M
SiO2Calculate after adopting X fluorescent method [Yang Cuiding etc., petrochemical complex analytical procedure (RIPP test method), Science Press, 1990, P380] working sample to form.
Described k value is 0.4-15A (cm
2G)
-1Silica-alumina, can be commercially available or adopt any one prior art for preparing.The k value of preferred silica-alumina is 0.5-13A (cm
2G)
-1, further preferred silica-alumina is that the k value is 0.5-13A (cm
2G)
-1And silica-alumina with one or more X-ray diffraction spectrogram among γ, η, θ, δ and the χ of feature.Several X-ray diffraction spectrograms that satisfy the silica-alumina with gama-alumina X-ray diffraction spectrogram of requirement of the present invention are seen a, b, c, d, the e among Fig. 1 respectively, h among Fig. 1 is the X-ray diffraction spectrogram of gama-alumina, with the catalyzer is benchmark, the content of silica-alumina is 10-90 weight %, is preferably 15-70 weight %.
A kind of k value is 0.5-13A (cm
2G)
-1And the silica-alumina with gama-alumina X-ray diffraction spectrogram of feature is the Siral series silica-alumina that German Condea company produces.For example, the trade mark is that silica-alumina k value after high roasting of Siral40 is 0.58A (cm
2G)
-1, X-ray diffraction spectrogram (seeing Fig. 1 d) is consistent with the X-ray diffraction spectrogram of gama-alumina.
A preferred preparation k value is 0.5-13A (cm
2G)
-1And the method with silica-alumina of one or more aluminum oxide X-ray diffraction spectrogram among γ, η, θ, δ and the χ of feature is: containing si molecular sieves or containing the composition that disordering contains si molecular sieves and mix the hydrate of aluminum oxide and at least a disordering, in 350-850 ℃ of roasting 2-8 hour, preferably in 450-650 ℃ of roasting 3-6 hour.The hydrate of described aluminum oxide is selected from one or more the mixture among hibbsite, monohydrate alumina and the amorphous hydroted alumina; Or one or more the mixture among one or more hibbsite, monohydrate alumina and the amorphous hydroted alumina in siliceous, the titanium, magnesium, boron, zirconium, thorium, niobium, rare earth; Can also be: will be selected from containing si molecular sieves or contain the composition that disordering contains si molecular sieves and directly mixing of the aluminum oxide of one or more crystal formations among γ, η, θ, δ and the χ and at least a disordering.With the silica-alumina is benchmark, and the content of silicon oxide is 1-60 weight %, is preferably 1-45 weight %.
The condition that the disordering molecular sieve should satisfy is: when adopting XRD to characterize, be that 100% characteristic peak is a benchmark with original molecule sieve relative intensity, the relative intensity that disordering contains this characteristic peak of si molecular sieves is below 15%.
Described disordering molecular sieve comprises any one siliceous molecular sieve of disordering, for example silicon metal-the aluminate of disordering, silicon-phosphorus-aluminate, faujusite, ZSM series are boiled (as among ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and the ZSM-38 one or more), are preferably in the ZSM series zeolite of the faujusite of disordering and disordering one or more.
The hydrate of described aluminum oxide and disordering contain si molecular sieves or contain composition blended ratio that disordering contains si molecular sieves that should to make the silica content in the poriness silicon oxide-aluminum oxide that finally makes be 1-60 weight %, be preferably 1-45 weight %.
Described disordering contains si molecular sieves and can obtain by following two kinds of approach:
Article one, approach is to prepare the partially-crystallized si molecular sieves that contains.This partially-crystallized method can adopt in the prior art incomplete crystallization to prepare the method for low-crystallinity molecular sieve, for example C.P.Nicolaides is at ANovel Family of Solid Acid Catalysts:Substantially Amorphous orPartially Crystalline Zeolitic Materials, Applied Catalysis A:General 185,1999, reported among the 211-217.
The second approach is that the si molecular sieves that contains with complete crystallization carries out disordering and handles.For example to X type and Y zeolite, in exsiccant atmosphere (as steam partial pressure less than 0.0069 MPa, preferably less than 0.00138 MPa) roasting down; And for example, at high temperature and V
2O
5Or MoO
3Make the Y zeolite disordering under existing, this disordering trend increases (J.Thoret with the rising of temperature and/or the increase of metal oxide content, etc.Solid-State Interaction Between NaY Zeolite andVanadium Pentoxide, Molybdenum Trioxide, or Tungsten Trioxide, Zeolites, 13,1993,269-275); For another example, in the presence of water vapor, use V
2O
5Make Y zeolite disordering (Carlos A.Trujillo, etc.The Mechnism of Zeolite YDestruction by Steam in the Presence of Vanadium, Journal ofCatalysis 168,1-15,1997); Under certain condition, adopt halogenide to handle Y zeolite and can cause disordering (Kurt A.Becker equally, Catalytic Properties of SyntheticFaujasites Modified with Fluoride Anions, J, Chem.Soc., FaradayTrans.I, 1987,83,535-545), (Kurt A.Becker, etc., Modificationof HY-Zeolite with Trifluoromethane, React.Kinet.Catal.Lett., Vol.29, No.1,1-7,1985).
Beta-zeolite is the known zeolites of people, and its The Nomenclature Composition and Structure of Complexes is at U.S.Patent.No.3,308,069 and Re28341 in existing narration.According to catalyzer provided by the invention, wherein suitable beta-zeolite can be commercially available commodity, also can adopt any one prior art for preparing.Preferred β zeolite is that silica (mol ratio) is at least 25, beta-zeolite as 30-500, more preferred β zeolite is that silica (mol ratio) is 30-200, EP164 is seen in description for this beta-zeolite, 939, U.S.Patent.No.4,923,690, U.S.Patent.No.5,164,169, patent such as CN 1108213A, CN1108214A, CN 1086792A.With the catalyzer is benchmark, and the content of described beta-zeolite is the heavy % of 1-50, the heavy % of preferred 1-45.
According to catalyzer provided by the invention, described iron, cobalt, the nickel that is selected from least a group VIII is preferably nickel, and the molybdenum in the VI family, tungsten are preferably tungsten.In oxide compound and with the catalyzer is benchmark, the content of group VIII metal component is 1-10 weight %, be preferably 2-8 weight %, the content of group vib metal component is 5-40 weight %, be preferably 10-35 weight %, described metal component can be simple substance, oxide compound and/or sulfide and composition thereof.
The invention provides the Preparation of catalysts method comprises described silica-alumina is mixed with beta-zeolite, under the condition that is enough at least a iron, cobalt or the nickel that is selected from group VIII and at least a molybdenum that is selected from group vib or tungsten metal component be deposited on the mixture, mixture after the described roasting and the iron that contains at least a group VIII, cobalt or nickel are selected from the molybdenum of group vib or the solution of tungsten metallization compound contacts with at least a, for example by methods such as ion-exchange, dipping, co-precipitation, preferred pickling process.
Iron in the said group VIII, cobalt, nickel metallic compound are selected from one or more in the soluble compound of these metals, can be in the nitrate, acetate, soluble carbon hydrochlorate, muriate, soluble complexes of these metals one or more as them.
Molybdenum in the said group vib, tungsten metallization compound are selected from one or more in the soluble compound of these metals, can be in molybdate, paramolybdate, tungstate, metatungstate, the ethyl metatungstate one or more as them.
According to catalyzer provided by the invention, look the forming composition that various objectives or requirement can be made into various easy handlings, for example microballoon, sphere, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.
In the embodiment preferred, method for preparing catalyst comprises that with described k value be 0.4-15A (cm
2G)
-1Silica-alumina mix with a kind of beta-zeolite, moulding and at 400-650 ℃ of roasting 2-8 hour; With the iron that contains at least a group VIII, cobalt or nickel and at least a described forming composition of solution impregnation that is selected from the molybdenum or the tungsten metallization compound of group vib.
According to the ordinary method in this area, catalyzer provided by the invention is before using, usually can be in the presence of hydrogen, under 140-370 ℃ temperature, carry out prevulcanized with sulphur, hydrogen sulfide or sulfur-bearing raw material, this prevulcanized can be carried out also can original position vulcanizing in device outside device, is translated into sulfide type.
Catalyzer provided by the invention is applicable to hydrocarbon raw material carried out hydrocracking, has hydrocarbon fraction than lower boiling and lower molecular weight with production.Described hydrocarbon raw material can be various heavy mineral oils or synthetic oil or their mixed fraction oil, as straight run gas oil (straight run gas oil), vacuum gas oil (vacuum gas oil), metal removal oil (demetallized oils), long residuum (atmosphericresidue), diasphaltene vacuum residuum (deasphalted vacuum residue), coker distillate (coker distillates), catalytic cracking distilled oil (cat craker distillates), shale oil (shale oil), asphalt sand oil (tar sand oil), liquefied coal coil (coal liquid) etc.The hydrocracking that catalyzer provided by the invention is specially adapted to heavy and inferior distillate oil is 149-371 ℃ to produce boiling range, and especially boiling range is the hydrocracking process of 180-370 ℃ of intermediate oil.
When catalyzer provided by the invention is used for distillate hydrocracking, can under the hydrocracking process condition of routine, use, as temperature of reaction 200-510 ℃, preferred 300-450 ℃, reaction pressure 3-24 MPa, preferred 4-15 MPa, liquid hourly space velocity 0.1-10 hour-1 preferred 0.2-5 hour-1, hydrogen to oil volume ratio 100-5000, preferred 200-1000.
To the present invention be described by example below.
Agents useful for same in the example except that specifying, is chemically pure reagent.
The hydrogenation activity component concentration adopts x-ray fluorescence spectrometry [Yang Cuiding etc., petrochemical complex analytical procedure (RIPP test method), Science Press, 1990, P380].
The X-ray diffraction experiment carries out on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44KV, 40mA, sweep velocity is 2 °/minute.
Example 1-5 has described and has been applicable to silica-alumina of the present invention and preparation method thereof.
Example 1
With 800 gram NaY type molecular sieve (SiO
2/ Al
2O
3=4.8, degree of crystallinity is defined as 100%, Chang Ling refinery product) placing 4000 milliliters, concentration is ammonium chloride (Beijing Chemical Plant's product of 1.0 moles, analytical pure) in the aqueous solution, exchange is 1 hour under 90 ℃ of stirrings, filters, and does not detect to there being chlorion with deionized water wash, 120 ℃ of oven dry, 550 ℃ of roastings 4 hours.Repeat the Y zeolite A that said process obtains sodium content (in sodium oxide) 0.35 weight % (flame atomic absorption spectrometry mensuration) for twice, recording sample degree of crystallinity with x-ray diffraction method is 76%, getting Y zeolite A 200 gram, to place 1000 milliliters, concentration be Neutral ammonium fluoride (Beijing Chemical Plant's product of 0.2 mole, analytical pure) in the aqueous solution, at 1 hour after-filtration of stirring at normal temperature, 120 ℃ of oven dry, 600 ℃ of roastings 4 hours obtain disordering Y zeolite B (the X ray diffracting characteristic peak of B disappears); Getting 1.5 liters of concentration is 60 gram Al
2O
3/ liter sodium aluminate solution, place one 2 liters one-tenth glue jar, 60 ℃ of initial temperatures feed CO from the bottom that becomes the glue jar
2Content is carbonic acid gas and the Air mixing gas of 90 body %, and the flow of gas mixture is 1.5 meters
3/ hour, reaction is 15 minutes, and pH drops to 8.8, and this moment, temperature of reaction was 73 ℃, stopped into the glue reaction, added yellow soda ash rapidly, made slurries pH rise to 11.0.Be warming up to 90 ℃ aging 4 hours, filter, with 20 times to 90 ℃ of deionized water wash of solid content 4 times, filtration obtains wet cake C; Get disordering Y zeolite B 80 grams and mix making beating with C, filter back 120 ℃ of oven dry, obtain the precursor Si-1 (butt 73 heavy %) of poriness silicon oxide-aluminum oxide, with Si-1 in 550 ℃ of roastings 4 hours, its x-ray diffraction spectra is seen Fig. 1 a, and silica content and k value see Table 1.
Example 2
Taking by weighing 12 gram example 1 disordering Y zeolite B and 100 gram SB powder (diaspore that German Condea company produces) mixes, obtain the precursor Si-2 (butt 74 weight %) of silica-alumina, with Si-2 in 550 ℃ of roastings 4 hours, its x-ray diffraction spectra is seen Fig. 1 b, and silica content and k value see Table 1
Example 3
Contain the rare-earth five-membered ring structure zeolite by example among the CN1020269C 12 is synthetic, obtain containing rare-earth five-membered ring structure zeolite D; According to identical condition is that crystallization temperature is 90 ℃ and synthetic obtains the partially-crystallized rare-earth five-membered ring structure zeolite E that contains.Contain rare-earth five-membered ring structure zeolite E silica content 93.3 weight %, alumina content 4.5 weight %, RE
2O
31.5 weight % (RE
2O
3Represent rare earth oxide, wherein lanthanum trioxide accounts for 26 weight % of total amount of the rare earth oxide, and oxidation Cerium accounts for 51 weight % of rare earth oxide gross weight, and other rare earth oxide accounts for 23 weight % of rare earth oxide gross weight).To contain rare-earth five-membered ring structure zeolite D is that the degree of crystallinity that benchmark is measured part crystallization ZSM-5-5 molecular sieve E is 6%.
Getting pseudo-boehmite powder (Shandong Aluminum Plant's production) 150 grams respectively mixes with partially-crystallized rare-earth five-membered ring structure zeolite E 38 grams that contain, in mixture, add 300 milliliters of deionized waters, normal temperature stirred 30 minutes down, filter, 150 ℃ of dryings 6 hours obtain silica-alumina precursor Si-3 (butt 73 weight %), with Si-3 in 550 ℃ of roastings 4 hours, its x-ray diffraction spectra is seen Fig. 1 c, and silica content and k value see Table 1.
Example 4
This example silica-alumina is through 550 ℃ of roastings 4 hours, and the commodity Siral40 of its X-ray diffracting spectrum such as Fig. 1 d (German Codea company product, silica content 40 weight %) is numbered Si-4, and silica content and k value see Table 1.
Example 5
Precursor Si-4 104 gram, SB powder (diaspore that German Condea company produces) 26 grams of getting silica-alumina mix, and obtain Si-4/SB, and in 550 ℃ of roastings 4 hours, its x-ray diffraction spectra was seen Fig. 1 e with Si-4/SB, and silica content and k value see Table 1.
Silica-alumina that Comparative Examples 1-2 explanation preparation reference catalyst is used and preparation method thereof.
Comparative Examples 1
Synthetic silica-aluminum oxide in accordance with the following methods: get 90 gram Al
2O
3/ liter 934 milliliters of aluminum trichloride solutions, place one 2 liters one-tenth glue jar, stir a following concentration and be 22% ammoniacal liquor to pH6.0, intensification degree to 60 ℃, constant temperature splashes into the sodium silicate solution that 162.5 ml concns are 6 gram silicon oxide/100 milliliter after one hour, with concentration is that 25 heavy % sulfuric acid are reconciled pH to 8.5, reacted 1 hour, filter, with 20 times to 90 ℃ of deionized water wash of solid content 4 times, 120 ℃ of oven dry, obtain the precursor Q (butt 76 weight %) of silica-alumina, in 550 ℃ of roastings 4 hours, its x-ray diffraction spectra was seen Fig. 1 f with Q, and silica content and k value see Table 1.
Comparative Examples 2
Precursor Q 202.4 grams that prepare silica-alumina according to 1 method of Comparative Examples and SB powder (diaspore that German Condea company produces) 63.3 restrains and mixes, obtain Q/SB, in 550 ℃ of roastings 4 hours, its x-ray diffraction spectra was seen Fig. 1 g with Q/SB, and silica content and k value see Table 1;
Table 1
| Example | ??1 | ??2 | ??3 | ??4 | ??5 | Comparative Examples 1 | Comparative Examples 2 |
| Numbering | ??Si-1 | ??Si-2 | ??Si-3 | ??Si-4 | ??Si-4/SB | ??Q | ??Q/SB |
| ??SiO 2(weight %) | ??32.5 | ??6.8 | ??25.0 | ??40.0 | ??32.5 | ??32.5 | ??25.0 |
| ??M SiO2 | ??0.45 | ??0.11 | ??0.36 | ??0.5 | ??0.45 | ??0.45 | ??0.36 |
| ??B[A·(cm 2·g) -1] | ??5.4 | ??0.7 | ??0.76 | ??0.3 | ??0.26 | ??0.15 | ??0.13 |
| ??K[A·(cm 2·g) -1] | ??12.1 | ??6.4 | ??2.1 | ??0.6 | ??0.58 | ??0.33 | ??0.36 |
Example 6-11 illustrates catalyzer provided by the invention and preparation process thereof.
Example 6
Precursor Si-2 (butt) and 147.2 gram β zeolite (Chang Ling refinery catalyst plant products with 93.9 gram silica-aluminas, silica alumina ratio 28, butt 80 heavy %) mix, be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, heat-up rate with 2 ℃/minute under air atmosphere is warming up to 500 ℃, constant temperature 4 hours, get 180 grams with containing ammonium metawolframate (Sichuan Zigong Hard Alloy Foundry product after being cooled to room temperature, tungsten oxide content is 82 weight %) 79.8 grams, nickelous nitrate (the new Photochemical agents in Beijing factory product, nickel oxide content is 27.85 weight %) 59.2 aqueous solution dippings that restrain, 120 ℃ of oven dry 480 ℃ of roastings 4 hours, obtain catalyzer CH-1, with the catalyzer is benchmark, wherein molecular sieve, nickel oxide, the content of Tungsten oxide 99.999 sees Table 2.
Example 7
The precursor Si-3 that gets 194.2 gram silica-aluminas mixes with 20 gram β zeolites (with example 6), be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, heat-up rate with 2 ℃/minute under air atmosphere is warming up to 580 ℃, constant temperature 4 hours, get 230 grams with containing ammonium metawolframate (with example 6) 116.4 grams after being cooled to room temperature, the aqueous solution dipping of nickelous nitrate (with example 6) 47.09 grams, 120 ℃ of oven dry, 480 ℃ of roastings 4 hours, obtain catalyzer CH-2, with the catalyzer is benchmark, wherein molecular sieve, nickel oxide, the content of Tungsten oxide 99.999 sees Table 2.
Comparative Examples 3
This Comparative Examples explanation reference catalyst and preparation thereof.
The precursor Q/SB that gets 194.2 gram silica-aluminas mixes with 20 gram β zeolites (with example 6), be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, heat-up rate with 2 ℃/minute under air atmosphere is warming up to 580 ℃, constant temperature 4 hours, get 230 grams with containing the aqueous solution dipping that ammonium metawolframate (with example 6) 116.4 restrains, nickelous nitrate (with example 6) 47.09 restrains after being cooled to room temperature, 120 ℃ of oven dry, 480 ℃ of roastings 4 hours, obtain catalyzer X, with the catalyzer is benchmark, and wherein the content of molecular sieve, nickel oxide, Tungsten oxide 99.999 sees Table 2.
Example 8
With 150 gram Si-3 silica-alumina precursor and 25.7 gram β zeolite (Chang Ling refinery catalyst plant products, silica alumina ratio 110, butt 86 heavy %) mix, be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, heat-up rate with 2 ℃/minute under air atmosphere is warming up to 450 ℃, constant temperature 4 hours, get 110 grams with containing ammonium metawolframate (with example 6) 49.51 grams after being cooled to room temperature, the aqueous solution dipping of nickelous nitrate (with example 6) 27.76 grams, 120 ℃ of oven dry 480 ℃ of roastings 4 hours, obtain catalyzer CH-3, with the catalyzer is benchmark, wherein molecular sieve, nickel oxide, the content of Tungsten oxide 99.999 sees Table 2.
Example 9
150 gram Si-1 are mixed with 185.9 gram β zeolites (with example 6), be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, heat-up rate with 2 ℃/minute under air atmosphere is warming up to 450 ℃, constant temperature 4 hours, get 310 grams with containing the aqueous solution dipping that ammonium metawolframate (with example 6) 118.78 restrains, nickelous nitrate (with example 6) 99.2 restrains after being cooled to room temperature, 120 ℃ of oven dry, 480 ℃ of roastings 4 hours, obtain catalyzer CH-4, with the catalyzer is benchmark, and wherein the content of molecular sieve, nickel oxide, Tungsten oxide 99.999 sees Table 2.
Comparative Examples 4
This Comparative Examples explanation reference catalyst and preparation thereof
The precursor Q that gets 150 gram silica-aluminas mixes with 185.9 gram β zeolites (with example 6), be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, heat-up rate with 2 ℃/minute under air atmosphere is warming up to 450 ℃, constant temperature 4 hours, get 310 grams with containing the aqueous solution dipping that ammonium metawolframate (with example 6) 118.78 restrains, nickelous nitrate (with example 6) 99.2 restrains after being cooled to room temperature, 120 ℃ of oven dry, 480 ℃ of roastings 4 hours, obtain catalyzer W, with the catalyzer is benchmark, and wherein the content of molecular sieve, nickel oxide, Tungsten oxide 99.999 sees Table 2.
Example 10
150 gram Si-4/SB are mixed with 185.91 gram β zeolites (with example 6), be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, heat-up rate with 2 ℃/minute under air atmosphere is warming up to 580 ℃, constant temperature 4 hours, get 280 grams with containing the aqueous solution dipping that ammonium metawolframate (with example 6) 118.78 restrains, nickelous nitrate (with example 6) 99.2 restrains after being cooled to room temperature, 120 ℃ of oven dry, 480 ℃ of roastings 4 hours, obtain catalyzer CH-5, with the catalyzer is benchmark, and wherein the content of molecular sieve, nickel oxide, Tungsten oxide 99.999 sees Table 2.
Example 11
150 gram Siral40 are mixed with 44.51 gram β zeolites (with example 6), be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, heat-up rate with 2 ℃/minute under air atmosphere is warming up to 450 ℃, constant temperature 4 hours, get 118 grams with containing the aqueous solution dipping that ammonium metawolframate (with example 6) 63.8 restrains, nickelous nitrate (with example 6) 23.0 restrains after being cooled to room temperature, 120 ℃ of oven dry, 480 ℃ of roastings 4 hours, obtain catalyzer CH-6, with the catalyzer is benchmark, and wherein the content of molecular sieve, nickel oxide, Tungsten oxide 99.999 sees Table 2.
Table 2
| Example | Catalyzer | Silica-alumina, weight % | β zeolite weight % | NiO weight % | ??WO 3Weight % |
| ??6 | ??HC-1 | ??Si-2，31.9 | ??40 | ??5.6 | ??22.5 |
| ??7 | ??HC-2 | ??Si-3，60.7 | ??5 | ??4.1 | ??30.2 |
| Comparative Examples 3 | ??X | ??Q/SB，60.7 | ??5 | ??4.1 | ??30.2 |
| ??8 | ??HC-3 | ??Si-3，67.9 | ??10 | ??3.5 | ??18.6 |
| ??9 | ??HC-4 | ??Si-1，35.3 | ??35 | ??6.5 | ??23.2 |
| ??10 | ??HC-5 | ??Si-4/SB， ??35.3 | ??35 | ??6.5 | ??23.2 |
| Comparative Examples 4 | ??Y | ??Q，35.3 | ??35 | ??6.5 | ??23.2 |
| ??11 | ??HC-6 | ??Siral40， ??60.9 | ??15 | ??2.6 | ??21.5 |
Example 12-13
The hydrocracking performance of this example explanation catalyzer of the present invention.
With the n-decane is raw material, the hydrogenation cracking activity of evaluate catalysts CH-4, CH-5 on the small fixed hydroeracking unit, the catalyzer loading amount is 0.2 milliliter, the granules of catalyst diameter is the 0.3-0.45 millimeter, 390 ℃ of temperature of reaction, reaction pressure 4.0 MPas, hydrogen-oil ratio (volume ratio) is 25, liquid hourly space velocity is 60 hours-1, and the n-decane per-cent that transforms in forming with product is represented the transformation efficiency of catalyzer, and evaluation result sees Table 3.
Comparative Examples 5
The evaluation method of catalyzer W is with example 12, and the results are shown in Table 3 for gained.
Table 3
| Example 12 | Example 13 | Comparative Examples 3 | |
| Catalyzer | ??CH-4 | ??CH-5 | ??W |
| Transformation efficiency, % | ??68.9 | ??66.7 | ??62.5 |
Catalyzer CH-5 is identical with the composition of comparative catalyst W, and the k value of different the is contained silica-alumina of catalyzer CH-5 is 0.58, and the k value of the contained silica-alumina of comparative catalyst W is 0.33.But from the result of table 3 as can be seen, improved 4.2 percentage points, illustrated that catalyzer of the present invention has better hydrocracking performance with respect to the transformation efficiency of comparative catalyst W catalyzer CH-5 provided by the invention.
Example 14
The hydrocracking performance of this example explanation catalyzer of the present invention.
Raw materials used oil is Iraq's vacuum gas oil, and its physico-chemical property sees Table 4.
Catalyzer CH-2 is broken into the particle of diameter 0.5-1.0 millimeter, in 30 milliliters of small stationary bed bioreactors, pack into 30 milliliters of this catalyzer, under nitrogen atmosphere, use earlier before the reaction and contain the kerosene of 2 heavy % dithiocarbonic anhydride 300 ℃ of following prevulcanizeds 25 hours, switch reaction raw materials then, estimate at 360 ℃, 6.4 MPas, the results are shown in Table 5.
Comparative Examples 6
The evaluation method of catalyzer X is with example 14, and the results are shown in Table 5 for gained.
Table 4
| Stock oil | |
| Density (20 ℃), grams per milliliter | ??0.9017 |
| S, heavy % | ??2.38 |
| N, mg/litre | ??1080 |
| Simulation distil (ASTM D-2887) | |
| ?IBP | ??243 |
| ?50 | ??437 |
| ?90 | ??497 |
Table 5
| Catalyzer | Example 14 | Comparative Examples 6 |
| Simulation distil (ASTM D-2887) | ??CH-2 | ??X |
| ?65℃ -，％ | ??6.1 | ??5.6 |
| ?65-370℃，％ | ??77.5 | ??75.2 |
| ?370℃ +，％ | ??16.4 | ??21.2 |
As can be seen from Table 5, under identical reaction conditions, in the generation oil of example 14,370 ℃
+Cut is lower by 4.8% than Comparative Examples 6, and the yield of 65-370 ℃ of intermediate oil exceeds 2.3% than Comparative Examples 6, and this illustrates that catalyzer provided by the invention has comparison than higher hydrogenation cracking activity of catalyzer and intermediate oil selectivity preferably.
Claims (13)
1, a kind of monox-alumina containning hydrocracking catalyst, this catalyzer contains a kind of silica-alumina, a kind of beta-zeolite, at least a iron, cobalt or nickel and at least a molybdenum or the tungsten metal component that is selected from group vib that is selected from group VIII, it is characterized in that the k value of described silica-alumina is 0.4-15A (cm
2G)
-1, be benchmark with the catalyzer, the content of silica-alumina is 10-90 weight %, and the content of beta-zeolite is 1-50 weight %, and in oxide compound, the content of group VIII metal component is that the content of 1-10 weight %, group vib metal component is 5-40 weight %; Said k=B/M
SiO2, B is the protonic acid amount of silica-alumina, M
SiO2Molar fraction for silicon oxide in the silica-alumina.
According to the described catalyzer of claim 1, it is characterized in that 2, the k value of described silica-alumina is 0.5-13A (cm
2G)
-1, be benchmark with the silica-alumina, the content of silicon oxide is 1-60 weight %.
According to the described catalyzer of claim 2, it is characterized in that 3, described silica-alumina has the X-ray diffraction spectrogram that is selected from one or more aluminum oxide among γ, η, θ, δ and the χ of feature, the content of silicon oxide is 1-45 weight %.
According to the described catalyzer of claim 3, it is characterized in that 4, described silica-alumina has the X-ray diffraction spectrogram of the gama-alumina of feature.
5, according to the described catalyzer of claim 1, it is characterized in that, with the catalyzer is benchmark, the content of silica-alumina is 15-70 weight %, the content of beta-zeolite is 1-45 weight %, in oxide compound, the content of group VIII metal component is that the content of 2-8 weight %, group vib metal component is 10-35 weight %.
6, the described Preparation of catalysts method of claim 1, this method comprises mixes iron, cobalt or nickel and at least a molybdenum or the tungsten metal component that is selected from group vib that is incorporated at least a group VIII of introducing in this mixture with a kind of silica-alumina and a kind of beta-zeolite, it is characterized in that the k value of described silica-alumina is 0.4-15A (cm
2G)
-1Said k=B/M
SiO2, B is the protonic acid amount of silica-alumina, M
SiO2Molar fraction for silicon oxide in the silica-alumina.
7, in accordance with the method for claim 6, it is characterized in that the k value of described silica-alumina is 0.5-13A (cm
2G)
-1, be benchmark with the silica-alumina, silica content is 1-60 weight %.
8, in accordance with the method for claim 7, it is characterized in that described silica-alumina has the X-ray diffraction spectrogram that is selected from one or more aluminum oxide among γ, η, θ, δ and the χ of feature, the content of silicon oxide is 1-45 weight %.
9, in accordance with the method for claim 8, it is characterized in that, described silica-alumina is by having containing si molecular sieves or contain composition that disordering contains si molecular sieves and directly mixing and obtain of the aluminum oxide that is selected from one or more crystal formations among γ, η, θ, δ and the χ and at least a disordering.
10, in accordance with the method for claim 8, it is characterized in that, described silica-alumina is mixed by containing si molecular sieves or containing the composition that disordering contains si molecular sieves of the hydrate of aluminum oxide and at least a disordering, obtains in 350-850 ℃ of roasting 2-8 hour.
11, in accordance with the method for claim 10, it is characterized in that the hydrate of described aluminum oxide is selected from one or more the mixture among hibbsite, monohydrate alumina and the amorphous hydroted alumina; Or one or more the mixture among one or more hibbsite, monohydrate alumina and the amorphous hydroted alumina in siliceous, the titanium, magnesium, boron, zirconium, thorium, niobium, rare earth.
According to claim 10 or 11 described methods, it is characterized in that 12, described disordering contains one or more in the ZSM series zeolite of faujusite that si molecular sieves is a disordering and disordering.
According to claim 10 or 11 described methods, it is characterized in that 13, described disordering molecular sieve is by preparing partially-crystallized molecular sieve or the si molecular sieves that contains of complete crystallization being carried out disordering and handles and to obtain.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306371B (en) * | 2007-05-16 | 2011-05-18 | 中国石油化工股份有限公司 | Selective hydrodesulfurization catalyst and its preparation method |
| CN101578353B (en) * | 2007-01-12 | 2013-01-16 | 环球油品公司 | Selective hydrocracking process using beta zeolite |
-
2004
- 2004-04-29 CN CN 200410037668 patent/CN1281310C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101578353B (en) * | 2007-01-12 | 2013-01-16 | 环球油品公司 | Selective hydrocracking process using beta zeolite |
| CN101306371B (en) * | 2007-05-16 | 2011-05-18 | 中国石油化工股份有限公司 | Selective hydrodesulfurization catalyst and its preparation method |
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