CN112742451A - Hydro-upgrading catalyst and preparation method and application thereof - Google Patents
Hydro-upgrading catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN112742451A CN112742451A CN201911046230.0A CN201911046230A CN112742451A CN 112742451 A CN112742451 A CN 112742451A CN 201911046230 A CN201911046230 A CN 201911046230A CN 112742451 A CN112742451 A CN 112742451A
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- CN
- China
- Prior art keywords
- molecular sieve
- acid
- treatment
- water
- ammonium
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 147
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 228
- 239000002808 molecular sieve Substances 0.000 claims abstract description 227
- 239000002253 acid Substances 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002283 diesel fuel Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 238000000449 magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 102
- 238000011282 treatment Methods 0.000 claims description 96
- 229910001868 water Inorganic materials 0.000 claims description 73
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 57
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 54
- 239000003795 chemical substances by application Substances 0.000 claims description 50
- 238000002156 mixing Methods 0.000 claims description 39
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 29
- 150000003863 ammonium salts Chemical class 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 239000012298 atmosphere Substances 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 23
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 22
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 16
- 150000007522 mineralic acids Chemical class 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 15
- -1 ammonium fluorosilicate Chemical compound 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 7
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 29
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 15
- 238000007142 ring opening reaction Methods 0.000 abstract description 15
- 238000012986 modification Methods 0.000 abstract description 12
- 230000004048 modification Effects 0.000 abstract description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 11
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 238000004537 pulping Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 13
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 11
- 238000005336 cracking Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229940097789 heavy mineral oil Drugs 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention provides a hydro-upgrading catalyst and a preparation method and application thereof. The hydro-upgrading catalyst comprises a carrier and an active metal component loaded on the carrier, wherein the carrier comprises a substrate and a Y molecular sieve, and the unit cell constant of the Y molecular sieve is 2.415-2.440 nm; of the Y molecular sieve27The proportion of the peak area of the resonance signal with the chemical shift of 0 +/-2 ppm in the Al MAS NMR spectrum to the total peak area is not more than 4 percent; the strong acid content of the Y molecular sieve accounts for more than 70 percent of the total acid content. The hydrogenation modification catalyst of the invention strengthens the polycyclic aromatic hydrocarbon hydrogenation saturation and ring-opening performance of the catalyst by using the Y molecular sieve with high silicon-aluminum ratio, less non-framework aluminum, large specific surface area, rich secondary pores and high strong acid center ratio, so that the catalyst has high aromatic hydrocarbon selective hydrogenation ring-opening performance and good selectivity, and is used for hydrogenation of inferior diesel oilThe cetane number of the diesel oil can be obviously improved while the high diesel oil yield is kept in the modification process.
Description
Technical Field
The invention relates to the field of catalysis, in particular to a hydro-upgrading catalyst and application thereof.
Background
With the increasing of the heavy and inferior degree of crude oil and the application of catalytic cracking technologies such as improving the quality of gasoline or increasing the yield of propylene, the quality of secondary processing diesel oil fractions such as catalytic cracking diesel oil and coking diesel oil is increasingly deteriorated. It is characterized by high density, high nitrogen content, high aromatic hydrocarbon content and low cetane number. On the other hand, the upgrading pace of the quality of the finished oil is accelerated, 1 month and 1 day in 2019 are required, national six-standard diesel oil is supplied comprehensively, and common diesel oil is cancelled. The key to realize the vehicle-to-general integration is to improve the cetane number and reduce the aromatic hydrocarbon content. For secondary processing diesel fuel, especially catalytic diesel fuel, which is poor in quality but accounts for a high proportion of the diesel fuel pool, selective hydrogenation saturation and selective ring opening of aromatic hydrocarbons are ideal paths for reducing the content of aromatic hydrocarbons and increasing the cetane number. Catalysts are key factors affecting the process, such as:
CN 201110350797.4 discloses a diesel hydro-upgrading catalyst and a preparation method thereof, wherein a catalyst carrier comprises a modified beta molecular sieve and alumina, and the beta molecular sieve has the characteristics of high silica-alumina ratio, large specific surface area, proper acidity and acid distribution and reasonable pore structure through modification, so that the beta molecular sieve has proper cracking effect and higher isomerization effect on long-chain alkane, aromatic hydrocarbon and long-side chain alkyl of cycloalkane, and further the diesel condensation point is greatly reduced and the cetane number is improved.
CN201210109193.5 discloses a catalytic cracking diesel hydro-upgrading catalyst, which comprises a hydrogenation active metal component and a carrier of a modified Y molecular sieve, amorphous silicon aluminum and alumina. With a catalystThe content of the Y molecular sieve is 5-20%, the content of amorphous silicon aluminum accounts for 10-20%, wherein SiO in the amorphous silicon aluminum accounts for220-75% of the total amount of the inorganic filler, 0.25-0.80 mL/g of pore volume, and 150-500 m of specific surface area2Per g, average grain size of Y molecular sieve is less than 100nm, SiO2/Al2O3The molar ratio is 9-20: 1, the relative crystallinity is more than 75%, and the specific surface area is 500-800 m2/g. When the catalyst is used for the hydrogenation modification of catalytic diesel, the cetane number can be improved while the high diesel yield is kept.
CN201210194486.8 discloses a diesel oil hydrogenation catalyst, which contains rare earth modified USY molecular sieve, amorphous silicon-aluminum, macroporous aluminum oxide and hydrogenation active components. The catalyst is used as a reference, the content of the rare earth modified USY molecular sieve is 5-60%, the content of amorphous silicon-aluminum is 5-80%, and the content of group VIII metal is 0.1-10%. The catalyst can improve the cetane number of diesel oil under the condition of mild hydrogenation.
Although various catalysts for diesel hydro-upgrading have been disclosed, the diesel yield and the diesel cetane number in the diesel hydro-upgrading process still need to be further improved, and thus there is a need for improving the performance of the catalysts.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a hydrogenation modification catalyst with high ring opening performance and good selectivity for selective hydrogenation of aromatic hydrocarbon, which is used in the diesel hydrogenation modification process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hydro-upgrading catalyst comprises a carrier and an active metal component loaded on the carrier, wherein the carrier comprises a substrate and a Y molecular sieve,
wherein the unit cell constant of the Y molecular sieve is 2.415-2.440 nm; of the Y molecular sieve27Chemical shift of 0. + -.2 ppm resonance in Al MAS NMR spectrumThe proportion of the peak area of the signal to the total peak area is not more than 4%; the strong acid content of the Y molecular sieve accounts for more than 70 percent of the total acid content.
In some embodiments, the Y molecular sieve has a unit cell constant of 2.422-2.438 nm; of the Y molecular sieve27The proportion of the peak area of the resonance signal with the chemical shift of 0 +/-2 ppm in the Al MAS NMR spectrum to the total peak area is not more than 3 percent; the strong acid amount of the Y molecular sieve accounts for more than 75 percent of the total acid amount.
In some embodiments, the Y molecular sieve has a micropore specific surface area of 650m2A ratio of 700m or more, preferably 700m2More than g; the proportion of the mesoporous volume of the Y molecular sieve in the total pore volume is 30-50%, preferably 33-45%.
In some embodiments, the matrix is selected from one or more of alumina, silica, and silica-alumina.
In some embodiments, the active metal component comprises at least one metal component selected from group VIII and at least one metal component selected from group VIB.
In some embodiments, the hydro-upgrading catalyst comprises 1 to 10 wt% of a group VIII metal component and 5 to 50 wt% of a group VIB metal component, calculated as oxides, based on the hydro-upgrading catalyst.
In some embodiments, the hydro-upgrading catalyst comprises 2 to 8 wt% of a group VIII metal component and 10 to 35 wt% of a group VIB metal component, calculated as oxides, based on the hydro-upgrading catalyst.
In some embodiments, the Y molecular sieve is present in an amount of 10 to 60 wt% and the matrix is present in an amount of 40 to 90 wt%, based on the support.
In some embodiments, the Y molecular sieve is present in an amount of 15 to 45 wt% and the matrix is present in an amount of 55 to 85 wt%, based on the support.
In another aspect, the present invention provides a method for preparing the above hydrogenation reforming catalyst, comprising:
uniformly mixing the Y molecular sieve and the matrix, molding, and roasting to obtain the carrier;
and (3) impregnating the carrier with a solution containing the active metal component, and drying and roasting to obtain the hydro-upgrading catalyst.
In some embodiments, prior to mixing the Y molecular sieve with the matrix, further comprising preparing the Y molecular sieve by:
mixing the NaY molecular sieve with ammonium salt and water to carry out primary ammonium exchange treatment to obtain a primary ammonium exchange molecular sieve;
carrying out first hydrothermal roasting treatment on the first ammonium exchange molecular sieve in a steam atmosphere to obtain a first water-roasted molecular sieve;
mixing the first water-baked molecular sieve with water, and adding a first dealuminizing agent to carry out first dealuminization treatment to obtain a first dealuminized molecular sieve;
carrying out second hydrothermal roasting treatment on the first dealuminized molecular sieve in a steam atmosphere to obtain a second hydrothermal roasted molecular sieve;
mixing the second water-baked molecular sieve with water, and adding a second dealuminizing agent for second dealuminization treatment to obtain a second dealuminized molecular sieve;
carrying out third hydrothermal roasting treatment on the second dealuminized molecular sieve in a steam atmosphere to obtain a third water-roasted molecular sieve;
mixing the third-time water-baked molecular sieve with water, and adding a third dealuminizing agent to carry out third dealuminizing treatment to obtain a third dealuminized molecular sieve; and
mixing the third dealuminized molecular sieve with water, adding a fourth dealuminizing agent for fourth dealuminization treatment, filtering and washing to obtain the Y molecular sieve,
wherein the ammonium salt is selected from one or more of ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium oxalate, ammonium sulfate and ammonium bisulfate, and the fourth dealuminating agent comprises a dealuminating agent containing silicon.
In some embodiments, the first, second, and third dealuminating agents are each independently selected from one or more of organic acids selected from ethylenediaminetetraacetic acid, oxalic acid, citric acid, and sulfosalicylic acid, inorganic acids selected from fluorosilicic acid, hydrochloric acid, sulfuric acid, and nitric acid, and organic and inorganic salts selected from ammonium oxalate, ammonium fluoride, ammonium fluorosilicate, and ammonium fluoroborate.
In some embodiments, the silicon-containing dealuminating agent is fluorosilicic acid, ammonium fluorosilicate, or a mixture of fluorosilicic acid and ammonium fluorosilicate.
In some embodiments, the fourth dealuminating agent further comprises an organic acid and/or an inorganic acid, and the mass ratio of the silicon-containing dealuminating agent to the organic acid and/or the inorganic acid is 0.02-0.3: 0-0.07, the organic acid is selected from one or more of ethylenediamine tetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, and the inorganic acid is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid.
In some embodiments, the first hydrothermal roasting treatment, the second hydrothermal roasting treatment and the third hydrothermal roasting treatment are performed at a temperature of 350 to 700 ℃, a water vapor concentration of 1 to 100%, and a roasting time of 0.5 to 10 hours; the temperature of the first ammonium exchange treatment is room temperature to 95 ℃, and the treatment time is 0.5 to 5 hours; the temperature of the first dealuminization treatment is between room temperature and 90 ℃, and the treatment time is between 0.5 and 6 hours; the temperature of the second dealuminization treatment is between room temperature and 100 ℃, and the treatment time is between 0.5 and 6 hours; the temperature of the third dealuminization treatment is between room temperature and 100 ℃, and the treatment time is 0.5 to 6 hours; the temperature of the fourth dealuminization treatment is between room temperature and 100 ℃, and the treatment time is between 0.5 and 6 hours.
In some embodiments, the ammonium salt is added to at least one of the first dealumination treatment, the second dealumination treatment, the third dealumination treatment and the fourth dealumination treatment.
In some embodiments, the NaY molecular sieve in the first ammonium exchange treatment is: the ammonium salt: water 1: 0.3-1.0: 5-10; in the first dealumination treatment, the first water-calcined molecular sieve: the ammonium salt: the first dealuminizing agent: water 1: 0-0.50: 0.02-0.3: 5-10; in the second dealumination treatment, the second water-calcined molecular sieve: the ammonium salt: the second dealuminizing agent: water 1: 0-0.50: 0.02-0.3: 5-10; in the third dealumination treatment, the third water-calcined molecular sieve: the ammonium salt: the third dealuminizing agent: water 1: 0-0.70: 0.02-0.3: 5-10; in the fourth dealumination treatment, the third dealumination molecular sieve: the ammonium salt: the silicon-containing dealuminizing agent comprises the following components: water 1: 0-0.70: 0.02-0.3: 5 to 10.
In another aspect, the present invention provides a use of the above hydro-upgrading catalyst in diesel oil processing, including: contacting the diesel fraction with the hydro-upgrading catalyst under hydro-upgrading conditions.
The hydrogenation modification catalyst of the invention uses the Y molecular sieve with high silicon-aluminum ratio, less non-framework aluminum, large specific surface area, rich secondary pores and high strong acid center ratio to strengthen the polycyclic aromatic hydrocarbon hydrogenation saturation and ring-opening performance of the catalyst, so that the catalyst has high aromatic hydrocarbon selective hydrogenation ring-opening performance and good selectivity, and can remarkably improve the cetane number of diesel oil while keeping high diesel oil yield when being used in the hydrogenation modification process of poor diesel oil.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
In the present invention, anything or matters not mentioned is directly applicable to those known in the art without any change except those explicitly described. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.
All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a hydro-upgrading catalyst comprising a carrier and an active metal component supported on the carrier, the carrier comprising a matrix and a molecular sieve.
In the catalyst of the invention, the substrate is a heat-resistant inorganic oxide selected from one or more of alumina, silica and silica-alumina. The alumina used in the invention is one or more transition phase alumina selected from gamma, eta, theta, delta and chi, also can be one or more transition phase alumina selected from gamma, eta, theta, delta and chi containing one or more additive components selected from silicon, titanium, magnesium, boron, zirconium, thorium, niobium and rare earth, and is preferably gamma-alumina and gamma-alumina containing one or more additive components selected from silicon, phosphorus, titanium, magnesium, boron, zirconium, thorium, niobium and rare earth. They may be commercially available or obtained by any of the existing methods.
The unit cell constant of the Y molecular sieve used in the catalyst is 2.415-2.440 nm, and the unit cell constant is preferably 2.422-2.438 nm; specific surface area of micropores is 650m2A ratio of 700m or more, preferably 700m2More than g; the mesopore volume accounts for 30 to 50 percent of the total pore volume, preferably 33 to 45 percent; of molecular sieves27The proportion of the peak area of the resonance signal with the chemical shift of 0 +/-2 ppm in the Al MAS NMR spectrum to the total peak area is not more than 4 percent, and preferably not more than 3 percent; the proportion of the strong acid amount of the molecular sieve to the total acid amount is 70% or more, preferably 75% or more.
The strong acid of the Y molecular sieve in the invention is NH3Temperature programmed desorption (NH)3-TPD) The proportion of strong acid to total acid in the curve of acid with desorption temperature higher than 320 ℃ is NH3The desorption temperature in the TPD results is greater than the ratio of the amount of strong acid at 320 ℃ to the total acid.
Based on the carrier, the content of the Y molecular sieve is 10-60 wt%, the content of the matrix is 40-90 wt%, preferably, the content of the Y molecular sieve is 15-45 wt%, and the content of the matrix is 55-85 wt%.
In the catalyst of the present invention, the active metal component comprises at least one metal component selected from group VIII and at least one metal component selected from group VIB. The metal component of group VIII may be iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc., and the metal component of group VIB may be chromium, molybdenum, tungsten, etc. The active metal component is usually supported on the support in the form of a metal oxide.
Taking a hydro-upgrading catalyst as a reference, wherein the hydro-upgrading catalyst contains 1-10 wt% of a VIII group metal component, 5-50 wt% of a VIB group metal component and the balance of a carrier in terms of oxides; preferably, the hydro-upgrading catalyst contains 2-8 wt% of VIII group metal component, 10-35 wt% of VIB group metal component and the balance of carrier.
The hydro-upgrading catalyst can be prepared by the following method:
uniformly mixing the Y molecular sieve and the matrix, molding, and roasting to obtain a carrier;
preparing an impregnation solution of a compound containing an active metal component; and
impregnating the carrier by using an impregnating solution, and drying and roasting to obtain the hydro-upgrading catalyst.
In the catalyst of the invention, the carrier is made of molecular sieve and matrix, and can be made into various easy-to-handle molded objects according to different requirements, such as microspheres, spheres, tablets or strips. The shaping can be carried out by conventional methods, for example, by extruding the molecular sieve and the matrix into strips and calcining the strips. When the carrier is extruded and molded, a proper amount of extrusion aid and/or adhesive can be added into the carrier, and then the carrier is extruded and molded. The kind and amount of the extrusion aid and the peptizing agent are well known to those skilled in the art, for example, common extrusion aid may be one or more selected from sesbania powder, methyl cellulose, starch, polyvinyl alcohol, and polyvinyl alcohol.
The supporting method is not particularly limited in the present invention on the premise that it is sufficient to support the active metal component on the carrier, and a preferable method is an impregnation method comprising preparing an impregnation solution of the metal component-containing compound and thereafter impregnating the carrier with the solution. The impregnation method is a conventional method, and for example, it may be an excess liquid impregnation method, a pore saturation method impregnation method. Wherein the specified amount of catalyst can be prepared by adjusting and controlling the concentration, amount or support amount of the impregnation solution containing the metal component, as will be readily understood and realized by those skilled in the art.
The compound containing the metal component selected from the VIB group is selected from one or more soluble compounds thereof, such as one or more of molybdenum oxide, molybdate and paramolybdate, preferably molybdenum oxide, ammonium molybdate and paramolybdate; one or more of tungstate, metatungstate and ethyl metatungstate, preferably ammonium metatungstate and ethyl metatungstate.
The compound containing the metal component selected from the group VIII is selected from one or more soluble compounds thereof, such as one or more soluble complexes of cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride and cobalt, preferably cobalt nitrate and basic cobalt carbonate; one or more of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and soluble complex of nickel, preferably nickel nitrate and basic nickel carbonate.
The preparation of the Y molecular sieve is also included prior to mixing the acidic component with the matrix. The Y molecular sieve is prepared by taking an NaY molecular sieve as a raw material and performing multiple times of exchange, dealumination and three times of hydrothermal roasting, wherein dealumination treatment is performed at least once before the second hydrothermal roasting and the third hydrothermal roasting, dealumination is performed at least twice continuously after the third hydrothermal roasting, and a silicon-containing dealumination agent is used in the last dealumination process.
Specifically, the preparation method of the Y molecular sieve of the invention can comprise the following steps:
mixing the NaY molecular sieve with ammonium salt and water to carry out primary ammonium exchange treatment to obtain a primary ammonium exchange molecular sieve;
carrying out first hydrothermal roasting treatment on the first-time ammonium exchange molecular sieve in a steam atmosphere to obtain a first-time water-roasted molecular sieve;
mixing the first water-baked molecular sieve with water, and adding a first dealuminizing agent to carry out first dealuminization treatment to obtain a first dealuminized molecular sieve;
carrying out second hydrothermal roasting treatment on the first dealuminized molecular sieve in a steam atmosphere to obtain a second hydrothermal roasted molecular sieve;
mixing the second water-baked molecular sieve with water, and adding a second dealuminizing agent for second dealuminization treatment to obtain a second dealuminized molecular sieve;
carrying out third hydrothermal roasting treatment on the second dealuminized molecular sieve in a steam atmosphere to obtain a third hydrothermal roasted molecular sieve;
mixing the third-time water-baked molecular sieve with water, and adding a third dealuminizing agent to carry out third dealuminizing treatment to obtain a third dealuminized molecular sieve; and
mixing the third dealuminized molecular sieve with water, adding a fourth dealuminizing agent for fourth dealuminization treatment, filtering and washing to obtain a Y molecular sieve,
wherein the fourth dealuminizing agent comprises a silicon-containing dealuminizing agent.
In the production method of the present invention, the ammonium salts used in the ammonium exchange treatment are each independently one or more selected from the group consisting of ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium hydrogencarbonate, ammonium oxalate, ammonium sulfate and ammonium bisulfate.
In the preparation method of the invention, the first ammonium exchange treatment is to mix NaY zeolite (namely NaY molecular sieve) with ammonium salt and water according to the weight ratio of NaY molecular sieve: ammonium salt: water 1: 0.3-1.0: 5-10 to obtain slurry, treating the slurry at room temperature to 95 ℃ for 0.5-5 hours, washing and drying the slurry to obtain the first ammonium exchange molecular sieve. Wherein, the NaY molecular sieve is based on the weight of a dry basis (the weight of the molecular sieve after being calcined for 1 hour at 800 ℃ in the invention).
In the preparation method, the first hydrothermal roasting treatment is to roast the first ammonium exchange molecular sieve for 0.5 to 10 hours at the temperature of 350 to 700 ℃ in the atmosphere of 1 to 100 percent of water vapor to obtain the first hydrothermal roasting molecular sieve.
In the preparation method of the invention, the first dealumination treatment is carried out according to the following steps of first water roasting molecular sieve: optional ammonium salts: a first dealuminizing agent: water 1: 0-0.50: 0.02-0.3: 5-10, mixing water with the first-time water-baked molecular sieve and optional ammonium salt, adding a first dealumination agent, treating at room temperature to 90 ℃ for 0.5-6 hours, filtering, and washing to obtain a first-time dealumination molecular sieve, wherein the first-time water-baked molecular sieve is based on dry weight.
In the preparation method, the second hydrothermal roasting treatment is to roast the first dealuminized molecular sieve for 0.5 to 10 hours at the temperature of 350 to 700 ℃ in the atmosphere of 1 to 100 percent of water vapor to obtain the second hydrothermal roasted molecular sieve.
In the preparation method of the invention, the second dealumination treatment is carried out according to the following steps of water roasting molecular sieve for the second time: optional ammonium salts: a second dealuminizing agent: water 1: 0-0.50: 0.02-0.3: 5-10, mixing water with the second-time water-baked molecular sieve and optional ammonium salt, adding a second dealuminizing agent, treating at room temperature to 100 ℃ for 0.5-6 hours, filtering, and washing to obtain a second-time dealuminized molecular sieve, wherein the second-time water-baked molecular sieve is based on dry weight.
In the preparation method, the third hydrothermal roasting treatment is to roast the second dealuminized molecular sieve for 0.5 to 10 hours at the temperature of 350 to 700 ℃ in the atmosphere of 1 to 100 percent of water vapor to obtain the third hydrothermal roasted molecular sieve.
In the preparation method of the invention, the third dealuminization treatment is carried out according to the following steps of water roasting molecular sieve: optional ammonium salts: a third dealuminizing agent: water 1: 0-0.70: 0.02-0.3: 5-10, mixing water with the third-time water-baked molecular sieve and optional ammonium salt, adding a third dealuminizing agent, treating at room temperature to 100 ℃ for 0.5-6 hours, filtering, and washing to obtain a third-time dealuminized molecular sieve, wherein the third-time water-baked molecular sieve is based on dry weight.
In the preparation method of the invention, the fourth dealumination treatment is carried out according to the third dealumination molecular sieve: optional ammonium salts: silicon-containing dealuminizing agent: organic and/or inorganic acids: water 1: 0-0.70: 0.02-0.3: 0-0.07: 5-10, mixing the third dealuminized molecular sieve with optional ammonium salt and water, adding a fourth dealuminizing agent (at least comprising a silicon-containing dealuminizing agent, and further comprising organic acid and/or inorganic acid), treating at room temperature-100 ℃ for 0.5-6 hours, filtering and washing to obtain the fourth dealuminized molecular sieve, wherein the third dealuminized molecular sieve is based on dry weight.
In the preparation method of the present invention, the first dealuminating agent, the second dealuminating agent and the third dealuminating agent may be the same or different and are each independently selected from one or more of organic acids, inorganic acids and organic and inorganic salts, wherein the organic acids are selected from ethylenediaminetetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, the inorganic acids are selected from fluorosilicic acid, hydrochloric acid, sulfuric acid and nitric acid, and the organic and inorganic salts are selected from ammonium oxalate, ammonium fluoride, ammonium fluorosilicate and ammonium fluoroborate.
In the preparation method of the invention, the dealumination agent used in the last dealumination treatment (i.e. the fourth dealumination treatment) comprises a silicon-containing dealumination agent, and can further comprise organic acid and/or inorganic acid, wherein the silicon-containing dealumination agent is fluosilicic acid, ammonium fluosilicate or a mixture of fluosilicic acid and ammonium fluosilicate, the organic acid in the organic acid and/or the inorganic acid is selected from one or more of ethylenediamine tetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, and the inorganic acid is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid.
The Y molecular sieve is prepared by multiple dealumination and three times of water roasting, aluminum vacancies formed in the dealumination process can be filled with silicon as much as possible in the water roasting process, generated non-framework aluminum is gradually stripped through multiple dealumination, and the three times of hydrothermal roasting and the multiple dealumination supplement each other, so that the completeness of crystals is kept, and more strong acid centers are reserved.
Therefore, the Y molecular sieve has high silicon-aluminum ratio, less non-framework aluminum, high strong acid center ratio, large specific surface area, rich secondary pores, higher reaction activity in hydrocarbon cracking reactions such as hydrocracking and the like, less secondary reactions, good ring-opening reaction selectivity, good acid stability and slow inactivation.
In another aspect, the present invention also provides an application of the above hydro-upgrading catalyst in diesel oil processing, including: contacting the diesel fraction with the hydro-upgrading catalyst under hydro-upgrading conditions.
Specifically, the diesel oil fraction is used as raw material, and the hydrogenation modification catalyst is used to perform hydrogenation modification reaction on inferior diesel oil with high impurity content, low cetane number and the like to produce high-quality diesel oil with low impurity content such as sulfur, nitrogen and the like and high cetane number.
Under hydrogen atmosphere, the diesel oil fraction is sequentially contacted with a hydrofining catalyst and a hydro-upgrading catalyst to produce high-quality diesel oil, and the reaction conditions of hydrofining and hydro-upgrading can be the same or different and respectively and independently comprise: the hydrogen partial pressure is 3.0-25.0 MPa, the reaction temperature is 250-450 ℃, and the liquid hourly space velocity is 0.2-10 h-1The volume ratio of hydrogen to oil is 100-2000: 1.
The diesel fraction treated by the method is prepared from one or more of crude oil processing procedures such as crude oil distillation, catalytic cracking, thermal cracking, hydrocracking, petroleum coking and the like, and can also be prepared from other heavy mineral oil and/or synthetic oil processing procedures such as shale oil and/or coal liquefied oil and the like, wherein the boiling point of the product is 180-410 ℃; the inferior diesel oil fraction with high aromatic hydrocarbon content and low cetane number is preferred.
In the invention, the catalyst used in the hydrofining reaction can be various commercial catalysts, such as diesel hydrofining catalysts RS-1000, RS-2000 and the like developed by petrochemical engineering scientific research institute, and can also be prepared according to the prior art in the field.
The key step of catalyzing hydrocracking of low-cetane-number components such as polycyclic aromatic hydrocarbon in diesel oil to convert the low-cetane-number components such as long-side chain alkyl benzene or alkyl naphthenic hydrocarbon is hydrogenation saturation of polycyclic aromatic hydrocarbon and selective ring-opening reaction of saturated products of the polycyclic aromatic hydrocarbon, and in order to keep high diesel yield and high ideal product selectivity, secondary cracking of the selective ring-opening products is required to be inhibited to generate small molecular products. Researches find that the product saturation depth is mainly influenced by the hydrogenation performance, the acid property of the catalyst and the synergistic effect of the hydrogenation function and the cracking function are key factors influencing the ring-opening activity and the secondary cracking performance of the ring-opening product, and the improvement of the diffusion channel of the catalyst, the shortening of the distance between the hydrogenation center and the cracking center, and the enhancement of the synergistic effect of the hydrogenation function and the cracking function are both beneficial to the improvement of the selectivity of the ring-opening product and the activity of the secondary cracking reaction. In addition, the property of the acidic component in the catalyst not only affects the acidity, but also affects the dispersion state and the active phase structure of the metal component on the catalyst, and further affects the activity and selectivity of the selective hydrogenation saturation and selective ring-opening reaction of the polycyclic aromatic hydrocarbon in the poor diesel, namely the yield and the quality of the diesel.
The hydrogenation modification catalyst of the invention improves the diffusion channel of the catalyst by using the Y molecular sieve with high silicon-aluminum ratio, less non-framework aluminum, large specific surface area, rich secondary pores and high strong acid center ratio, improves the synergistic effect of the hydrogenation function and the cracking function of the catalyst, optimizes the acid property of the catalyst, improves the selective hydrogenation saturation and selective ring-opening performance of polycyclic aromatic hydrocarbon, inhibits the non-ideal reactions such as secondary cracking and the like, namely the catalyst has higher aromatic hydrocarbon ring-opening activity and lower secondary cracking performance, and can obviously improve the cetane number of diesel oil while keeping high diesel oil yield when being used in the hydrogenation modification process of inferior diesel oil.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
Examples
Reagents, instruments and tests
In the following examples, preparations and comparative examples, the specifications of the raw materials used are as follows:
NaY molecular sieve, industrial product, silicon-aluminium ratio is greater than 4.7, crystallinity is greater than 85%
Sulfuric acid, chemical purity
Hydrochloric acid, chemical purity
Nitric acid, chemical purity
Oxalic acid, solid, chemically pure
Fluosilicic acid, technical grade
Ammonium nitrate, chemical purity
Ammonium chloride, chemical purity
Ammonium oxalate, chemical purity
Ammonium sulfate, chemical purity
In the following examples, preparations and comparative examples, the apparatus and the test methods involved are as follows:
the cell constants were measured by X-ray diffraction (XRD) using RIPP145-90 standard method (see "analytical methods in petrochemical industry (RIPP test method)", Yangshui et al, scientific Press, 1990 edition).
Measuring the micropore specific surface area of the molecular sieve by adopting a nitrogen adsorption BET specific surface area method; the mesoporous refers to a molecular sieve pore canal with the pore diameter larger than 2 nanometers and smaller than 50 nanometers, and the pore volume is determined by adopting a GB/T5816-.
27The Al MAS NMR is tested by a Bruker Avance III 500MHz nuclear magnetic resonance instrument, and each peak area is calculated by an integration method after a resonance peak spectrogram is subjected to peak-splitting fitting.
The acid amount is NH3TPD, see [ methods for investigating solid catalysts ], petrochemical, 30(12), 2001: 952 ], where the amount of strong acid is NH3The peak temperature of desorption peak is larger than the acid center number above 320 ℃.
The chemical silica-alumina ratio was measured by X-ray fluorescence. Namely, the content of the silicon oxide and the aluminum oxide is calculated, and the content of the silicon oxide and the aluminum oxide is measured by adopting the GB/T30905-2014 standard method.
The kind and content of each metal element in the catalyst were measured by an X-ray fluorescence spectrum analysis method specified in RIPP 132-92 (compiled in methods of petrochemical engineering (RIPP experiments), Yangroi, etc., science publishers, 1 st edition at 1990, 9 months, p. 371-. When the catalyst was tested, a sample of the catalyst was stored under an argon atmosphere.
The composition of the catalyst after calcination is the composition of a sample obtained by calcining the catalyst at 400 to 600 ℃ for 4 hours in an atmospheric atmosphere.
Preparation example 1 preparation of molecular Sieve Y-1
(1) Exchanging NaY zeolite serving as a raw material by using an ammonium sulfate solution, wherein the treatment conditions are as follows: according to NaY molecular sieve (dry basis): ammonium sulfate: water 1: 1.0: 10, exchange at 90 ℃ for 2h, filter, wash with deionized water, and dry at 120 ℃ for 4 h.
(2) And (2) carrying out first hydrothermal roasting treatment on the molecular sieve obtained in the step (1), wherein the roasting temperature is 520 ℃, and roasting for 2h in a 100% steam atmosphere.
(3) And (3) mixing the molecular sieve obtained in the step (2) according to the mass ratio of the molecular sieve (dry basis): sulfuric acid: ammonium chloride: water 1: 0.06: 0.40: 9, pulping the molecular sieve by adding water, slowly dripping 20 percent sulfuric acid, controlling the dripping time for 30min, heating, treating at 70 ℃ for 40min, filtering, washing by deionized water, and drying at 120 ℃ for 4 h.
(4) And (4) carrying out second hydrothermal roasting treatment on the molecular sieve obtained in the step (3), wherein the roasting temperature is 620 ℃, and roasting for 2 hours in a 100% steam atmosphere.
(5) And (3) mixing the molecular sieve obtained in the step (4) according to the mass ratio of the molecular sieve (dry basis): sulfuric acid: water 1: 0.09: and 8, adding water into the molecular sieve, pulping, slowly dropwise adding 20% sulfuric acid, controlling the dropwise adding time for 30min, heating to 70 ℃, treating for 60min, filtering, washing with deionized water, and drying at 120 ℃ for 4 h.
(6) And (5) carrying out a third hydrothermal roasting treatment on the molecular sieve obtained in the step (5), wherein the roasting temperature is 650 ℃, and roasting for 2 hours in a 100% water vapor atmosphere.
(7) And (3) mixing the molecular sieve obtained in the step (7) according to the mass ratio of the molecular sieve (dry basis): sulfuric acid: water 1: 0.09: and 8, adding water into the molecular sieve, pulping, slowly dropwise adding 30% sulfuric acid, controlling the dropwise adding time for 40min, heating, treating at 70 ℃ for 60min, filtering, and washing with deionized water.
(8) And (3) mixing the molecular sieve obtained in the step (7) according to the following molecular sieve: ammonium sulfate: fluosilicic acid, sulfuric acid: h2Adding water into the molecular sieve for pulping, adding ammonium sulfate, slowly dropwise adding 30% fluosilicic acid and 20% sulfuric acid, controlling the dropwise adding time for 40min, heating, treating at 80 ℃ for 90min, filtering, washing with deionized water to obtain the molecular sieve Y-1, wherein each parameter is as shown in Table 1Shown in the figure.
Preparation example 2 preparation of molecular Sieve Y-2
(1) Exchanging NaY zeolite serving as a raw material by using an ammonium sulfate solution, wherein the treatment conditions are as follows: according to NaY molecular sieve (dry basis): ammonium sulfate: water 1:0.5: 7, exchange at 80 ℃ for 1h, filter, wash with deionized water, and dry at 120 ℃ for 4 h.
(2) And (2) carrying out first hydrothermal roasting treatment on the molecular sieve obtained in the step (1), wherein the roasting temperature is 670 ℃, and roasting for 2h in a 100% steam atmosphere.
(3) And (3) mixing the molecular sieve obtained in the step (2) according to the mass ratio of the molecular sieve (dry basis): oxalic acid: ammonium nitrate: water 1: 0.20: 0.40: 9, firstly adding water into the molecular sieve for pulping, adding ammonium nitrate and oxalic acid under stirring at room temperature, stirring for 60min, filtering, washing twice by deionized water, and drying at 120 ℃ for 3 h.
(4) And (4) carrying out second hydrothermal roasting treatment on the molecular sieve obtained in the step (3), wherein the roasting temperature is 645 ℃, and roasting for 2.5 hours in a 100% steam atmosphere.
(5) Adding 7 times of water into the molecular sieve obtained in the step (4), pulping, heating the pulp to 60 ℃, and then adding the following components in percentage by weight: nitric acid: ammonium oxalate: water 1: 0.13: 0.2, preparing ammonium oxalate, nitric acid and water into a solution, adding the aqueous solution into the molecular sieve slurry, controlling the dropping time to be 30min, continuously stirring at 60 ℃ for 40min, filtering, washing by deionized water, and drying at 105 ℃ for 2 h.
(6) And (5) carrying out a third hydrothermal roasting treatment on the molecular sieve obtained in the step (5), wherein the roasting temperature is 670 ℃, and roasting for 2h in a 100% water vapor atmosphere.
(7) And (3) mixing the molecular sieve obtained in the step (6) according to the mass ratio of the molecular sieve (dry basis): sulfuric acid: ammonium nitrate: water 1: 0.13: 0.30: 9, firstly adding a proper amount of water into the molecular sieve, pulping, then adding ammonium nitrate, then adding 30% sulfuric acid aqueous solution at a constant speed, controlling the dropping time for 40min, heating, treating at 70 ℃ for 60min, filtering, washing by deionized water, and drying at 120 ℃ for 4 h.
(8) And (3) mixing the molecular sieve obtained in the step (7) according to the following molecular sieve: ammonium sulfate: h2SiF 6: H2O ═ 1:0.2: 0.15: 7, adding water into the molecular sieve, pulping, adding ammonium sulfate, slowly adding 30% fluosilicic acid dropwise, controlling the dropwise adding time for 60min, heating, treating at 60 ℃ for 50min, filtering, washing with deionized water, and drying at 120 ℃ to obtain the molecular sieve Y-2, wherein all parameters are shown in table 1.
Preparation example 3 preparation of molecular Sieve Y-3
(1) Exchanging NaY zeolite serving as a raw material with an ammonium chloride solution, wherein the treatment conditions are as follows: according to NaY molecular sieve (dry basis): ammonium chloride: water 1: 0.7: 10, exchange at 85 ℃ for 1h, filter, wash with deionized water, and dry at 120 ℃ for 4 h.
(2) And (2) carrying out first hydrothermal roasting treatment on the molecular sieve obtained in the step (1), wherein the roasting temperature is 600 ℃, and roasting for 2h in a 100% steam atmosphere.
(3) And (3) mixing the molecular sieve obtained in the step (2) according to the mass ratio of the molecular sieve (dry basis): citric acid: sulfuric acid: water 1: 0.15: 0.05: and 8, adding water into the molecular sieve, pulping, heating, adding 20% sulfuric acid at a constant speed at 70 ℃ under stirring, controlling the dropping time for 30min, adding 20% citric acid aqueous solution, controlling the dropping time for 20min, continuously stirring at 70 ℃ for 1h after the addition is finished, filtering, washing with deionized water, and drying at 120 ℃ for 4 h.
(4) And (4) carrying out second hydrothermal roasting treatment on the molecular sieve obtained in the step (3), wherein the roasting temperature is 600 ℃, and roasting for 2 hours in a 100% steam atmosphere.
(5) And (3) mixing the molecular sieve obtained in the step (4) according to the mass ratio of the molecular sieve (dry basis): hydrochloric acid: ammonium sulfate: water 1: 0.06: 0.1: 10, adding water into the molecular sieve, pulping, adding ammonium sulfate, stirring uniformly, slowly dropwise adding hydrochloric acid with the concentration of 15%, controlling the dropwise adding time to be 1h, heating to 60 ℃, treating for 40min, filtering, washing with deionized water, and drying at 120 ℃ for 4 h.
(6) And (4) carrying out third hydrothermal roasting treatment on the molecular sieve obtained in the step (5), wherein the roasting temperature is 550 ℃, and roasting for 3 hours in a 100% water vapor atmosphere.
(7) And (3) mixing the molecular sieve obtained in the step (6) according to the mass ratio of the molecular sieve (dry basis): hydrochloric acid: oxalic acid: ammonium sulfate: water 1: 0.05: 0.19: 0.1: 10, adding water into the molecular sieve, pulping, adding ammonium sulfate, slowly dripping hydrochloric acid with the concentration of 10%, controlling the dripping time for 40min, adding oxalic acid, heating, treating at 70 ℃ for 60min, filtering, and washing with deionized water.
(8) Sieving the molecular sieve obtained in the step (7) according to a molecular sieve; ammonium chloride: fluosilicic acid, hydrochloric acid: h2Adding water into the molecular sieve for pulping, adding ammonium chloride, slowly dropwise adding 30% fluosilicic acid and 20% hydrochloric acid at the same time, controlling the dropwise adding time for 60min, heating, treating at 60 ℃ for 50min, filtering, and washing with deionized water to obtain the molecular sieve Y-3, wherein each parameter is shown in table 1.
Preparation example 4 preparation of molecular Sieve Y-4
(1) Exchanging NaY zeolite serving as a raw material by using an ammonium sulfate solution, wherein the treatment conditions are as follows: according to NaY molecular sieve (dry basis): ammonium sulfate: water 1: 1.0: 10, exchange at 90 ℃ for 2h, filter, wash with deionized water, and dry at 120 ℃ for 4 h.
(2) And (2) carrying out first hydrothermal roasting treatment on the molecular sieve obtained in the step (1), wherein the roasting temperature is 520 ℃, and roasting for 2h in a 100% steam atmosphere.
(3) And (3) mixing the molecular sieve obtained in the step (2) according to the mass ratio of the molecular sieve (dry basis): sulfuric acid: ammonium chloride: water 1: 0.06: 0.40: 9, pulping the molecular sieve by adding water, slowly dripping 20 percent sulfuric acid, controlling the dripping time for 30min, heating, treating at 70 ℃ for 40min, filtering, washing by deionized water, and drying at 120 ℃ for 4 h.
(4) And (4) carrying out second hydrothermal roasting treatment on the molecular sieve obtained in the step (3), wherein the roasting temperature is 620 ℃, and roasting for 2 hours in a 100% steam atmosphere.
(5) And (3) mixing the molecular sieve obtained in the step (4) according to the mass ratio of the molecular sieve (dry basis): sulfuric acid: water 1: 0.09: and 8, adding water into the molecular sieve, pulping, slowly dropwise adding 20% sulfuric acid, controlling the dropwise adding time for 30min, heating to 70 ℃, treating for 60min, filtering, washing with deionized water, and drying at 120 ℃ for 4 h.
(6) And (5) carrying out a third hydrothermal roasting treatment on the molecular sieve obtained in the step (5), wherein the roasting temperature is 650 ℃, and roasting for 2 hours in a 100% water vapor atmosphere.
(7) And (3) mixing the molecular sieve obtained in the step (7) according to the mass ratio of the molecular sieve (dry basis): ammonium sulfate: fluosilicic acid: sulfuric acid: h2Adding water into a molecular sieve, pulping, adding ammonium sulfate, slowly dropwise adding 30% fluosilicic acid and 20% sulfuric acid, controlling the dropwise adding time for 40min, heating, treating at 80 ℃ for 90min, filtering, and washing with deionized water.
(8) And (3) mixing the molecular sieve obtained in the step (7) according to the following molecular sieve: ammonium sulfate: fluosilicic acid, sulfuric acid: h2Adding water into the molecular sieve for pulping, adding ammonium sulfate, slowly dropwise adding 30% fluosilicic acid and 20% sulfuric acid, controlling the dropwise adding time for 40min, heating, treating at 80 ℃ for 90min, filtering, and washing with deionized water to obtain the molecular sieve Y-4, wherein all parameters are shown in Table 1.
TABLE 1 parameters of the respective molecular sieves in the preparation examples and comparative examples
| Molecular sieves | Unit cell constant/nm | Fraction of mesopores% | Proportion of strong acid/%) | Specific surface area of micropores/(m)2/g) | A0±2ppm/AGeneral assembly/％* |
| Y-1 | 2.426 | 42 | 80 | 685 | 3.2 |
| Y-2 | 2.420 | 36 | 75 | 710 | 4.0 |
| Y-3 | 2.434 | 40 | 77 | 674 | 1.0 |
| Y-4 | 2.423 | 39 | 84 | 700 | 1.0 |
| D-1 | 2.453 | 20 | 61 | 617 | 7.2 |
Note: denotes27The ratio of the peak area of the resonance signal with a chemical shift of 0. + -.2 ppm in the Al MAS NMR spectrum to the total peak area.
Example 1
200.0 g of pseudo-boehmite (manufactured by catalyst Changling division) with a dry basis of 70% and 73.2 g of molecular sieve Y-1 (manufactured by preparation example 1) with a dry basis of 82% are weighed and mixed uniformly, extruded into a three-blade bar shape with the excircle diameter of 1.6 mm on a bar extruder, dried for 3 hours at 120 ℃, and calcined for 4 hours at 600 ℃ to obtain a catalyst carrier Z1.
Taking 1100 g of vector Z and using 80ml of the vector Z containing WO respectively3275.0 g/l, NiO 25.0 g/l, P2O512.5 g/L of mixed solution of ammonium metatungstate, basic nickel carbonate, phosphoric acid and citric acid is soaked for 3 hours, dried at 120 ℃ for 3 hours and activated at 180 ℃ for 3 hours to obtain the catalyst C1.
The composition of catalyst C1 after calcination, based on the catalyst, is shown in Table 2.
Example 2
200.0 g of pseudo-boehmite (catalyst Changling division) with a dry basis of 70% and 74.1 g of molecular sieve Y-2 (prepared in preparation example 2) with a dry basis of 81% are weighed and mixed uniformly, extruded into a three-blade bar shape with the circumscribed circle diameter of 1.6 mm on a bar extruder, dried for 3 hours at 120 ℃, and calcined for 4 hours at 600 ℃ to obtain a catalyst carrier Z2.
Taking 2100 g of vector Z and adding 81 ml of WO3271.6 g/L, NiO 24.7 g/L, P2O512.3 g/L of mixed solution of ammonium metatungstate, basic nickel carbonate, phosphoric acid and citric acid is soaked for 3 hours, dried at 120 ℃ for 3 hours and activated at 180 ℃ for 3 hours to obtain the catalyst C2.
The composition of catalyst C2 after calcination, based on the catalyst, is shown in Table 2.
Example 3
200.0 g of pseudo-boehmite (catalyst Changling division) with a dry basis of 70% and 72.3 g of molecular sieve Y-3 (prepared in preparation example 3) with a dry basis of 83% are weighed and mixed uniformly, extruded into a three-blade bar shape with the circumscribed circle diameter of 1.6 mm on a bar extruder, dried for 3 hours at 120 ℃, and calcined for 4 hours at 600 ℃ to obtain a catalyst carrier Z3.
Collecting Z3100 g of vector, adding 81 ml of WO3271.6 g/L, NiO 24.7 g/L, P2O512.3 g/l of metatungstateAnd (3) soaking the mixed solution of ammonium salt, basic nickel carbonate, phosphoric acid and citric acid for 3 hours, drying the mixed solution at the temperature of 120 ℃ for 3 hours, and activating the mixed solution at the temperature of 180 ℃ for 3 hours to obtain the catalyst C3.
The composition of catalyst C3 after calcination, based on the catalyst, is shown in Table 2.
Example 4
200.0 g of pseudo-boehmite (catalyst Changling division) with a dry basis of 70% and 70.6 g of molecular sieve Y-4 (prepared in preparation example 4) with a dry basis of 85% are weighed and mixed uniformly, extruded into a three-blade bar shape with the circumscribed circle diameter of 1.6 mm on a bar extruder, dried at 120 ℃ for 3 hours and calcined at 600 ℃ for 4 hours to obtain a catalyst carrier Z4.
Taking 4100 g of vector Z, and using 83 ml of vector Z containing WO respectively3265.1 g/L, NiO 24.1 g/L, P2O512.0 g/L of mixed solution of ammonium metatungstate, basic nickel carbonate, phosphoric acid and citric acid is soaked for 3 hours, dried at 120 ℃ for 3 hours and activated at 180 ℃ for 3 hours to obtain the catalyst C4.
The composition of catalyst C4 after calcination, based on the catalyst, is shown in Table 2.
Example 5
Taking 4100 g of vector Z, and using 83 ml of vector Z containing WO respectively390.4 g/l, NiO 12.0 g/l, P2O56.0 g/L of mixed solution of ammonium metatungstate, basic nickel carbonate, phosphoric acid and citric acid is soaked for 3 hours, dried at 120 ℃ for 3 hours and activated at 180 ℃ for 3 hours to obtain the catalyst C5.
The composition of catalyst C5 after calcination, based on the catalyst, is shown in Table 2.
Example 6
Taking 4100 g of vector Z, and using 83 ml of vector Z containing WO respectively3530.1 g/l, NiO 108.4 g/l, P2O5Soaking the mixed solution of 24.1 g/L ammonium metatungstate, basic nickel carbonate, phosphoric acid and citric acid for 3 hours, drying the mixed solution at 120 ℃ for 3 hours, and activating the mixed solution at 180 ℃ for 3 hours to obtain the catalyst C6.
The composition of catalyst C6 after calcination, based on the catalyst, is shown in Table 2.
Example 7
Taking vector Z4100 g, 83 ml of MoO3180.7 g/l, NiO 24.1 g/l, P2O5The mixed solution of 12.0 g/L of molybdenum trioxide, basic nickel carbonate, phosphoric acid and citric acid is soaked for 3 hours, dried at 120 ℃ for 3 hours and activated at 180 ℃ for 3 hours to obtain the catalyst C7.
The composition of catalyst C7 after calcination, based on the catalyst, is shown in Table 2.
Example 8
251.4 g of pseudoboehmite (catalyst Chang Ling division) with dry basis of 70% and 28.2 g of molecular sieve Y-4 (prepared by preparation example 4) with dry basis of 85% are weighed and mixed evenly, extruded into a three-blade bar shape with the circumscribed circle diameter of 1.6 mm on a bar extruder, dried for 3 hours at 120 ℃, and calcined for 4 hours at 600 ℃ to obtain the catalyst carrier Z5.
The vector Z5100 g is taken, and 80ml of the vector respectively contains WO3275.0 g/l, NiO 25.0 g/l, P2O512.5 g/L of mixed solution of ammonium metatungstate, basic nickel carbonate, phosphoric acid and citric acid is soaked for 3 hours, dried at 120 ℃ for 3 hours and activated at 180 ℃ for 3 hours to obtain the catalyst C8.
The composition of catalyst C8 after calcination, based on the catalyst, is shown in Table 2.
Example 9
142.9 g of pseudo-boehmite (manufactured by catalyst Changling division) with a dry basis of 70% and 117.6 g of molecular sieve Y-4 (manufactured by preparation example 4) with a dry basis of 85% are weighed and mixed uniformly, extruded into a three-leaf bar shape with the circumscribed circle diameter of 1.6 mm on a bar extruder, dried for 3 hours at 120 ℃, and calcined for 4 hours at 600 ℃ to obtain the catalyst carrier Z6.
Taking Z6100 g of carrier, using 85 ml to respectively contain WO3258.8 g/l, NiO 23.5 g/l, P2O5The mixed solution of 11.8 g/L ammonium metatungstate, basic nickel carbonate, phosphoric acid and citric acid is soaked for 3 hours, dried at 120 ℃ for 3 hours and activated at 180 ℃ for 3 hours to obtain the catalyst C9.
The composition of catalyst C9 after calcination, based on the catalyst, is shown in Table 2.
Example 10
114.3 g of pseudo-boehmite (catalyst Changling division) with a dry basis of 70%, 70.6 g of molecular sieve Y-4 (prepared by preparation example 4) with a dry basis of 85% and 78.9 g of silica-alumina (Sasol company, Germany) with a dry basis of 76% are weighed and mixed uniformly, extruded into a three-leaf bar shape with a circumscribed circle diameter of 1.6 mm on a bar extruder, dried for 3 hours at 120 ℃, and calcined for 4 hours at 600 ℃ to obtain the catalyst carrier Z7.
Taking the carrier Z7100 g, using 88 ml to respectively contain WO3250.0 g/L, NiO 22.7 g/L, P2O5The mixed solution of 11.4 g/L ammonium metatungstate, basic nickel carbonate, phosphoric acid and citric acid is soaked for 3 hours, dried at 120 ℃ for 3 hours and activated at 180 ℃ for 3 hours to obtain the catalyst C10.
The composition of catalyst C10 after calcination, based on the catalyst, is shown in Table 2.
Comparative example 1
100.0 g of pseudoboehmite (catalyst Chang Ling division) with a dry basis of 70% and 78.9 g of the existing Y molecular sieve (marked as D-1, catalyst Chang Ling division, trade mark LAY, the property of which is shown in Table 1) with a dry basis of 76% are weighed and mixed uniformly, extruded into a three-blade bar shape with the circumscribed circle diameter of 1.6 mm on an extruding machine, dried for 3 hours at 120 ℃, and calcined for 4 hours at 600 ℃ to obtain a catalyst carrier D.
Taking 100 g of the vector D and using 75 ml of the vector D containing WO respectively3293.3 g/l, NiO 26.7 g/l, P2O513.3 g/L of mixed solution of ammonium metatungstate, basic nickel carbonate, phosphoric acid and citric acid is soaked for 3 hours, dried at 120 ℃ for 3 hours and activated at 180 ℃ for 3 hours to obtain the catalyst D1.
The composition of catalyst D after calcination, based on the catalyst, is shown in Table 2.
TABLE 2 compositions of catalysts in examples 1-10 and comparative examples
The performance of the hydroupgrading catalyst provided by the present invention was tested by the following application examples.
Application example 1
The performance of the catalyst C1 provided by the invention is evaluated on a 30 ml fixed bed device by taking catalytic cracking diesel oil with the density of 0.9561 g/cm < 3 >, the sulfur content of 9800ppm, the nitrogen content of 743ppm and the total aromatic hydrocarbon content of 85.7% as a raw material, wherein the upper part of a bed layer is filled with an industrial refined catalyst, the lower part of the bed layer is filled with the catalyst C1, and the loading of the catalyst C1 is 15 ml.
Pre-vulcanizing catalyst C1 before feeding raw oil, wherein the vulcanization conditions are as follows: 2 hours at 110 ℃ and 4 hours at 300 ℃, and the vulcanized oil is kerosene containing 6 weight percent of carbon disulfide.
Reaction conditions in the hydrofining reaction zone: the reaction temperature is 350 ℃, the hydrogen partial pressure is 6.5MPa, and the liquid hourly space velocity is 1.5h-1And the volume ratio of hydrogen to oil is 800. The reaction conditions of the hydro-upgrading reaction zone are as follows: the reaction temperature is 370 ℃, the hydrogen partial pressure is 6.5MPa, and the hourly space velocity of the modifier liquid is 1.2h-1And the volume ratio of hydrogen to oil is 800.
The test results are listed in table 3.
Application example 2
The performance of catalyst C2 was tested under the same conditions as in application example 1, and the test results are shown in Table 3.
Application example 3
The performance of catalyst C3 was tested under the same conditions as in application example 1, and the test results are shown in Table 3.
Application example 4
The performance of catalyst C4 was tested under the same conditions as in application example 1, and the test results are shown in Table 3.
Comparative application example 1
The catalyst D1 was tested for performance under the same conditions and with the same feed as in application example 1, and the test results are shown in Table 3.
TABLE 3 catalyst reaction Performance
| Application example 1 | Application example 2 | Application example 3 | Application example 4 | Comparative application example 1 | |
| Catalyst and process for preparing same | C1 | C2 | C3 | C4 | D1 |
| Diesel yield/% | 96.5 | 97.2 | 95.7 | 96.8 | 94.6 |
| Cetane number increase value | 11.4 | 9.7 | 9.5 | 12.8 | 8.2 |
The test results in table 3 show that, compared with the existing catalyst, the catalyst provided by the invention can greatly improve the cetane number of diesel oil while keeping higher diesel oil yield; meanwhile, the catalyst provided by the invention is found to have higher activity stability.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (18)
1. A hydro-upgrading catalyst, which is characterized by comprising a carrier and an active metal component loaded on the carrier, wherein the carrier comprises a substrate and a Y molecular sieve,
wherein the unit cell constant of the Y molecular sieve is 2.415-2.440 nm; of the Y molecular sieve27The proportion of the peak area of the resonance signal with the chemical shift of 0 +/-2 ppm in the Al MAS NMR spectrum to the total peak area is not more than 4 percent; the strong acid content of the Y molecular sieve accounts for more than 70 percent of the total acid content.
2. The hydro-upgrading catalyst of claim 1, wherein the Y molecular sieve has a unit cell constant of 2.422-2.438 nm; of the Y molecular sieve27The proportion of the peak area of the resonance signal with the chemical shift of 0 +/-2 ppm in the Al MAS NMR spectrum to the total peak area is not more than 3 percent; the strong acid amount of the Y molecular sieve accounts for more than 75 percent of the total acid amount.
3. The hydro-upgrading catalyst of claim 1, wherein the Y molecular sieve has a micropore specific surface area of 650m2A ratio of 700m or more, preferably 700m2More than g; the proportion of the mesoporous volume of the Y molecular sieve in the total pore volume is 30-50%, preferably 33-45%.
4. The hydro-upgrading catalyst of any of claims 1 to 3, wherein the substrate is selected from one or more of alumina, silica and silica-alumina.
5. The hydro-upgrading catalyst of any of claims 1 to 3, characterized in that the active metal components comprise at least one metal component selected from group VIII and at least one metal component selected from group VIB.
6. The hydro-upgrading catalyst according to claim 5, wherein the hydro-upgrading catalyst comprises 1 to 10 wt% of the VIII group metal component and 5 to 50 wt% of the VIB group metal component in terms of oxides based on the hydro-upgrading catalyst.
7. The hydro-upgrading catalyst according to claim 6, wherein the hydro-upgrading catalyst comprises 2 to 8 wt% of the VIII group metal component and 10 to 35 wt% of the VIB group metal component in terms of oxides based on the hydro-upgrading catalyst.
8. The hydro-upgrading catalyst according to any one of claims 1 to 3, wherein the Y molecular sieve is contained in an amount of 10 to 60 wt% and the matrix is contained in an amount of 40 to 90 wt%, based on the support.
9. The hydro-upgrading catalyst according to claim 8, wherein the Y molecular sieve is 15 to 45 wt% and the matrix is 55 to 85 wt% based on the support.
10. The method of producing a hydro-upgrading catalyst according to any one of claims 1 to 9, comprising:
uniformly mixing the Y molecular sieve and the matrix, molding, and roasting to obtain the carrier;
and (3) impregnating the carrier with a solution containing the active metal component, and drying and roasting to obtain the hydro-upgrading catalyst.
11. The method of claim 10, further comprising, prior to mixing the Y molecular sieve with the matrix, preparing the Y molecular sieve by:
mixing the NaY molecular sieve with ammonium salt and water to carry out primary ammonium exchange treatment to obtain a primary ammonium exchange molecular sieve;
carrying out first hydrothermal roasting treatment on the first ammonium exchange molecular sieve in a steam atmosphere to obtain a first water-roasted molecular sieve;
mixing the first water-baked molecular sieve with water, and adding a first dealuminizing agent to carry out first dealuminization treatment to obtain a first dealuminized molecular sieve;
carrying out second hydrothermal roasting treatment on the first dealuminized molecular sieve in a steam atmosphere to obtain a second hydrothermal roasted molecular sieve;
mixing the second water-baked molecular sieve with water, and adding a second dealuminizing agent for second dealuminization treatment to obtain a second dealuminized molecular sieve;
carrying out third hydrothermal roasting treatment on the second dealuminized molecular sieve in a steam atmosphere to obtain a third water-roasted molecular sieve;
mixing the third-time water-baked molecular sieve with water, and adding a third dealuminizing agent to carry out third dealuminizing treatment to obtain a third dealuminized molecular sieve; and
mixing the third dealuminized molecular sieve with water, adding a fourth dealuminizing agent for fourth dealuminization treatment, filtering and washing to obtain the Y molecular sieve,
wherein the ammonium salt is selected from one or more of ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium oxalate, ammonium sulfate and ammonium bisulfate, and the fourth dealuminating agent comprises a dealuminating agent containing silicon.
12. A method of producing as claimed in claim 11 wherein the first, second and third dealuminants are each independently selected from one or more of organic acids selected from ethylenediaminetetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, inorganic acids selected from fluorosilicic acid, hydrochloric acid, sulfuric acid and nitric acid and organic and inorganic salts selected from ammonium oxalate, ammonium fluoride, ammonium fluorosilicate and ammonium fluoroborate.
13. A method of producing as claimed in claim 11 wherein the silicon-containing dealuminating agent is fluorosilicic acid, ammonium fluorosilicate or a mixture of fluorosilicic acid and ammonium fluorosilicate.
14. The preparation method according to claim 11, wherein the fourth dealuminating agent further comprises an organic acid and/or an inorganic acid, and the mass ratio of the silicon-containing dealuminating agent to the organic acid and/or the inorganic acid is 0.02-0.3: 0-0.07, the organic acid is selected from one or more of ethylenediamine tetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, and the inorganic acid is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid.
15. The production method according to claim 11, wherein the temperature of the first hydrothermal calcination treatment, the second hydrothermal calcination treatment, and the third hydrothermal calcination treatment is 350 to 700 ℃, the water vapor concentration is 1 to 100%, and the calcination time is 0.5 to 10 hours; the temperature of the first ammonium exchange treatment is room temperature to 95 ℃, and the treatment time is 0.5 to 5 hours; the temperature of the first dealuminization treatment is between room temperature and 90 ℃, and the treatment time is between 0.5 and 6 hours; the temperature of the second dealuminization treatment is between room temperature and 100 ℃, and the treatment time is between 0.5 and 6 hours; the temperature of the third dealuminization treatment is between room temperature and 100 ℃, and the treatment time is 0.5 to 6 hours; the temperature of the fourth dealuminization treatment is between room temperature and 100 ℃, and the treatment time is between 0.5 and 6 hours.
16. The production method according to any one of claims 11 to 15, characterized in that the ammonium salt is added in at least one of the first dealumination treatment, the second dealumination treatment, the third dealumination treatment and the fourth dealumination treatment.
17. The method according to claim 16, wherein in the first ammonium exchange treatment, the NaY molecular sieve: the ammonium salt: water 1: 0.3-1.0: 5-10; in the first dealumination treatment, the first water-calcined molecular sieve: the ammonium salt: the first dealuminizing agent: water 1: 0-0.50: 0.02-0.3: 5-10; in the second dealumination treatment, the second water-calcined molecular sieve: the ammonium salt: the second dealuminizing agent: water 1: 0-0.50: 0.02-0.3: 5-10; in the third dealumination treatment, the third water-calcined molecular sieve: the ammonium salt: the third dealuminizing agent: water 1: 0-0.70: 0.02-0.3: 5-10; in the fourth dealumination treatment, the third dealumination molecular sieve: the ammonium salt: the silicon-containing dealuminizing agent comprises the following components: water 1: 0-0.70: 0.02-0.3: 5 to 10.
18. Use of a hydro-upgrading catalyst according to any of claims 1-9 in diesel fuel processing, comprising contacting a diesel fraction with the hydro-upgrading catalyst under hydro-upgrading conditions.
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