CN117085725A - Distillate oil hydrofining catalyst and preparation method and application thereof - Google Patents
Distillate oil hydrofining catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN117085725A CN117085725A CN202210527275.5A CN202210527275A CN117085725A CN 117085725 A CN117085725 A CN 117085725A CN 202210527275 A CN202210527275 A CN 202210527275A CN 117085725 A CN117085725 A CN 117085725A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- distillate
- catalyst
- phosphorus
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 150
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003921 oil Substances 0.000 claims abstract description 54
- -1 phosphorus modified SBA-15 molecular sieve Chemical class 0.000 claims description 59
- 239000010936 titanium Substances 0.000 claims description 48
- 229910052719 titanium Inorganic materials 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000011574 phosphorus Substances 0.000 claims description 34
- 229910052698 phosphorus Inorganic materials 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 239000003607 modifier Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 238000005470 impregnation Methods 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims description 3
- 150000003609 titanium compounds Chemical class 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- VSOYJNRFGMJBAV-UHFFFAOYSA-N N.[Mo+4] Chemical compound N.[Mo+4] VSOYJNRFGMJBAV-UHFFFAOYSA-N 0.000 claims description 2
- ZGRBQKWGELDHSV-UHFFFAOYSA-N N.[W+4] Chemical compound N.[W+4] ZGRBQKWGELDHSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 13
- 239000011593 sulfur Substances 0.000 abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 12
- 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 10
- 238000004523 catalytic cracking Methods 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000003209 petroleum derivative Substances 0.000 abstract description 2
- 239000010724 circulating oil Substances 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 30
- 238000011156 evaluation Methods 0.000 description 28
- 239000002283 diesel fuel Substances 0.000 description 26
- 239000003502 gasoline Substances 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 241000219793 Trifolium Species 0.000 description 13
- 238000007598 dipping method Methods 0.000 description 12
- 238000011068 loading method Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 241000219782 Sesbania Species 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 8
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 8
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 8
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000004939 coking Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 101710169849 Catalase isozyme A Proteins 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 3
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 3
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 3
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 108091006231 SLC7A2 Proteins 0.000 description 3
- 108091006230 SLC7A3 Proteins 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000005504 petroleum refining Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AXDZBUZLJGBONR-UHFFFAOYSA-N 1,2-dimethyldibenzothiophene Chemical compound C1=CC=C2C3=C(C)C(C)=CC=C3SC2=C1 AXDZBUZLJGBONR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 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
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001930 tungsten oxide 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/307—Cetane number, cetane index
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The invention discloses a distillate oil hydrofining catalyst and a preparation method and application thereof. The catalyst is suitable for hydrofining petroleum distillate oil at 150-400 ℃, and is particularly suitable for hydrofining catalytic cracking hydrogen circulating oil with high sulfur, nitrogen and aromatic hydrocarbon content and lower cetane number. The catalyst of the invention can reduce the contents of sulfur, nitrogen and aromatic hydrocarbon under the milder hydrofining condition, and greatly improve the cetane number of the product.
Description
Technical Field
The invention relates to a distillate oil hydrofining catalyst and a preparation method and application thereof, which are suitable for producing clean oil products by hydrofining of low-quality gasoline and diesel oil fractions in the field of petroleum refining.
Background
In the petroleum refining industry, with the development of catalytic cracking technology and delayed coking technology, the proportion of secondary processing distillate oil such as catalytic gasoline and diesel oil, coking gasoline and diesel oil and the like in the total amount of gasoline and diesel oil is increased. However, the catalytic gasoline and diesel oil and the coking gasoline and diesel oil have high content of sulfur, nitrogen and other impurities, and particularly have high content of aromatic hydrocarbon, poor stability and lower cetane number in the catalytic diesel oil and the coking diesel oil. As the oil refining technology is developed towards the deep processing direction, the quality of the catalytic gasoline and diesel oil and the coking gasoline and diesel oil is poorer and worse. And the specification standard and environmental protection regulation of new clean fuels put more severe requirements on the quality of distillate oil. Therefore, how to further improve the quality of the secondary processed distillate oil, particularly the secondary processed diesel oil, is an important issue.
Because of the shortage of petroleum resources, catalytic diesel is mainly used for blending and producing vehicle diesel after hydrofining in China. At present, the annual processing capacity of the catalytic cracking device in China is over 1 hundred million tons, and in the composition of gasoline and diesel products, the catalytic cracking gasoline accounts for about 80 percent and the catalytic diesel accounts for about 30 percent. In recent years, with the increasing heavy quality of crude oil processed in China, raw materials processed by catalytic cracking are increasingly heavy and poor in quality, and in addition, in order to achieve the purposes of improving the quality of gasoline or increasing the yield of propylene, a plurality of enterprises reform a catalytic cracking device or improve the operation severity of the catalytic cracking device, so that the quality of catalytic cracked products, particularly catalytic diesel oil, is further deteriorated, and the catalytic cracked diesel oil is mainly high in density and low in cetane number, and is difficult to meet the increasingly strict environmental protection regulations by adopting the conventional hydrofining technology. Catalytic diesel has become a limiting factor affecting product quality upgrades and benefit increases for enterprises.
Because of high content of catalytic diesel aromatic hydrocarbon, the density is high, the cetane number is low, and the catalytic diesel is the diesel blending component with the worst property and the diesel component with the greatest processing difficulty in quality upgrading. Typically, the aromatic hydrocarbon content is 64.5% -78.3%, the total content of bi-and tri-cyclic aromatic hydrocarbons is more than 60%, and the total aromatic hydrocarbon content is more than 50%. For diesel fractions, it is disadvantageous to be rich in aromatics. In order to realize deep desulfurization, denitrification and dearomatization of the inferior diesel oil fraction and produce clean diesel oil, various special processes and catalysts are developed at home and abroad. For example, USP5114562 describes a two-stage process hydrotreating technique in which a non-noble metal catalyst is used to remove most of the sulfur in the first stage, and a noble metal platinum catalyst having a higher ability to saturate in the second stage is used to enhance the properties of the oil by deep hydrodearomatization. However, the hydrogenation process is relatively complex, the original device also needs to be partially modified, and the noble metal catalyst is used, so that the processing cost is relatively high.
Disclosure of Invention
The invention mainly aims to provide a distillate oil hydrofining catalyst and a preparation method and application thereof, so as to solve the problems that the distillate oil hydrofining catalyst in the prior art is difficult to meet hydrogenation requirements, has high catalyst cost or has severe distillate oil hydrogenation process conditions.
In order to achieve the above object, the present invention provides a distillate hydrofining catalyst comprising a catalyst carrier and an active component, wherein the catalyst carrier comprises a phosphorus-modified SBA-15 molecular sieve and/or a titanium-modified SBA-15 molecular sieve, and the active component comprises a group VIB metal oxide and/or a group VIII metal oxide.
The distillate oil hydrofining catalyst of the invention, wherein the total mass of the distillate oil hydrofining catalyst is usedBased on the mass content of the phosphorus modified SBA-15 molecular sieve, the mass content of the titanium modified SBA-15 molecular sieve is 5-40%; p in the phosphorus-modified SBA-15 molecular sieve 2 O 5 /SiO 2 The molar ratio is 0.1-0.5; in the titanium modified SBA-15 molecular sieve, tiO 2 /SiO 2 The molar ratio is 0.1-0.5.
The distillate oil hydrofining catalyst of the present invention, wherein the catalyst carrier further comprises alumina, the distillate oil hydrofining catalyst further comprises a modifier oxide, the modifier oxide is at least one of silicon, phosphorus, fluorine, titanium, zirconium and gallium oxide, and the mass content of the modifier oxide is 0.5-5% based on the total mass of the distillate oil hydrofining catalyst.
The distillate oil hydrofining catalyst of the present invention, wherein the group VIB metal oxide is molybdenum oxide and/or tungsten oxide, and the group VIII metal oxide is at least one of iron, nickel and cobalt oxide; the mass content of the VIB group metal oxide is 15-30% and the mass content of the VIII group metal oxide is 2-10 w% based on the total mass of the distillate oil hydrofining catalyst.
In order to achieve the above purpose, the invention also provides a preparation method of the distillate oil hydrofining catalyst, which comprises the following steps:
step 1, extruding a phosphorus modified SBA-15 molecular sieve and/or a titanium modified SBA-15 molecular sieve to obtain a catalyst carrier;
step 2, preparing an impregnating solution comprising a compound of a VIB metal and/or a compound of a VIII metal, impregnating the catalyst carrier obtained in the step 1, drying and roasting to obtain the distillate hydrofining catalyst.
The invention relates to a preparation method of a distillate oil hydrofining catalyst, wherein, step 1 is also added with alumina and step 1 or step 2 is also added with a modifier compound, and the modifier compound is at least one of a silicon-containing compound, a phosphorus-containing compound, a fluorine-containing compound, a titanium-containing compound, a zirconium-containing compound and a gallium-containing compound; the compound of the VIB metal is molybdenum ammonium salt and/or tungsten ammonium salt, and the compound of the VIII metal is at least one of nitrate, carbonate or acetate of iron, cobalt and nickel.
The preparation method of the distillate oil hydrofining catalyst comprises the steps of taking the total mass of the distillate oil hydrofining catalyst as a reference, wherein the mass content of the phosphorus-modified SBA-15 molecular sieve is 5% -40%, the mass content of the titanium-modified SBA-15 molecular sieve is 5% -40%, the mass content of the compound of the VIB group metal in terms of oxide is 15% -30%, and the mass content of the compound of the VIII group metal in terms of oxide is 2% -10%.
The preparation method of the distillate oil hydrofining catalyst comprises the step 2, wherein the impregnation is single-component impregnation or double-component impregnation, and the impregnation mode is excessive impregnation or isovolumetric impregnation.
The preparation method of the distillate oil hydrofining catalyst provided by the invention comprises the following steps of: mixing SBA-15 molecular sieve with phosphorus-containing compound, ultrasonic treating, drying and roasting to obtain phosphorus-modified SBA-15 molecular sieve; the preparation method of the titanium modified SBA-15 molecular sieve comprises the following steps: mixing SBA-15 molecular sieve with titanium compound, ultrasonic treating, drying and roasting to obtain titanium modified SBA-15 molecular sieve.
In order to achieve the above purpose, the invention further provides an application of the distillate oil hydrofining catalyst in distillate oil hydrogenation.
The invention has the beneficial effects that:
the catalyst of the invention adopts the titanium modified SBA-15 molecular sieve and/or the phosphorus modified SBA-15 molecular sieve as the carrier, so that the dispersibility of the active components can be improved, and the hydrodesulfurization performance of the catalyst can be improved; furthermore, through the synergistic effect of the two molecular sieves, the hydrofining performance of the catalyst can be improved, so that the catalyst can process inferior gasoline and diesel under milder process conditions, and the effects of deep desulfurization, denitrification, olefin reduction and aromatic hydrocarbon reduction are achieved.
Detailed Description
The following describes the present invention in detail, and the present examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and processes are given, but the scope of protection of the present invention is not limited to the following examples, in which the experimental methods of specific conditions are not noted, and generally according to conventional conditions.
The invention provides a distillate oil hydrofining catalyst, which is suitable for hydrofining of petroleum distillate oil at 150-400 ℃, is suitable for hydrofining of poor-quality gasoline and diesel oil fractions (such as catalytic gasoline and diesel oil and coking gasoline and diesel oil) in the field of petroleum refining, and is particularly suitable for hydrofining of catalytic cracking light cycle oil with high contents of sulfur, nitrogen and aromatic hydrocarbon and lower cetane number. The catalyst of the invention can reduce the contents of sulfur, nitrogen and aromatic hydrocarbon under the milder hydrofining condition, and greatly improve the cetane number of the product. The distillate hydrofining catalyst comprises a catalyst carrier and an active component, wherein the catalyst carrier comprises a phosphorus modified SBA-15 molecular sieve and/or a titanium modified SBA-15 molecular sieve, and the active component comprises a VIB group metal oxide and/or a VIII group metal oxide.
The titanium modified SBA-15 molecular sieve is characterized in that a metal chloride or an organic metal compound of titanium reacts with silanol bonds (Si-OH) on the surface of SBA-15 to form Ti-O covalent bonds, and then metal Ti is fixed on a framework of SBA-15, so that a large number of metal ions or other active centers can be introduced into a pore canal, and metal active species such as Ni, W, co, mo of the catalyst have better dispersibility and catalytic activity. The titanium modified SBA-15 molecular sieve has a titanium loading of 2-10wt%, preferably 4-8wt%.
The SBA-15 molecular sieve is modified by phosphoric acid or phosphotungstic acid, the phosphorus modified SBA-15 molecular sieve has certain acid strength, and the BET specific surface area of the SBA-15 molecular sieve before modification can reach 649m 2 Per gram, pore volume 1.05cm 3 Per gram, the average pore diameter is 6.5nm, and the BET specific surface area after phosphorus modification can reach 900m 2 Per gram, pore volume 1.15cm 3 The average pore diameter of the catalyst is 8.1nm, and the catalyst prepared by adopting the phosphorus modified SBA-15 molecular sieve has the functions of macromolecular sulfides such as dibenzothiophene, dimethyldibenzothiophene and the likeBetter hydrodesulfurization effect.
The catalyst of the invention adopts the titanium modified SBA-15 molecular sieve and/or the phosphorus modified SBA-15 molecular sieve as a carrier, and further utilizes the synergistic effect of the two molecular sieves by adding the modified SBA-15 molecular sieve, so that the hydrofining performance of the catalyst can be improved, and poor gasoline and diesel oil can be processed under milder process conditions, thereby achieving the effects of deep desulfurization, denitrification, olefin reduction and aromatic hydrocarbon reduction.
In one embodiment, the catalyst support of the present invention further comprises alumina, i.e., the catalyst support is composed of phosphorus-modified SBA-15 molecular sieves and/or titanium-modified SBA-15 molecular sieves, and alumina. In another embodiment, the active components are at least one group VIII metal oxide and at least one group VIB metal oxide. In yet another embodiment, the group VIB metal oxide is an oxide of molybdenum and/or tungsten, i.e., an oxide of molybdenum and/or an oxide of tungsten; the group VIII metal oxide is at least one of iron, nickel and cobalt, namely at least one of iron oxide, nickel oxide and cobalt oxide.
In one embodiment, the distillate hydrofining catalyst of the present invention further comprises a modifier oxide, wherein the modifier oxide is at least one oxide of silicon, phosphorus, fluorine, titanium, zirconium and gallium, i.e. the modifier oxide is at least one oxide of silicon oxide, phosphorus oxide, fluorine oxide, titanium oxide, zirconium oxide and gallium oxide. In another embodiment, the distillate hydrofining catalyst of the present invention further comprises a binder, an extrusion aid, etc., but the present invention is not particularly limited. In general, the modifier can jump the acidity of the catalyst, and facilitate the adsorption of macromolecular complex heteroatom compounds on the catalyst.
In one embodiment, the mass content of the phosphorus-modified SBA-15 molecular sieve in the catalyst is 0.5-40%, preferably 5-30% based on the total mass of the distillate hydrofining catalyst; the mass content of the titanium modified SBA-15 molecular sieve is 0.5% -40%, preferably 5% -30%. In another embodiment, the catalyst of the present invention further comprises alumina in an amount of 20% to 90%, preferably 30% to 80% by mass, based on the total mass of the distillate hydrofining catalyst of the present invention; the mass content of the modifier oxide is 0.5-5%, the mass content of the binder is 0-30%, and preferably 0-20%; the mass content of the extrusion aid is 0-10%, preferably 3-8%.
In one embodiment, the mass content of group VIB metal oxide in the catalyst of the present invention is from 10 to 30%, preferably from 15 to 25%, based on the total mass of the distillate hydrofining catalyst of the present invention; the mass content of the group VIII metal oxide is 1-10%, preferably 3-8%.
In one embodiment, the distillate oil hydrofining catalyst of the invention takes alumina, phosphorus modified SBA-15 molecular sieve and titanium modified SBA-15 molecular sieve as carriers, wherein the alumina is a main carrier component of the catalyst, and has good thermal stability and proper pore size distribution; two different molecular sieves are used as main acidic components of the catalyst, and the acidity is adjustable and the specific surface area of the carrier can be increased through proper modification treatment.
The specific surface area of the distillate hydrofining catalyst of the invention is 180m 2 /g～240m 2 And/g, wherein the pore volume is 0.30 ml/g-0.35 ml/g, and the pore distribution of pore diameters of 4 nm-10 nm accounts for 70% -90% of the total pore volume.
The invention also discloses a preparation method of the distillate oil hydrofining catalyst, which comprises the following steps:
step 1, extruding a phosphorus modified SBA-15 molecular sieve and/or a titanium modified SBA-15 molecular sieve to obtain a catalyst carrier;
step 2, preparing an impregnating solution comprising a compound of a VIB metal and/or a compound of a VIII metal, impregnating the catalyst carrier obtained in the step 1, drying and roasting to obtain the distillate hydrofining catalyst.
In one embodiment, the phosphorus-modified SBA-15 molecular sieve of the invention is prepared by: mixing SBA-15 molecular sieve with phosphorus-containing compound, ultrasonic treating, drying and roasting to obtain phosphorus-modified SBA-15 molecular sieve. The phosphorus-containing compound is, for example, phosphoric acid or a phosphate solution. In another embodiment, the phosphorus-modified SBA-15 molecular sieve of the invention is prepared by: adding phosphoric acid or phosphate solution into an ultrasonic reaction kettle, adding SBA-15 molecular sieve, and stirring uniformly; and (3) carrying out solid-liquid separation on the reaction product, and then washing, drying (the drying temperature is 100-120 ℃, the drying time is 4-8 h) and roasting (the roasting temperature is 500-600 ℃ and the roasting time is 4-6 h) to obtain the phosphorus modified SBA-15 molecular sieve.
In one embodiment, the preparation method of the titanium modified SBA-15 molecular sieve comprises the following steps: mixing SBA-15 molecular sieve with titanium compound, ultrasonic treating, drying and roasting to obtain titanium modified SBA-15 molecular sieve. The titanium-containing compound may be a titanate OR an inorganic titanium salt, such as Ti (OR) 4, tiCl3, C 10 H 10 Cl 2 Ti, etc., wherein R is, for example, a hydrocarbon group having 1 to 6 carbons, and further an alkyl group having 1 to 6 carbons. In another embodiment, the process for preparing the titanium modified SBA-15 molecular sieve of the present invention is: fully contacting titanium-containing compound with SBA-15 molecular sieve in organic solvent (such as toluene, cyclohexane, chloroform, etc.) in ultrasonic reactor, separating solid from liquid, washing, drying (drying temperature is 100-120 deg.C, drying time is 4-8), roasting (roasting temperature is 500-600 deg.C, roasting time is 4-6 h) to obtain the invented titanium-modified SBA-15 molecular sieve.
In one embodiment, the phosphorus-modified SBA-15 molecular sieve of the invention has the following properties: p (P) 2 O 5 /SiO 2 Molar ratio of 0.1 to 0.5, preferably 0.2 to 0.3, na 2 O weight content<0.2%, preferably<0.15%. Based on the total mass of the distillate hydrofining catalyst, the mass content of the phosphorus modified SBA-15 molecular sieve in the catalyst is 0.5-40%, preferably 5-30%.
In another embodiment, the titanium modified SBA-15 molecular sieve of the invention has the following properties: tiO (titanium dioxide) 2 /SiO 2 Molar ratio of 0.1 to 0.5, preferably 0.2 to 0.3, na 2 O weight content<0.2%, preferably<0.15%. Based on the total mass of the distillate hydrofining catalyst, the mass content of the titanium modified SBA-15 molecular sieve is 0.5 to 40 percent, preferably 5 percent～30％。
In one embodiment, step 1 is further adding alumina; the alumina may be a commercially available pseudo-boehmite, or a commercially available alumina support having a pore distribution. The total mass of the distillate oil hydrofining catalyst is taken as a reference, and the mass content of the alumina is 20-90%, preferably 30-80%.
In another embodiment, the modifier compound is further added in step 1 or step 2, and the modifier compound may be at least one of a silicon-containing compound, a phosphorus-containing compound, a fluorine-containing compound, a titanium-containing compound, a zirconium-containing compound, and a gallium-containing compound. The mass content of the modifier oxide is 0.5-5% based on the total mass of the distillate oil hydrofining catalyst.
In one embodiment, in step 1, a binder is further added, which may be one or more of refractory inorganic oxides, such as clay, silica, alumina, silica-alumina, zirconia, and titania, and the weight content of the binder in the final catalyst is 0-40%. The catalyst carrier of the invention can be directly added with silica sol without adding binder during preparation, and is molded by kneading and extruding strips.
In one embodiment, in the step 1 of the present invention, an extrusion aid is further added, and the extrusion aid may be one or more of sesbania powder, citric acid, oxalic acid, cellulose, starch and a high molecular surfactant, preferably sesbania powder and citric acid. The mass content of the extrusion aid is 0-10%, preferably 3-8% based on the total mass of the distillate hydrofining catalyst.
In one embodiment, the group VIB metals used in the distillate hydrofinishing catalyst of the present invention are most commonly Mo and/or W, and the group VIII metals are most commonly one or more of Fe, ni and Co. The group VIB metal compound may be a soluble salt of a group VIB metal, such as an ammonium salt of molybdenum or an ammonium salt of tungsten, and the group VIII metal compound may be a soluble salt of a group VIII metal, such as iron, cobalt, nickel nitrate, carbonate or acetate, i.e., iron nitrate, carbonate or acetate, cobalt nitrate, carbonate or acetate, or nickel nitrate, carbonate or acetate.
In one embodiment, the mass content of group VIB metal oxide in the catalyst of the present invention is from 10 to 30%, preferably from 15 to 25%, based on the total mass of the distillate hydrofining catalyst of the present invention; the mass content of the group VIII metal oxide is 1-10%, preferably 3-8%.
In one embodiment, the preparation steps of the distillate hydrofining catalyst of the present invention specifically comprise:
(1) Mixing the phosphorus modified SBA-15 molecular sieve, the titanium modified SBA-15 molecular sieve and alumina uniformly according to a certain proportion;
(2) Adding a binder or directly adding a peptizing agent solution into the step (1), kneading into paste, extruding strips and forming;
(3) Drying the molded product in the step (2) at 100-150 ℃ for 1-12 h, and roasting at 450-650 ℃ for 1-12 h to obtain a catalyst carrier;
(4) Preparing an impregnating solution containing a group VIB metal compound and/or a group VIII metal compound;
(5) And (3) impregnating the catalyst carrier obtained in the step (3) with the impregnating solution prepared in the step (4), drying at 100-150 ℃ for 1-12 h, and roasting at 450-650 ℃ for 1-12 h to obtain a catalyst finished product.
Wherein, the drying temperature in the steps (3) and (5) is preferably 100-120 ℃, and the drying time is preferably 4-8 h; the roasting temperature in the steps (3) and (5) is preferably 500-600 ℃, and the roasting time is preferably 4-8 h.
Wherein, the impregnation can be excessive impregnation or equal volume impregnation; the catalyst carrier is impregnated with the active components by preparing the active components into impregnating solutions respectively, and the catalyst carrier is impregnated with the active components by preparing the active components into an impregnating solution simultaneously.
The catalyst of the present invention may be in the form of a sheet, sphere, cylinder or profiled bar (clover ), preferably cylinder or profiled bar (clover ). The diameter of the catalyst may be 0.8mm to 2.0mm thin strips or >2.5mm thick strips, preferably 1.0mm to 1.8mm thin strips.
The invention provides a distillate oil hydrofining catalyst, which is characterized in that a phosphorus modified SBA-15 molecular sieve and/or a titanium modified SBA-15 molecular sieve are added into a catalyst carrier, so that the hydrodesulfurization rate and the hydrodenitrogenation rate of the catalyst are obviously improved, the contents of sulfur, nitrogen and aromatic hydrocarbon can be effectively reduced under the milder hydrofining condition, and the cetane number of a product is greatly improved.
The catalyst of the invention can react at 240-400 ℃ and with hydrogen partial pressure of 2.0-10.0 MPa and liquid hourly space velocity of 0.1h -1 ～3.5h -1 Hydrogen oil volume ratio 200-1000: 1, processing inferior gasoline, wherein the sulfur content can be reduced to below 50 mug/g, the nitrogen content is reduced to below 50 mug/g, the olefin content is reduced to below 30v%, and the octane number loss of the product is less than 3 units; the sulfur content of the processed inferior diesel oil can be reduced to below 50 mug/g, the nitrogen content is reduced to below 350 mug/g, the aromatic hydrocarbon content is reduced to below 30v%, the cetane number of the product is increased by more than 3 units, and the diesel oil yield is more than 98.0%.
The distillate hydrotreating catalyst of the present invention will be further described by way of examples, but the present invention is not limited thereto.
Example 1
The preparation of the distillate oil hydrofining catalyst CAT-1 comprises the following steps:
200g of pseudo-boehmite produced by Shanxi aluminum industry Co., ltd, 25g of P-SBA-15 molecular sieve with phosphorus loading of 6wt%, 15g of Ti-SBA-15 molecular sieve with titanium loading of 4wt% and 10g of sesbania powder are taken, evenly mixed, mixed solution composed of 15g of nitric acid, 10g of citric acid and 200g of deionized water is dripped for kneading, extruded into clover shape with the size of 1.5mm, dried for 2h at the temperature of 110 ℃, and then baked for 4h at the temperature of 550 ℃ to prepare the carrier. Then dipping with dipping liquid prepared by nickel nitrate and ammonium metatungstate, drying for 4 hours at 120 ℃, and roasting for 4 hours at 550 ℃ to prepare the catalyst CAT-1.
Example 2
The preparation of the distillate oil hydrofining catalyst CAT-2 comprises the following steps:
200g of pseudo-boehmite produced by Shanxi aluminum industry Co., ltd, 25g of P-SBA-15 molecular sieve with phosphorus loading of 6wt%, 15g of Ti-SBA-15 molecular sieve with titanium loading of 4wt% and 10g of sesbania powder are taken, evenly mixed, mixed solution composed of 15g of nitric acid, 10g of citric acid, 20g of silica sol and 200g of deionized water is dripped, kneaded, extruded into strips of clover with the size of 1.5mm, dried for 2h at the temperature of 110 ℃, and then baked for 4h at the temperature of 550 ℃ to prepare the carrier. Impregnating with an impregnating solution prepared from ammonium fluoride, drying at 120 ℃ for 4h, roasting at 350 ℃ for 4h, impregnating with an impregnating solution prepared from nickel nitrate and ammonium metatungstate, drying at 120 ℃ for 4h, and roasting at 550 ℃ for 4h to obtain the catalyst CAT-2.
Example 3
The preparation of the distillate oil hydrofining catalyst CAT-3 comprises the following steps:
200g of pseudo-boehmite produced by Shanxi aluminum industry Co., ltd, 40g of P-SBA-15 molecular sieve with a phosphorus load of 6wt% and 10g of sesbania powder are taken and uniformly mixed, a mixed solution consisting of 15g of nitric acid, 10g of citric acid and 200g of deionized water is dripped into the mixture to be kneaded, extruded into strips to form clover with the size of 1.5mm, the clover is dried for 2 hours at the temperature of 110 ℃, and then the clover is baked for 4 hours at the temperature of 550 ℃ to prepare the carrier. Then dipping with dipping liquid prepared by nickel nitrate and ammonium metatungstate, drying for 4 hours at 120 ℃, and roasting for 4 hours at 550 ℃ to prepare the catalyst CAT-3.
Example 4
The preparation of the distillate oil hydrofining catalyst CAT-4 comprises the following steps:
200g of pseudo-boehmite produced by Shanxi aluminum industry Co., ltd, 40g of Ti-SBA-15 molecular sieve with titanium load of 4wt% and 10g of sesbania powder are taken and uniformly mixed, mixed solution consisting of 15g of nitric acid, 10g of citric acid and 200g of deionized water is dripped into the mixture for kneading, the mixture is extruded into strips to form clover with the size of 1.5mm, the clover is dried for 2 hours at the temperature of 110 ℃, and then the mixture is baked for 4 hours at the temperature of 550 ℃ to prepare the carrier. Then dipping with dipping liquid prepared by nickel nitrate and ammonium metatungstate, drying for 4 hours at 120 ℃, and roasting for 4 hours at 550 ℃ to prepare the catalyst CAT-4.
Example 5
The preparation of the distillate oil hydrofining catalyst CAT-5 comprises the following steps:
200g of pseudo-boehmite produced by Shanxi aluminum industry Co., ltd, 25g of P-SBA-15 molecular sieve with phosphorus loading of 6wt%, 15g of Ti-SBA-15 molecular sieve with titanium loading of 4wt% and 10g of sesbania powder are taken, evenly mixed, mixed solution composed of 15g of nitric acid, 10g of citric acid and 200g of deionized water is dripped for kneading, extruded into clover shape with the size of 1.5mm, dried for 2h at the temperature of 110 ℃, and then baked for 4h at the temperature of 550 ℃ to prepare the carrier. Then impregnating with impregnating solution prepared from basic nickel carbonate and ammonium molybdate, drying at 120 ℃ for 4 hours, and roasting at 550 ℃ for 4 hours to obtain the catalyst CAT-5.
Example 6
The preparation of the distillate oil hydrofining catalyst CAT-6 comprises the following steps:
200g of pseudo-boehmite produced by Shanxi aluminum industry Co., ltd, 25g of P-SBA-15 molecular sieve with phosphorus loading of 6wt%, 25g of Ti-SBA-15 molecular sieve with titanium loading of 4wt% and 10g of sesbania powder are taken, evenly mixed, mixed solution composed of 15g of nitric acid, 10g of citric acid and 200g of deionized water is dripped for kneading, extruded into clover shape with the thickness of 1.5mm, dried for 2h at the temperature of 110 ℃, and then baked for 4h at the temperature of 550 ℃ to prepare the carrier. Then dipping with dipping liquid prepared by nickel nitrate and ammonium metatungstate, drying for 4 hours at 120 ℃, and roasting for 4 hours at 550 ℃ to prepare the catalyst CAT-6.
Example 7
The preparation of the distillate oil hydrofining catalyst CAT-7 comprises the following steps:
200g of pseudo-boehmite produced by Shanxi aluminum industry Co., ltd, 15g of P-SBA-15 molecular sieve with phosphorus loading of 6wt%, 15g of Ti-SBA-15 molecular sieve with titanium loading of 4wt% and 10g of sesbania powder are taken, evenly mixed, mixed solution composed of 15g of nitric acid, 10g of citric acid and 200g of deionized water is dripped for kneading, extruded into clover shape with the thickness of 1.5mm, dried for 2h at the temperature of 110 ℃, and then baked for 4h at the temperature of 550 ℃ to prepare the carrier. Then dipping with dipping liquid prepared by nickel nitrate and ammonium metatungstate, drying for 4 hours at 120 ℃, roasting for 4 hours at 550 ℃, and obtaining the catalyst CAT-7.
Example 8
The preparation of the distillate oil hydrofining catalyst CAT-8 comprises the following steps:
taking 200g of pseudo-boehmite produced by Shanxi aluminum industry Co., ltd, adding 10g of sesbania powder, uniformly mixing, dropwise adding a mixed solution consisting of 10g of nitric acid, 10g of citric acid and 200g of deionized water, kneading, extruding into strips to form clover with the thickness of 1.5mm, drying at 110 ℃ for 2h, and roasting at 550 ℃ for 4h to prepare the carrier. Then dipping with dipping liquid prepared by nickel nitrate and ammonium metatungstate, drying for 4 hours at 120 ℃, and roasting for 4 hours at 550 ℃ to prepare the catalyst CAT-8.
Comparative example 1
The industrial diesel oil hydrogenating refined agent CAT-A has carrier of titanium modified alumina with titanium load of 3-5wt% and hydrogenating active metal of tungsten, nickel and fluorine.
TABLE 1 catalyst composition
Example 9
This example describes the results of the micro-reverse evaluation of the above-described catalysts.
The catalyst used for the micro-reaction evaluation was 1.5g, and a decane solution containing dibenzothiophene (1000. Mu.g/g in terms of sulfur) and a decane solution containing indole (500. Mu.g/g in terms of nitrogen) were used as evaluation materials, respectively, and hydrodesulfurization and hydrodenitrogenation performance comparative tests were conducted under the reaction conditions shown in Table 2, and the micro-reaction hydrogenation evaluation results of the catalyst were shown in Table 3.
TABLE 2 micro-inverse hydrogenation evaluation conditions
TABLE 3 micro-inverse hydrogenation evaluation results
As shown in Table 3, the activity of hydrodesulphurisation and hydrodenitrogenation of the catalysts CAT-1 to CAT-7 added with the molecular sieve is greatly improved compared with that of the catalyst CAT-8 without the molecular sieve; and after the phosphorus modified SBA-15 molecular sieve and the titanium modified SBA-15 molecular sieve are added at the same time, the hydrodesulfurization and hydrodenitrogenation performances of the catalysts CAT-1, CAT-6 and CAT-7 are further improved compared with the catalyst CAT-3 of the single phosphorus modified SBA-15 molecular sieve and the catalyst CAT-4 of the single titanium modified SBA-15 molecular sieve; the introduction of the auxiliary agent fluorine slightly reduces the hydrodesulfurization and denitrification performance of the catalyst CAT-2. The catalyst CAT-1, CAT-6 and CAT-7 using tungsten and nickel as active metals has higher hydrodesulfurization and hydrodenitrogenation performance than the catalyst CAT-5 using molybdenum and nickel as active metals. In addition, the hydrogenation performance of the hydrofining catalyst with the modified SBA-15 molecular sieve is superior to that of the industrial hydrogenation catalyst CAT-A prepared by the traditional process.
Example 10
In the embodiment, a 100ml hydrogenation evaluation device is adopted, catalytic diesel oil with higher sulfur and nitrogen content and mixed diesel oil (weight ratio of 1:1) of catalytic diesel oil and coked diesel oil are respectively used as raw materials, the catalysts CAT-1 and CAT-A are subjected to single-stage single-agent hydrogenation performance evaluation, the reaction conditions are shown in Table 4, and the hydrogenation evaluation results are shown in Table 5.
Table 4 evaluation conditions of 100ml hydrogenation evaluation apparatus
Table 5 hydrogenation evaluation results of catalyst in 100ml hydrogenation evaluation apparatus
Example 11
In the embodiment, a 100ml hydrogenation evaluation device is adopted, catalytic gasoline with higher sulfur and nitrogen content and straight-run naphtha mixed oil (weight ratio of 6:4) are used as raw materials, single-stage single-agent hydrogenation performance evaluation is carried out on catalysts CAT-1 and CAT-A, reaction conditions are shown in Table 6, and hydrogenation evaluation results are shown in Table 7.
Table 6 evaluation conditions in 100ml hydrogenation evaluation apparatus
Table 7 evaluation results of catalysts in a 100ml hydrogenation evaluation apparatus
Example 12
In the embodiment, a 100ml hydrogenation evaluation device is adopted, canadian oil sand asphalt with higher sulfur and nitrogen content is used as a raw material, single-stage single-agent hydrogenation performance evaluation is carried out on the catalysts CAT-1 and CAT-A, the reaction conditions are shown in Table 8, and the hydrogenation evaluation results are shown in Table 9.
Table 8 evaluation conditions in 100ml hydrogenation evaluation apparatus
Table 9 evaluation results of catalysts in a 100ml hydrogenation evaluation apparatus
As shown by the evaluation results, the distillate oil hydrofining catalyst can process inferior gasoline and the like under a milder process condition, achieves the effects of deep desulfurization, denitrification, olefin and aromatic hydrocarbon reduction, and can also greatly improve the cetane number of diesel.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A distillate hydrofining catalyst, which is characterized by comprising a catalyst carrier and an active component, wherein the catalyst carrier comprises a phosphorus modified SBA-15 molecular sieve and/or a titanium modified SBA-15 molecular sieve, and the active component comprises a VIB group metal oxide and/or a VIII group metal oxide.
2. The distillate hydrofining catalyst according to claim 1, wherein the mass content of the phosphorus-modified SBA-15 molecular sieve is 5% to 40% and the mass content of the titanium-modified SBA-15 molecular sieve is 5% to 40% based on the total mass of the distillate hydrofining catalyst; p in the phosphorus-modified SBA-15 molecular sieve 2 O 5 /SiO 2 The molar ratio is 0.1-0.5; in the titanium modified SBA-15 molecular sieve, tiO 2 /SiO 2 The molar ratio is 0.1-0.5.
3. The distillate hydrofining catalyst according to claim 2, wherein the catalyst carrier further comprises alumina, the distillate hydrofining catalyst further comprises a modifier oxide, the modifier oxide is at least one of silicon, phosphorus, fluorine, titanium, zirconium and gallium oxide, and the mass content of the modifier oxide is 0.5-5% based on the total mass of the distillate hydrofining catalyst.
4. The distillate oil hydrofining catalyst according to claim 1, wherein the group vib metal oxide is an oxide of molybdenum and/or an oxide of tungsten, and the group viii metal oxide is at least one of oxides of iron, nickel, and cobalt; the mass content of the VIB group metal oxide is 15-30% and the mass content of the VIII group metal oxide is 2-10 w% based on the total mass of the distillate oil hydrofining catalyst.
5. The preparation method of the distillate oil hydrofining catalyst is characterized by comprising the following steps:
step 1, extruding a phosphorus modified SBA-15 molecular sieve and/or a titanium modified SBA-15 molecular sieve to obtain a catalyst carrier;
step 2, preparing an impregnating solution comprising a compound of a VIB metal and/or a compound of a VIII metal, impregnating the catalyst carrier obtained in the step 1, drying and roasting to obtain the distillate hydrofining catalyst.
6. The method for preparing a distillate oil hydrofining catalyst according to claim 5, wherein the step 1 is further added with alumina, and the step 1 or the step 2 is further added with a modifier compound, wherein the modifier compound is at least one of a silicon-containing compound, a phosphorus-containing compound, a fluorine-containing compound, a titanium-containing compound, a zirconium-containing compound and a gallium-containing compound; the compound of the VIB metal is molybdenum ammonium salt and/or tungsten ammonium salt, and the compound of the VIII metal is at least one of nitrate, carbonate or acetate of iron, cobalt and nickel.
7. The method for producing a distillate oil hydrofining catalyst according to claim 5, wherein the mass content of the phosphorus-modified SBA-15 molecular sieve is 5% to 40%, the mass content of the titanium-modified SBA-15 molecular sieve is 5% to 40%, the mass content of the group vi B metal compound is 15% to 30% in terms of oxide, and the mass content of the group viii metal compound is 2% to 10% in terms of oxide, based on the total mass of the distillate oil hydrofining catalyst.
8. The method for preparing a distillate hydrofining catalyst according to claim 5, wherein the impregnation in the step 2 is single component impregnation or two component impregnation, and the impregnation mode is excessive impregnation or equal volume impregnation.
9. The method for preparing the distillate oil hydrofining catalyst according to claim 5, wherein the phosphorus-modified SBA-15 molecular sieve is prepared by the following steps: mixing SBA-15 molecular sieve with phosphorus-containing compound, ultrasonic treating, drying and roasting to obtain phosphorus-modified SBA-15 molecular sieve; the preparation method of the titanium modified SBA-15 molecular sieve comprises the following steps: mixing SBA-15 molecular sieve with titanium compound, ultrasonic treating, drying and roasting to obtain titanium modified SBA-15 molecular sieve.
10. Use of the distillate hydrofining catalyst according to any one of claims 1-4 in distillate hydrogenation.
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