CN114425352B - Halogen-containing heavy oil hydrogenation catalyst, preparation method thereof and heavy oil hydrotreating method - Google Patents
Halogen-containing heavy oil hydrogenation catalyst, preparation method thereof and heavy oil hydrotreating method Download PDFInfo
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- CN114425352B CN114425352B CN202011185330.4A CN202011185330A CN114425352B CN 114425352 B CN114425352 B CN 114425352B CN 202011185330 A CN202011185330 A CN 202011185330A CN 114425352 B CN114425352 B CN 114425352B
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- Prior art keywords
- phosphorus
- carrier
- heavy oil
- alumina
- containing compound
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 79
- 239000000295 fuel oil Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 63
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 55
- 150000002367 halogens Chemical class 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 128
- 239000011148 porous material Substances 0.000 claims abstract description 111
- 229910052751 metal Inorganic materials 0.000 claims abstract description 92
- 239000002184 metal Substances 0.000 claims abstract description 92
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 90
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000011574 phosphorus Substances 0.000 claims abstract description 88
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 24
- 238000009826 distribution Methods 0.000 claims abstract description 17
- 230000002902 bimodal effect Effects 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims description 105
- 238000006243 chemical reaction Methods 0.000 claims description 83
- 239000000243 solution Substances 0.000 claims description 70
- 239000012752 auxiliary agent Substances 0.000 claims description 42
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- 239000002002 slurry Substances 0.000 claims description 27
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 25
- 239000011777 magnesium Substances 0.000 claims description 25
- 229910052749 magnesium Inorganic materials 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- 230000032683 aging Effects 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- -1 VIB metals Chemical class 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 235000011007 phosphoric acid Nutrition 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052755 nonmetal Inorganic materials 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000004645 aluminates Chemical class 0.000 claims description 6
- 229910052789 astatine Inorganic materials 0.000 claims description 6
- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine atom Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 5
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052730 francium Inorganic materials 0.000 claims description 4
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 4
- 239000000203 mixture Substances 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 27
- 239000012065 filter cake Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 20
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 19
- 238000002459 porosimetry Methods 0.000 description 17
- 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 16
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 12
- 239000001099 ammonium carbonate Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 5
- 235000012501 ammonium carbonate Nutrition 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000003518 caustics Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 4
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920001289 polyvinyl ether Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 239000002283 diesel fuel Substances 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 150000007522 mineralic acids Chemical group 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 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
- 238000005096 rolling process Methods 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 235000005765 wild carrot Nutrition 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01J35/615—
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- B01J35/638—
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of heavy oil hydrogenation, and discloses a halogen-containing heavy oil hydrogenation catalyst, a preparation method thereof and a heavy oil hydrogenation treatment method. The catalyst comprises an alumina carrier with a bimodal pore structure and hydrogenation active metal loaded on the carrier, wherein the carrier contains phosphorus and halogen elements, and the weight of the carrier is taken as reference, and the catalyst is prepared by the following steps of 2 O 5 The phosphorus content is 0.1-8.0 wt% and the halogen content is 0.1-6 wt% calculated as element; characterized by mercury intrusion, the first pores of the carrier are distributed as mesopores positioned at 3-100nm, and the pore volume V Middle hole 1.0-1.5mL/g, the second pore distribution is macropores at 100-5000nm, pore volume V Macropores are formed 1.0-1.8mL/g, total pore volume V Total (S) 2.0-3.3mL/g. The catalyst is used in the heavy oil hydrotreating process and has better hydrotreating performance.
Description
Technical Field
The invention relates to the field of heavy oil hydrogenation, in particular to a halogen-containing heavy oil hydrogenation catalyst, a preparation method thereof and a heavy oil hydrogenation treatment method.
Background
Alumina, particularly gamma-alumina, is often used as a support for catalyst preparation due to its relatively good pore structure, specific surface area and heat stability. Especially the pore structure of the alumina carrier is critical to the performance of the catalyst. The raw material of the alumina carrier is generally pseudo-boehmite, various different methods for preparing the phosphorus-containing pseudo-boehmite are disclosed in the prior art, the properties of the pseudo-boehmite and the alumina described in the prior art are excellent in some aspects in terms of controlling the pore distribution and pore volume of the alumina by different methods, but the phosphorus-containing alumina which has double-peak pores and has larger pore volume and total pore volume on two pore distributions is difficult to obtain.
At present, along with the aggravation of the heavy and inferior trend of crude oil, the processing difficulty of crude oil is increased, and higher requirements are put on a crude oil processing catalyst, and when the existing prepared alumina is used as a catalyst carrier, the performance of the catalyst needs to be further improved.
Disclosure of Invention
The invention aims to overcome the defect that the catalyst performance needs to be further improved in the heavy oil hydrotreating process in the prior art, and provides a halogen-containing heavy oil hydrotreating catalyst, a preparation method thereof and a heavy oil hydrotreating method. The catalyst is used in the heavy oil hydrotreating process and has better hydrotreating performance.
The first aspect of the invention provides a halogen-containing heavy oil hydrogenation catalyst, which comprises an alumina carrier with a bimodal pore structure and hydrogenation active metal loaded on the carrier, wherein the carrier contains phosphorus and halogen elements, the halogen elements are one or more selected from fluorine, chlorine, bromine, iodine and astatine, and the weight of the carrier is taken as the reference, and the reference is P 2 O 5 The phosphorus content is 0.1-8.0 wt% and the halogen content is 0.1-6 wt% calculated as element; the hydrogenation active metal is at least one metal selected from the group consisting of VIB metals and optionally at least one metal selected from the group consisting of VIII metals, and the hydrogenation active metal content is 0.3-20 wt% based on the total catalyst and calculated on oxide; characterized by mercury intrusion, the first pores of the carrier are distributed as mesopores positioned at 3-100nm, and the pore volume V Middle hole 1.0-1.5mL/g, the second pore distribution is macropores at 100-5000nm, pore volume V Macropores are formed 1.0-1.8mL/g, total pore volume V Total (S) 2.0-3.3mL/g.
Preferably, the phosphorus-containing alumina carrier contains a magnesium promoter and optionally other promoters.
The second aspect of the present invention provides a method for preparing a heavy oil hydrogenation catalyst containing halogen, comprising the steps of preparing an alumina carrier having a bimodal pore structure and introducing a hydrogenation active metal into the carrier, wherein the hydrogenation active metal is one or more selected from a group VIII metal and a group VIB metal, and the hydrogenation active metal is used in an amount such that the hydrogenation active metal content in terms of oxide in the final catalyst is 0.3-20 wt%; wherein, the steps for preparing the alumina carrier are as follows:
(1) The gelling reaction is carried out in the presence of an aluminum-containing compound and a phosphorus-containing compound to obtain a slurry containing hydrated alumina containing phosphorus, the phosphorus-containing compound enables P to be contained in the finally obtained carrier 2 O 5 The phosphorus content is 0.1-8.0 wt%;
(2) Regulating the pH value of the slurry containing the phosphorus-containing hydrated alumina obtained in the step (1) to 7-10.5, aging, filtering, washing and drying to obtain phosphorus-containing pseudo-boehmite;
(3) Shaping, drying and roasting the phosphorus-containing pseudo-boehmite obtained in the step (2) and a halogen-containing compound to obtain the alumina carrier, wherein the halogen element is one or more selected from fluorine, chlorine, bromine, iodine and astatine, and the halogen-containing compound is used in an amount such that the halogen content in the finally obtained carrier is 0.1-6 wt% in terms of elements;
the gel forming reaction in the step (1) is carried out under the condition of pH value of 4-7.
A third aspect of the present invention provides a heavy oil hydrogenation catalyst prepared by the method of the second aspect described above.
The fourth aspect of the invention provides a heavy oil hydroprocessing method comprising contacting a heavy oil feedstock with a heavy oil hydroprocessing catalyst under heavy oil hydroprocessing conditions, wherein the heavy oil hydroprocessing catalyst is a heavy oil hydroprocessing catalyst according to the first or third aspect of the invention.
Compared with the prior art, the method provided by the invention can slow down the generation and growth of pseudo-boehmite seed crystal due to the addition of inorganic hetero element halogen element in the preparation process of the carrier, thereby obtaining the alumina with a bimodal pore structure and higher total pore volume V Total (S) . The catalyst prepared by the carrier is applied to the heavy oil hydrogenation reaction process, and has good hydrodemetallization activity and deasphalting activity.
Detailed Description
The first aspect of the invention provides a halogen-containing heavy oil hydrogenation catalyst, which comprises an alumina carrier with a bimodal pore structure and hydrogenation active metal loaded on the carrier, wherein the carrier contains phosphorus and halogen elements, the halogen elements are one or more selected from fluorine, chlorine, bromine, iodine and astatine, and the weight of the carrier is taken as the reference, and the reference is P 2 O 5 The phosphorus content is 0.1-8.0 wt% and the halogen content is 0.1-6 wt% calculated as element; the hydrogenation active metal is at least one metal selected from the group consisting of VIB metals and optionally at least one metal selected from the group consisting of VIII metals, and the hydrogenation active metal content is 0.3-20 wt% based on the total catalyst and calculated on oxide; characterized by mercury intrusion, the first pores of the carrier are distributed as mesopores positioned at 3-100nm, and the pore volume V Middle hole 1.0-1.5mL/g, the second pore distribution is macropores at 100-5000nm, pore volume V Macropores are formed 1.0-1.8mL/g, total pore volume V Total (S) 2.0-3.3mL/g.
Pore volumes of the phosphorus-containing alumina of the present invention in different pore size ranges are determined by mercury porosimetry. The sample was first calcined at 600℃for 4 hours (same applies below) before measurement.
According to the present invention, preferably, the support is prepared from a phosphorus-containing pseudo-boehmite, the phosphorus-containing pseudo-boehmite having a bimodal pore structure as characterized by mercury intrusion, and the phosphorus-containing alumina having a pore distribution of pore volume V of 3 to 100nm 1 1.0-2.0mL/g, preferably 1.2-1.8mL/g, pore distribution at a pore volume V of 100-5000nm 2 2.0-5.0mL/g, preferably 2.1-3.5mL/g, and a total pore volume V of 3.0-7.0mL/g, preferably 3.3-5.3mL/g; the roasting conditions include: the temperature is 350-950 ℃ and the time is 2-8 hours.
The invention has wider selection range of the type of the VIB group active metal, and can be any VIB group active metal which is conventionally used in the field and can exert the hydrogenation performance of heavy oil, and preferably, the VIB group active metal is molybdenum and/or tungsten.
The invention has wide selection range of the type of the VIII group active metal, and can be any VIII group active metal which can exert the hydrogenation performance of heavy oil and is conventionally used in the field, and preferably, the VIII group active metal is cobalt and/or nickel.
Preferably, according to the present invention, the hydrogenation active metal is at least one group VIII metal selected from nickel or cobalt and at least one group VIB metal selected from molybdenum or tungsten.
Preferably, the group VIB metal content is 0.2 to 10 wt.% and the group VIII metal content is 0.2 to 5 wt.% based on the total catalyst and calculated as oxides.
According to the invention, the halogen content in elemental form in the support is preferably 0.3 to 4% by weight, more preferably 0.5 to 2.5% by weight.
According to the present invention, preferably, the halogen element is at least one selected from fluorine, chlorine and bromine, and further preferably fluorine.
According to a preferred embodiment of the invention, the phosphorus-containing alumina carrier contains magnesium promoter and optionally other promoters. The adoption of the preferred embodiment is more beneficial to improving the performance of the heavy oil hydrogenation catalyst.
According to the invention, it is preferred that the catalyst contains 0.1 to 5.0% by weight of P, calculated as oxide, based on the total amount of the alumina carrier 2 O 5 0.1 to 5.0% by weight of MgO.
The invention has a wide selection of the type and content of the further auxiliary agent, preferably the further auxiliary agent comprises a metallic auxiliary agent and/or a non-metallic auxiliary agent, the further auxiliary agent being present in an amount of 0 to 10.0 wt.%, more preferably 0.5 to 4.8 wt.%, calculated as oxide.
According to a more preferred embodiment of the present invention, the metal promoter is selected from at least one of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, calcium, zirconium and titanium elements, and the non-metal promoter element is selected from at least one of boron element and silicon element.
According to the present invention, preferably, the other auxiliary agent is selected from at least one of titanium, boron element and silicon element.
The catalyst provided by the invention adopts phosphorus-containing alumina with a bimodal pore structure, and halogen elements are added into the carrier, so that the catalyst has specific pore distribution and high pore volume characteristics, and particularly when the catalyst contains a magnesium auxiliary agent, the high pore volume characteristics of the alumina are more obvious, and the catalyst taking the alumina as the carrier also shows more excellent heavy oil hydrogenation performance.
The second aspect of the present invention provides a method for preparing a heavy oil hydrogenation catalyst containing halogen, comprising the steps of preparing an alumina carrier having a bimodal pore structure and introducing a hydrogenation active metal into the carrier, wherein the hydrogenation active metal is one or more selected from a group VIII metal and a group VIB metal, and the hydrogenation active metal is used in an amount such that the hydrogenation active metal content in terms of oxide in the final catalyst is 0.3-20 wt%; wherein, the steps for preparing the alumina carrier are as follows:
(1) The gelling reaction is carried out in the presence of an aluminum-containing compound and a phosphorus-containing compound to obtain a slurry containing hydrated alumina containing phosphorus, the phosphorus-containing compound enables P to be contained in the finally obtained carrier 2 O 5 The phosphorus content is 0.1-8.0 wt%;
(2) Regulating the pH value of the slurry containing the phosphorus-containing hydrated alumina obtained in the step (1) to 7-10.5, aging, filtering, washing and drying to obtain phosphorus-containing pseudo-boehmite;
(3) Shaping, drying and roasting the phosphorus-containing pseudo-boehmite obtained in the step (2) and a halogen-containing compound to obtain the alumina carrier, wherein the halogen element is one or more selected from fluorine, chlorine, bromine, iodine and astatine, and the halogen-containing compound is used in an amount such that the halogen content in the finally obtained carrier is 0.1-6 wt% in terms of elements;
the gel forming reaction in the step (1) is carried out under the condition of pH value of 4-7.
According to a preferred embodiment of the invention, the reactants in step (1) further comprise a magnesium-containing compound and optionally further auxiliary-containing compounds. By "optional further auxiliary-containing compounds" it is meant that the further auxiliary-containing compounds may or may not be added to the reactants of step (1). More preferably, the reactants in step (1) also include a magnesium-containing compound and other auxiliary-containing compounds.
The inventors of the present invention found during the course of the study that when the phosphorus-containing compound and the magnesium-containing compound auxiliary agent and optionally other auxiliary agent compounds are used simultaneously, the adjustment of grain growth is more advantageous, so that a bimodal pore structure is formed, and both pore positions have high pore volume characteristics.
The kind of the magnesium-containing compound is not particularly limited, and preferably, the magnesium-containing compound is one or more of magnesium sulfate, magnesium nitrate and magnesium chloride. Preferably, the phosphorus-containing compound and optionally the magnesium-containing compound are added during the gelling reaction. The above auxiliary agents are added during the gelling reaction, so that the aging reaction carried out later is carried out in the presence of the auxiliary agents as well. Preferably, no phosphorus-containing compounds and no magnesium-containing compounds and optionally further auxiliary compounds are added during the aging process.
The type of the other auxiliary compound is not particularly limited, and may be a water-soluble compound corresponding to the other auxiliary, and a person skilled in the art may select an appropriate type of the other auxiliary compound according to circumstances.
To further improve the alumina pore distribution and increase the pore volume, other metal and/or non-metal promoters may be added, preferably the reactants in step (1) further comprise a magnesium-containing compound and other promoter-containing compounds, the other promoters being selected from one or more of titanium, silicon, boron. When the metal auxiliary agent is titanium element, the titanium-containing compound can be potassium titanate; when the nonmetallic auxiliary agent element silicon element is sodium silicate and/or potassium silicate; when the nonmetallic auxiliary agent element is boron element, the boron-containing compound is selected from one or more of sodium borate, potassium borate and boric acid.
According to the present invention, the phosphorus-containing compound, the magnesium-containing compound and the other auxiliary agent may be used in amounts such that the finally produced phosphorus-containing alumina carrier has a different phosphorus content, magnesium content and other auxiliary agent-containing compound content, preferably in amounts such that the finally produced alumina carrier contains 0.1 to 5.0 wt% of P in terms of oxide 2 O 5 0.1-5.0% by weight of MgO, 0-10.0% by weight of other auxiliary agents.
According to the method provided by the invention, preferably, the other auxiliary agent comprises a metal auxiliary agent and/or a nonmetal auxiliary agent, and the content of the other auxiliary agent calculated as oxide is 0-10.0 wt%. More preferably, the metal promoter is selected from at least one of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, calcium, zirconium, and titanium; the nonmetallic auxiliary agent element is selected from at least one of boron element and silicon element.
In the preparation method provided by the invention, the gel forming reaction is carried out in the presence of a phosphorus-containing compound under the condition that the pH value is 4-7, so that the precipitation of phosphorus-containing hydrated alumina can be met, the lower pH value condition is maintained, the growth of pseudo-boehmite crystal grains under high pH value is prevented from being too fast, and the common regulation effect of phosphorus and an auxiliary agent on the growth of pseudo-boehmite can be enhanced under the preferable condition. The grain growth of pseudo-boehmite in the whole process of hydrated alumina generation and aging is carried out in the co-existence of a phosphorus-containing compound and an auxiliary agent (preferably), so that the prepared pseudo-boehmite has a special crystal structure, is particularly suitable for obtaining the alumina with specific pore distribution and large pore volume, is used in heavy oil hydrogenation catalysts, and is particularly beneficial to improving the heavy oil hydrogenation performance of the catalysts.
According to the preparation method provided by the invention, the adding mode of the phosphorus-containing compound is wide in selection range, the phosphorus-containing compound (or the phosphorus-containing compound aqueous solution) can be added independently, or the phosphorus-containing compound (or the phosphorus-containing compound aqueous solution) and one or more raw materials thereof can be mixed in advance, and then the raw materials containing the phosphorus-containing compound are reacted, so long as the gelling reaction is ensured to be carried out in the presence of the phosphorus-containing compound. The preparation method provided by the invention can ensure the regulation effect of the phosphorus-containing compound and the auxiliary agent on the grain growth.
The phosphorus-containing compound of the present invention is widely selected, and preferably the phosphorus-containing compound is at least one selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate and potassium phosphate.
According to the present invention, the gelling reaction in step (1) is preferably any one of the following:
a. the aluminum-containing compound is an inorganic aluminum-containing compound, the phosphorus-containing compound, the magnesium-containing compound and the optional compound containing other auxiliary agents are independently prepared into a solution, or the solution is prepared into a mixed solution, then all the solutions are added into an acidic or alkaline solution, the pH value of the system is regulated to be 4-7, and precipitation reaction is carried out to obtain slurry containing phosphorus-containing hydrated alumina;
b. Preparing a phosphorus-containing compound, a magnesium-containing compound and optionally a compound containing other auxiliary agents into an aqueous solution, contacting an organic aluminum-containing compound or a solution thereof with the aqueous solution for hydrolysis reaction, and regulating the pH value of the system to 4-7 to obtain slurry containing phosphorus-containing hydrated alumina.
According to the invention, preferably, the pH of the system is adjusted with an acid and/or a base during the gelling reaction of step (1). The invention selects the range of the kind of the acidThe acids may be, for example, various protonic acids or oxides which are acidic in aqueous media. Preferably, the acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid and oxalic acid, more preferably at least one of nitric acid, sulfuric acid and hydrochloric acid. The acid may be introduced in the form of a solution, and the concentration of the acid solution is not particularly limited, preferably H + The concentration of (2) is 0.2-2 mol/L.
In the present invention, the base may be a hydroxide or a salt which hydrolyzes in an aqueous medium to make an aqueous solution alkaline, and preferably, the base is at least one of ammonia water, sodium hydroxide, potassium hydroxide, sodium metaaluminate, potassium metaaluminate, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate, and potassium carbonate. Further preferably, the base is at least one of sodium metaaluminate, potassium metaaluminate, sodium hydroxide, potassium hydroxide, and aqueous ammonia. The base may be introduced in the form of a solution, and the concentration of the alkali solution is not particularly limited, and preferably OH - The concentration of (2) is 0.2-4 mol/L. When sodium metaaluminate and/or potassium metaaluminate are used as the base, the amount of the corresponding aluminum oxide in sodium metaaluminate and/or potassium metaaluminate is also considered.
The inorganic aluminum-containing compound is preferably an aluminum salt and/or aluminate, and more preferably one or more of aluminum sulfate, aluminum chloride, aluminum nitrate, sodium aluminate and potassium aluminate. Accordingly, the inorganic aluminum-containing compound solution may be various aluminum salt solutions and/or aluminate solutions, and the aluminum salt solution may be various aluminum salt solutions, for example, may be an aqueous solution of one or more of aluminum sulfate, aluminum chloride, and aluminum nitrate, and is preferably an aluminum sulfate solution and/or an aluminum chloride solution in terms of price. The aluminum salt may be used alone or in combination of two or more. Accordingly, the aluminate solution is any aluminate solution, such as sodium aluminate solution and/or potassium aluminate solution. Sodium aluminate solution is preferred because of its ease of availability and low cost. The aluminate solutions may likewise be used alone or in mixtures.
The concentration of the inorganic aluminum-containing compound solution is not particularly limited in the present invention, and preferably the concentration of the inorganic aluminum-containing compound solution in terms of alumina is 20 to 200 g/l.
In the present invention, the type of the organic aluminum-containing compound is selected from a wide range, and preferably, the organic aluminum-containing compound is at least one of aluminum alkoxides which can be hydrolyzed with water to produce alumina hydrate precipitate.
Preferably, the aluminum alkoxide may have 1 to 10 carbon atoms, preferably 3 to 8 carbon atoms. Specifically, the aluminum alkoxide is preferably at least one selected from aluminum isopropoxide, aluminum n-butoxide, aluminum triisopropoxide, aluminum tri-t-butoxide, aluminum isooctanolate, aluminum n-pentanol, aluminum n-hexanol, aluminum n-heptanol, and aluminum n-octanol.
According to the present invention, the organic aluminum-containing compound may be introduced directly or in the form of a solution, and when it is introduced in the form of a solution, the concentration thereof is not particularly limited as long as the gum-forming reaction can be ensured.
According to a preferred embodiment of the present invention, the pH of the gel forming reaction in step (1) is from 5 to 7, more preferably from 5 to 6.5. The preferred embodiment is more beneficial to obtaining a carrier with bimodal pores and large pore volume, thereby improving the catalytic performance of the prepared catalyst in heavy oil hydrogenation.
According to a preferred embodiment of the invention, the temperature of the gelling reaction is between 30 and 90 ℃. The preferred embodiment is more beneficial to obtaining a carrier with bimodal pores and large pore volume, thereby improving the catalytic performance of the prepared catalyst in heavy oil hydrogenation.
The conditions of the precipitation reaction are not particularly limited in the present invention, and preferably include: the reaction temperature is 40-90 ℃, preferably 45-80 ℃, and the reaction time is 10-60 minutes, preferably 10-30 minutes.
The conditions for the hydrolysis reaction are not particularly limited in the present invention, as long as the organic aluminum-containing compound is hydrolyzed with water to form hydrated alumina. The organic aluminum-containing compound solution may be an organic solution, and the solvent of the organic solution is a solvent which is common in the art and can dissolve the organic aluminum-containing compound. The water consumption in the hydrolysis reaction process is selected in a wider range, so long as the molar ratio of water to the organic aluminum-containing compound is greater than the stoichiometric ratio. Conditions under which hydrolysis specifically occurs are well known to those skilled in the art. Preferably, the conditions of the hydrolysis reaction include: the reaction temperature is 40-90 ℃, preferably 45-80 ℃, and the reaction time is 2-30 hours, preferably 4-20 hours.
According to the invention, preferably, the ageing of step (2) is carried out at a pH of 8-10.
In the present invention, the conditions other than pH for the aging in the step (2) are not particularly limited, and the temperature of the aging is preferably 50 to 95℃and more preferably 55 to 90 ℃. Preferably, the aging time is 0.5 to 8 hours, more preferably 2 to 6 hours.
The specific operations of filtering, washing and drying in the step (2) are not particularly limited, and may be performed according to conventional technical means in the art. For example, the detergent may be water. For example, the drying may be performed using at least one of drying, forced air drying, flash drying, and spray drying.
Preferably, the drying conditions may be: the drying temperature is 100-350deg.C, preferably 120-300deg.C; the drying time is 1 to 24 hours, preferably 2 to 12 hours.
According to the invention, the halogen-containing compound in step (3) is preferably used in such an amount that the halogen content in elemental form in the finally obtained carrier is 0.3 to 4% by weight, preferably 0.5 to 2.5% by weight.
According to the method provided by the invention, the halogen element is selected from the types as described above, and is preferably fluorine.
The introduction mode of the halogen-containing compound is wide in selection range, and the halogen-containing compound can be directly mixed with the phosphorus-containing pseudo-boehmite obtained in the step (2) and then molded, or can be prepared into an aqueous solution and then mixed with the phosphorus-containing pseudo-boehmite obtained in the step (2) and then molded.
In the present invention, the halogen-containing compound may be one or more of any halogen-containing water-soluble compounds. For example, one or more of the water-soluble inorganic salts of halogen. Preferably, the halogen-containing compound is at least one selected from the group consisting of ammonium fluoride, ammonium chloride and ammonium iodide.
According to different requirements, the phosphorus-containing pseudo-boehmite obtained in the step (2) and the halogen-containing compound can be prepared into various easy-to-handle molded products such as spheres, honeycombs, bird nests, tablets or strips (clover, butterfly, cylinder and the like).
In the present invention, the molding may be performed in a conventional manner, for example, one method or a combination of several methods among rolling, tabletting and extrusion molding. In the molding, for example, extrusion molding, water, an extrusion aid and/or an adhesive, with or without a pore-enlarging agent, may be added to the mixture of phosphorus-containing pseudo-boehmite and a halogen-containing compound obtained in the step (2) to ensure that the molding proceeds smoothly, followed by extrusion molding, followed by drying and firing. The kind and the amount of the extrusion aid and the use amount of the peptizer are well known to those skilled in the art, for example, the common extrusion aid can be one or more selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol and polyethylene glycol, the peptizer can be inorganic acid and/or organic acid, and the pore expanding agent can be one or more selected from starch, synthetic cellulose, polyalcohol and surfactant. The synthetic cellulose is preferably one or more of hydroxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy fiber fatty alcohol polyvinyl ether, the polymeric alcohol is preferably one or more of polyethylene glycol, polypropylene alcohol and polyvinyl alcohol, and the surfactant is preferably one or more of fatty alcohol polyvinyl ether, fatty alcohol amide and derivatives thereof, and acrylic alcohol copolymer and maleic acid copolymer with molecular weight of 200-10000.
The drying conditions and specific embodiments in the step (3) of the present invention may be as described above, and will not be described herein.
The conditions for the firing in step (3) of the present invention are selected in a wide range, and preferably the conditions for the firing include: the temperature is 350 to 950 ℃, further 450 to 750 ℃, more preferably 500 to 650 ℃, for 1 to 10 hours, further preferably 2 to 8 hours, more preferably 2 to 6 hours.
According to the present invention, preferably, the method of introducing the hydrogenation-active metal into the carrier is an impregnation method. Specifically, a solution containing a compound of a hydrogenation active metal (a group VIII metal and/or a group VIB metal) is prepared and the support is impregnated with the solution, followed by drying, calcination or no calcination. The group VIII metal and the group VIB metal may be introduced into the support together (co-impregnation) or may be introduced into the support sequentially (stepwise impregnation), which is not particularly limited in the present invention.
According to a preferred embodiment of the invention, the hydrogenation-active metal is at least one group VIII metal selected from nickel or cobalt and at least one group VIB metal selected from molybdenum or tungsten.
The present invention provides a wide range of group VIB metal-containing compounds, preferably, the group VIB metal-containing compound is one or more of molybdate, para-molybdate, tungstate, meta-tungstate, ethyl meta-tungstate, and heteropolyacid salt containing molybdenum or tungsten.
The invention has wide selection range for the compound containing the VIII metal, preferably, the compound containing the VIII metal can be one or more of nitrate, acetate, soluble carbonate, chloride and soluble complex corresponding to cobalt and/or nickel.
According to a preferred embodiment of the invention, the hydrogenation-active metal is used in such an amount that the resulting catalyst has a group VIB metal content of 0.2 to 10 wt.% and a group VIII metal content of 0.2 to 5 wt.% calculated as oxides.
The concentration and amount of the impregnating solution may be appropriately selected by those skilled in the art based on the above content requirements, and the specific operation is well known to those skilled in the art and will not be described herein.
After impregnation of the group VIII and group VIB metals, the method further comprises a drying and optionally calcination process. Preferably, the drying conditions after impregnation of the group VIII and group VIB metals include: the temperature is 100-250 ℃ and the time is 1-10 hours. Preferably, the calcination conditions after impregnation of the group VIII and group VIB metals include: the temperature is 360-500 ℃ and the time is 1-10 hours.
A third aspect of the present invention provides a heavy oil hydrogenation catalyst prepared by the method provided in the second aspect. The heavy oil hydrogenation catalyst carrier has specific structural composition parameters and specific element composition, and has better heavy oil hydrogenation performance when being used in the heavy oil hydrogenation reaction process.
In the present invention, the heavy oil hydrogenation catalyst may be presulfided prior to use in accordance with conventional methods in the art to convert the active metal component supported thereon to a metal sulfide component; the pre-vulcanization method can be as follows: the heavy oil hydrogenation catalyst is presulfided with sulfur, hydrogen sulfide or sulfur-containing raw materials in the presence of hydrogen at 140-400 ℃. The pre-vulcanization may be performed ex-situ or in-situ. The specific conditions for the prevulcanization may be carried out according to conventional means in the art, and the present invention will not be described herein.
The fourth aspect of the invention provides a heavy oil hydroprocessing method comprising contacting a heavy oil feedstock with a heavy oil hydroprocessing catalyst under heavy oil hydroprocessing conditions, wherein the heavy oil hydroprocessing catalyst is a heavy oil hydroprocessing catalyst according to the first or third aspect.
The hydrotreating reaction apparatus in the application of the heavy oil hydrotreating catalyst in the present invention is not particularly limited, and may be any reactor sufficient to allow the raw oil (heavy oil) to contact the heavy oil hydrotreating catalyst under the heavy oil hydrotreating conditions, such as a fixed bed reactor, a slurry bed reactor, a moving bed reactor or an ebullated bed reactor.
The application object of the heavy oil hydrogenation catalyst is not particularly limited, and the heavy hydrocarbon oil hydrogenation catalyst can be directly used for processing various heavy hydrocarbon oil raw materials. According to the method provided by the invention, the heavy oil raw material can be various heavy mineral oils or synthetic oils or mixed distillate thereof.
The invention is thatThe hydrogenation conditions for the application of the heavy oil hydrogenation catalyst are not particularly limited, and reaction conditions generally used in the art can be employed; preferably, the heavy oil hydroprocessing conditions include: the reaction temperature is 300-450 ℃, and more preferably 350-420 ℃; the pressure is 10-20MPa, more preferably 13-18MPa; the liquid hourly space velocity is 0.15 to 0.45 hours -1 More preferably 0.17 to 0.4 hours -1 The hydrogen oil volume ratio is 500 to 1000, more preferably 600 to 800.
The present invention will be described in detail by examples. In the following examples, XRD was measured on a SIMENS D5005 type X-ray diffractometer, with CuK alpha radiation, 44 kilovolts, 40 milliamps, scanning at a rate of 2/min.
XRF characterization the elemental content was quantitatively analyzed by external standard method using an X-ray fluorescence spectrometer, 3271, japan motor industries, inc. Tabletting and molding the powder sample, and forming a rhodium target, wherein the laser voltage is 50kV and the laser current is 50mA.
The pore distribution and pore volume determination of the present invention are characterized by mercury porosimetry, which refers to the distribution of pore diameters, which refers to the pore diameters, unless otherwise specified.
In the following preparation examples and examples, the raw materials involved are commercially available unless otherwise specified.
Preparation example 1
(1) Preparing Al 2 O 3 2L of an aluminum sulfate solution having a concentration of 50g/L was added 5mL of concentrated phosphoric acid (concentration: 85% by weight, the same applies hereinafter), and 9.5g of boric acid, to thereby obtain an aluminum sulfate solution containing phosphorus and boron. The above aluminum sulfate solution and 8% aqueous ammonia solution were added in a 5 liter reaction tank in parallel to conduct reaction precipitation, followed by filtration (the hydrated alumina precipitate was characterized as an amorphous structure by XRD), the reaction temperature was 40 ℃, and the flow rate of the aqueous ammonia solution was controlled so that the pH of the reaction system was 5.5. Mixing and pulping a filter cake, deionized water and ammonia water in a 5-liter reaction tank, wherein the dosage of the ammonia water is such that the pH value of the slurry is 8.0, aging the slurry at 65 ℃ for 60 minutes, filtering, pulping and washing the filter cake with deionized water for 2 times, and drying the filter cake at 120 ℃ for 24 hours to obtain hydrated alumina P1; p1 is roasted for 4 hours at 600 ℃,obtaining aluminum oxide Z1; by XRD characterization, P1 had pseudo-boehmite structure, A1 had gamma-alumina structure, and the A1 composition was characterized by XRF, and the results are shown in Table 1. Pore volumes of A1 measured by mercury porosimetry over a range of pore diameters are listed in table 1. Pore volumes within different pore size ranges were determined using mercury porosimetry. The sample was first calcined at 600℃for 4 hours (same applies below) before measurement.
(2) 1000 g of the hydrated alumina P1 prepared in the step (1) was weighed, 10 ml of an aqueous solution 1440 ml containing nitric acid (Tianjin chemical reagent three-factory product) and 9.8g of ammonium fluoride was added, and the mixture was extruded into butterfly-shaped strips with an outer diameter phi of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was baked at 600℃for 3 hours to obtain a carrier Z1. The properties of the carrier Z1 are shown in Table 2.
Preparation example 2
(1) Preparing Al 2 O 3 2L of aluminum sulfate solution with the concentration of 90g/L is added with 6mL of concentrated phosphoric acid and 51g of magnesium sulfate heptahydrate to obtain aluminum sulfate solution containing phosphorus and magnesium elements. The aluminum sulfate solution containing phosphorus and magnesium elements and 8% ammonia water solution are added in a 5-liter reaction tank in parallel to carry out reaction precipitation, then filtration (XRD is adopted to characterize the alumina hydrate precipitate to be an amorphous structure), the reaction temperature is 45 ℃, and the flow rate of the ammonia water solution is controlled to enable the pH value of a reaction system to be 6.0. The filter cake, deionized water and ammonium bicarbonate were mixed and pulped in a 5 liter reaction tank, the aqueous ammonia was used in an amount to bring the pH of the slurry to 9.2, the slurry was aged at 40℃for 240 minutes and then filtered, the filter cake was pulped and washed 2 times with deionized water, the filter cake was dried at 120℃for 14 hours to give hydrated alumina P2, which was characterized by XRD, P2 had a pseudo-boehmite structure, and P2 was calcined at 600℃for 4 hours to give alumina A2, which was characterized by XRD, A2 had a gamma-alumina structure, and the composition was characterized by XRF, and the results are shown in Table 1. Pore volumes of A2 measured by mercury porosimetry over a range of pore diameters are listed in table 1.
(2) 1000 g of the hydrated alumina P2 prepared in the step (1) was weighed, 10 ml of an aqueous solution 1440 ml containing nitric acid (Tianjin chemical reagent three-factory product) and 9.8g of ammonium fluoride was added, and the mixture was extruded into butterfly-shaped strips with an outer diameter phi of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was calcined at 600℃for 3 hours to obtain a carrier Z2. The properties of the support Z2 are shown in Table 2.
Preparation example 3
(1) Preparing Al 2 O 3 2L of aluminum sulfate solution with the concentration of 90g/L is added with 3mL of concentrated phosphoric acid, 12g of magnesium sulfate heptahydrate and 10g of boric acid to obtain aluminum sulfate solution containing phosphorus, magnesium and boron elements. The above aluminum sulfate solution and 8% aqueous ammonia solution were added in a 5 liter reaction tank in parallel to conduct reaction precipitation, followed by filtration (XRD was used to characterize the alumina hydrate precipitate as amorphous structure), the reaction temperature was 55 ℃, and the flow rate of the aqueous ammonia solution was controlled so that the pH of the reaction system was 6.2. The filter cake, deionized water and sodium carbonate were mixed in a 2 liter reaction tank, slurried, and the amount of sodium carbonate used was such that the pH of the slurry was 8.9, the slurry was aged at 38℃for 30 minutes, then filtered, the filter cake was slurried with deionized water and washed 2 times, the filter cake was dried at 120℃for 14 hours to give hydrated alumina P3, which was characterized by XRD, P3 had a pseudo-boehmite structure, and P3 was calcined at 600℃for 4 hours to give alumina A3, which was characterized by XRD, A3 had a gamma-alumina structure, and the composition was characterized by XRF, and the results are shown in Table 1. Pore volumes of A3 measured by mercury porosimetry over a range of pore diameters are listed in table 1.
(2) 1000 g of the hydrated alumina P3 prepared in the step (1) was weighed, 10 ml of an aqueous solution 1440 ml containing nitric acid (Tianjin chemical reagent three-factory product) and 9.8g of ammonium fluoride was added, and the mixture was extruded into butterfly-shaped strips with an outer diameter phi of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was baked at 600℃for 3 hours to obtain a carrier Z3. The properties of the carrier Z3 are shown in Table 2.
Preparation example 4
(1) Preparing Al 2 O 3 2L of aluminum sulfate solution with the concentration of 50g/L is added with 6mL of concentrated phosphoric acid and 25g of magnesium sulfate heptahydrate to obtain aluminum sulfate solution containing phosphorus and magnesium elements. SiO was added to a 2L sodium metaaluminate solution having an alumina content of 200g/L and a caustic ratio of 1.58 2 The content is 250g/L, and the modulus is 20mL of water glass solution with 2.8. In a 5 liter reaction tank, the aluminum sulfate solution containing the phosphorus and magnesium compounds and the partial water glass are parallel-flowThe sodium aluminate solution is subjected to reaction precipitation, and then is filtered (XRD is adopted to characterize the alumina hydrate precipitation into an amorphous structure), the reaction temperature is 50 ℃, and the flow rate of the sodium aluminate solution is controlled to enable the pH value of a reaction system to be 4.8. The filter cake, deionized water and ammonium carbonate (chemically pure, product of Beijing Yili Fine chemicals Co., ltd.) were mixed in a 5 liter reaction tank, slurried, and the amount of ammonium carbonate was such that the pH of the slurry was 8.7, the slurry was aged at 40℃for 5 hours and then filtered, the filter cake was slurried with deionized water and washed 2 times, the filter cake was dried at 120℃for 24 hours to give hydrated alumina P4, which was characterized by XRD, P4 had a pseudo-boehmite structure, and P4 was calcined at 600℃for 4 hours to give alumina A4, which was characterized by XRD, A4 had a gamma-alumina structure, and the composition was characterized by XRF, and the results are shown in Table 1. Pore volumes of A4 measured by mercury porosimetry over a range of pore diameters are listed in table 1.
(2) 1000 g of the hydrated alumina P4 prepared in the step (1) was weighed, 10 ml of an aqueous solution 1440 ml containing nitric acid (Tianjin chemical reagent three-factory product) and 9.8g of ammonium fluoride was added, and the mixture was extruded into butterfly-shaped strips with an outer diameter phi of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was calcined at 600℃for 3 hours to obtain a carrier Z4. The properties of the support Z4 are shown in Table 2.
Preparation example 5
(1) 1000 g of isopropyl alcohol-water azeotrope (water content: 15 wt%) was added to a 2 liter three-neck flask equipped with a stirring and reflux condenser, 4.6mL of 85% concentrated phosphoric acid was added, the pH was adjusted to 5.1 by adding aqueous ammonia, then heated to 60 ℃, 500 g of molten aluminum isopropoxide was slowly dropped into the flask via a separating funnel, after 2 hours of reaction, the pH was adjusted to 8.5 by adding aqueous ammonia, after 20 hours of reflux reaction, dehydrated isopropyl alcohol was distilled off, aged at 80 ℃ for 6 hours, aqueous isopropyl alcohol was distilled off while aging, and after the aged hydrated alumina was filtered, dried at 120 ℃ for 24 hours to obtain hydrated alumina P5. By XRD characterization, P5 had pseudo-boehmite structure, and P5 was calcined at 600℃for 4 hours to give alumina A5, by XRD characterization, A5 had gamma-alumina structure, and by XRF method, the composition was characterized, and the results are shown in Table 1. Pore volumes of A5 measured by mercury porosimetry over a range of pore diameters are listed in table 1.
(2) 1000 g of the hydrated alumina P5 prepared in the step (1) was weighed, 10 ml of an aqueous solution 1440 ml containing nitric acid (Tianjin chemical reagent three-factory product) and 9.8g of ammonium fluoride was added, and the mixture was extruded into butterfly-shaped strips with an outer diameter phi of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was calcined at 600℃for 3 hours to obtain a carrier Z5. The properties of the support Z5 are shown in Table 2.
(2) 1000 g of the hydrated alumina P5 prepared in the step (1) was weighed, 10 ml of an aqueous solution 1440 ml containing nitric acid (Tianjin chemical reagent three-factory product) and 19.6g of ammonium fluoride was added, and the mixture was extruded into butterfly-shaped strips with an outer diameter phi of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was calcined at 600℃for 3 hours to obtain a carrier Z5. The properties of the support Z5 are shown in Table 2.
Preparation example 6
(1) Preparing Al 2 O 3 2L of aluminum nitrate solution with the concentration of 50g/L is added with 5mL of phosphoric acid to obtain aluminum nitrate solution containing phosphorus element. The above aluminum nitrate solution and 200g/L sodium metaaluminate solution containing aluminum oxide and having a caustic coefficient of 1.58 were added in a 5 liter reaction tank in parallel to carry out reaction precipitation, followed by filtration (the hydrated aluminum oxide precipitate was characterized as an amorphous structure by XRD), the reaction temperature was 60 ℃, and the flow rate of the sodium metaaluminate solution was controlled so that the pH of the reaction system was 6.0. The filter cake, deionized water and ammonium bicarbonate (chemically pure, product of Beijing Yili Fine chemicals Co., ltd.) were mixed in a 5 liter reaction tank, slurried, and the amount of ammonium bicarbonate was such that the pH of the slurry was 8.0, the slurry was aged at 55℃for 4 hours, then filtered, the filter cake was slurried with deionized water and washed 2 times, the filter cake was dried at 120℃for 24 hours to give hydrated alumina P6, which was characterized by XRD, P6 had a pseudo-boehmite structure, and P6 was calcined at 600℃for 4 hours to give alumina A6, which was characterized by XRD, A6 had a gamma-alumina structure, and the composition was characterized by XRF, and the results were shown in Table 1. Pore volumes of A6 measured by mercury porosimetry over a range of pore diameters are listed in table 1.
(2) 1000 g of the hydrated alumina P6 prepared in the step (1) was weighed, 10 ml of an aqueous solution 1440 ml containing nitric acid (Tianjin chemical reagent three-factory product) and 19.6g of ammonium fluoride was added, and the mixture was extruded into butterfly-shaped strips with an outer diameter phi of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was calcined at 600℃for 3 hours to obtain a carrier Z6. The properties of the carrier Z6 are shown in Table 2.
Preparation example 7
The wet butterfly-shaped bar having an outer diameter of 1.4mm prepared in the step (2) of production example 1 was dried at 120℃for 4 hours to obtain a molded article, and the molded article was baked at 700℃for 3 hours to obtain a carrier Z7. The properties of the carrier Z7 are shown in Table 2.
Preparation example 8
The wet butterfly-shaped bar having an outer diameter of 1.4mm prepared in the step (2) of production example 3 was dried at 120℃for 4 hours to obtain a molded article, and the molded article was baked at 800℃for 3 hours to obtain a carrier Z8. The properties of the support Z8 are listed in Table 2.
Preparation example 9
The wet butterfly-shaped bar having an outer diameter of 1.4mm prepared in the step (2) of preparation example 6 was dried at 120℃for 4 hours to obtain a molded article, and the molded article was baked at 900℃for 3 hours to obtain a carrier Z9. The properties of the support Z9 are shown in Table 2.
Preparation of comparative examples 1-7 illustrate properties of existing alumina or alumina prepared by a comparative method
Preparation of comparative example 1
The procedure of preparation 1 was followed except that phosphoric acid and boric acid were not added, and specifically comprising:
(1) Preparing Al 2 O 3 The concentration of the aluminum sulfate solution was 2L at 50g/L, but concentrated phosphoric acid and boric acid were not added. The above aluminum sulfate solution and 8% aqueous ammonia solution were added in a 5 liter reaction tank in parallel to conduct reaction precipitation, followed by filtration (the hydrated alumina precipitate was characterized as an amorphous structure by XRD), the reaction temperature was 40 ℃, and the flow rate of the aqueous ammonia solution was controlled so that the pH of the reaction system was 5.5. Mixing and pulping a filter cake, deionized water and ammonia water in a 5-liter reaction tank, aging the slurry at 65 ℃ for 60 minutes and filtering the slurry, pulping and washing the filter cake with the deionized water for 2 times, drying the filter cake at 120 ℃ for 24 hours to obtain hydrated alumina CP1, adopting XRD to characterize that the CP1 has a pseudo-boehmite structure, and adopting the CP1 to be 60Calcination was carried out at 0℃for 4 hours to give alumina CA1, which was characterized by XRD, CA1 had a gamma-alumina structure, and its composition was characterized by XRF, and the results are shown in Table 1. Pore volumes of CA1 over a range of pore sizes as measured by mercury porosimetry are listed in Table 1.
(2) 1000 g of the hydrated alumina CP1 prepared in the step (1) was weighed, 10 ml of an aqueous solution 1440 ml containing nitric acid (Tianjin chemical reagent three-factory product) and 9.8g of ammonium fluoride was added, and the mixture was extruded into butterfly-shaped strips with an outer diameter phi of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was calcined at 600℃for 3 hours to obtain a carrier DZ1. The properties of the carrier DZ1 are shown in Table 2.
Preparation of comparative example 2
The procedure of preparation 4 was followed except that phosphoric acid, magnesium sulfate heptahydrate and water glass were not added, and specifically comprising:
(1) Preparing Al 2 O 3 2L of aluminum sulfate solution with the concentration of 50g/L, the aluminum sulfate solution and sodium metaaluminate solution with the alumina content of 200g/L and the caustic coefficient of 1.58 are added in a 5-liter reaction tank in parallel flow mode to carry out reaction precipitation, filtration (the hydrated alumina precipitate is characterized as an amorphous structure by XRD) is carried out, the reaction temperature is 50 ℃, and the flow rate of the sodium metaaluminate solution is controlled to enable the pH value of a reaction system to be 4.8. The filter cake, deionized water and ammonium carbonate (chemically pure, product of Beijing Yili Fine chemicals Co., ltd.) were mixed in a 5 liter reaction tank, slurried, and the amount of ammonium carbonate was such that the pH of the slurry was 8.7, the slurry was aged at 40℃for 5 hours and then filtered, the filter cake was slurried with deionized water and washed 2 times, the filter cake was dried at 120℃for 24 hours to give hydrated alumina CP2, which was characterized by XRD, CP2 had a pseudo-boehmite structure, and CP2 was calcined at 600℃for 4 hours to give alumina CA2, which was characterized by XRD, CA2 had a gamma-alumina structure, and the composition was characterized by XRF, and the results are shown in Table 1. Pore volumes of CA2 over the different pore size ranges as measured by mercury porosimetry are listed in table 1.
(2) 1000 g of the hydrated alumina CP2 prepared in the step (1) was weighed, 10 ml of an aqueous solution 1440 ml containing nitric acid (Tianjin chemical reagent three-factory product) and 9.8g of ammonium fluoride was added, and the mixture was extruded into butterfly-shaped strips with an outer diameter phi of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was calcined at 600℃for 3 hours to obtain carrier DZ2. The properties of the carrier DZ2 are shown in Table 2.
Preparation of comparative example 3
The procedure of preparation 6 was followed except that no phosphoric acid was added, specifically comprising:
(1) Preparing Al 2 O 3 2L of aluminum nitrate solution with the concentration of 50g/L, 1000 milliliters of aluminum nitrate solution with the concentration of 50g/L and sodium metaaluminate solution containing 200g/L of alumina and with the caustic coefficient of 1.58 are added in a 5-liter reaction tank in parallel flow mode to carry out reaction precipitation, filtration (the alumina hydrate is characterized by XRD to be precipitated into an amorphous structure) is carried out, the reaction temperature is 60 ℃, and the flow rate of the sodium metaaluminate solution is controlled to enable the pH value of a reaction system to be 6.0. The filter cake, deionized water and ammonium bicarbonate (chemically pure, product of Beijing Yili Fine chemicals Co., ltd.) were mixed in a 5 liter reaction tank, slurried, and the amount of ammonium bicarbonate was such that the pH of the slurry was 8.0, the slurry was aged at 55℃for 4 hours, then filtered, the filter cake was slurried with deionized water and washed 2 times, the filter cake was dried at 120℃for 24 hours to give hydrated alumina CP3, the alumina was characterized by XRD, CP3 had a pseudo-boehmite structure, and CP3 was calcined at 600℃for 4 hours to give alumina CA3, the alumina was characterized by XRD, CA3 had a gamma-alumina structure, and the composition was characterized by XRF, the results of which are shown in Table 1. Pore volumes of CA3 over the different pore size ranges as measured by mercury porosimetry are listed in table 1.
(2) 1000 g of the hydrated alumina CP3 prepared in the step (1) was weighed, 10 ml of an aqueous solution 1440 ml containing nitric acid (Tianjin chemical reagent three-factory product) and 9.8g of ammonium fluoride was added, and the mixture was extruded into butterfly-shaped strips with an outer diameter phi of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was calcined at 600℃for 3 hours to obtain carrier DZ3. The properties of the carrier DZ3 are shown in Table 2.
Preparation of comparative example 4
The commercial SB powder CP4 sold by Sasol company was calcined at 600℃for 4 hours to give alumina CA4, and the pore volumes measured by mercury porosimetry in the different pore size ranges are shown in Table 1. 1000 g of CP4 was weighed out and 1440 ml of an aqueous solution containing 10 ml of nitric acid (Tianjin chemical three-plant product) and 19.6g of ammonium fluoride was added. CP4 was extruded into butterfly strips with an outer diameter phi 1.4mm on a twin screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was calcined at 700℃for 3 hours to obtain carrier DZ4. The properties of the carrier DZ4 are shown in Table 2.
Preparation of comparative example 5
The commercial Shandong powder CP5 sold by Shandong corporation of aluminum industry in China was calcined at 600℃for 4 hours to obtain alumina CA5, and the pore volumes measured by the mercury porosimetry in the different pore size ranges are shown in Table 1. 1000 g of CP5 was weighed, 10 ml of an aqueous solution 1440 ml of nitric acid (Tianjin chemical three-factory product) and 19.6g of ammonium fluoride were added, and the CP5 was extruded into butterfly-shaped strips with an outer diameter of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was calcined at 800℃for 3 hours to obtain carrier DZ5. The properties of the carrier DZ5 are shown in Table 2.
Preparation of comparative example 6
The procedure of preparation 6 was followed except that the pH of the ammonium bicarbonate control system was not added during aging, the pH of the aging system was 6.0, alumina hydrate CP6 was obtained, the XRD was used to characterize the system, CP6 had a pseudo-boehmite structure, CP6 was calcined at 600℃for 4 hours, alumina CA6 was obtained, the XRD was used to characterize the system, CA6 had a gamma-alumina structure, and the XRF was used to characterize the composition, the results are shown in Table 1. Pore volumes of CA6 over a range of pore sizes as measured by mercury porosimetry are listed in Table 1. 1000 g of the hydrated alumina CP6 prepared in the step (1) was weighed, 10 ml of an aqueous solution 1440 ml containing nitric acid (Tianjin chemical reagent three-factory product) and 9.8g of ammonium fluoride was added, and the mixture was extruded into butterfly-shaped strips with an outer diameter phi of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was baked at 600℃for 3 hours to obtain carrier CZ6. The properties of carrier CZ6 are listed in table 2.
Preparation of comparative example 7
The procedure of preparation 6 was followed except that the flow rate of sodium metaaluminate solution was controlled during the precipitation reaction so that the pH of the reaction system was 8 to obtain alumina hydrate CP7, the alumina hydrate was characterized by XRD, CP7 had a pseudo-boehmite structure, CP6 was calcined at 600℃for 4 hours to obtain alumina CA7, the alumina hydrate was characterized by XRD, CA7 had a gamma-alumina structure, and the composition thereof was characterized by XRF, the results of which are shown in Table 1. Pore volumes of CA7 over the different pore size ranges as measured by mercury porosimetry are listed in table 1. 1000 g of the hydrated alumina CP7 prepared in the step (1) was weighed, 10 ml of an aqueous solution 1440 ml containing nitric acid (Tianjin chemical reagent three-factory product) and 9.8g of ammonium fluoride was added, and the mixture was extruded into butterfly-shaped strips with an outer diameter phi of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was baked at 600℃for 3 hours to obtain carrier CZ7. The properties of carrier CZ7 are listed in table 2.
Preparation of comparative example 8
Phosphorus-containing pseudo-boehmite and phosphorus-containing alumina were prepared according to the method of preparation example 6 except that 5mL of concentrated phosphoric acid was changed to 5.0g of anhydrous magnesium chloride to obtain hydrated alumina CP8, the hydrated alumina was characterized by XRD, CP8 had pseudo-boehmite structure, CP8 was calcined at 600℃for 4 hours to obtain alumina CA8, the alumina was characterized by XRD, CA8 had gamma-alumina structure, and the composition was characterized by XRF, and the results are shown in Table 1. Pore volumes of CA8 over the different pore size ranges as measured by mercury porosimetry are listed in table 1.
(2) 1000 g of the hydrated alumina CP8 prepared in the step (1) was weighed, 10 ml of an aqueous solution 1440 ml containing nitric acid (Tianjin chemical reagent three-factory product) and 9.8g of ammonium fluoride was added, and the mixture was extruded into butterfly-shaped strips with an outer diameter phi of 1.4mm on a twin-screw extruder. The wet strand was dried at 120℃for 4 hours to obtain a molded article, and the molded article was calcined at 600℃for 3 hours to obtain a carrier DZ8. The properties of the carrier DZ8 are shown in Table 2.
TABLE 1
TABLE 2
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The data presented in tables 1 and 2 shows that the pore volume and total pore volume of the mesoporous and macroporous portions of the alumina provided by the inventive process are significantly higher than the alumina provided by the comparative process, indicating that the alumina provided by the inventive process has a significantly bimodal pore distribution with a larger mesopore volume, macropore volume and total pore volume.
Example 1
200 g of carrier Z1 are taken and 220 ml of carrier Z1 containing MoO are used 3 80 g/l, 16 g/l of NiO, and nickel nitrate mixed solution are immersed for 1 hour, dried for 4 hours at 120 ℃ and roasted for 3 hours at 400 ℃, so as to obtain a heavy oil hydrogenation catalyst C1, wherein the composition of the C1 is shown in Table 3.
Example 2
200 g of carrier Z2 are taken and 220 ml of carrier Z2 containing MoO are used 3 80 g/l, 16 g/l of NiO, and nickel nitrate mixed solution are immersed for 1 hour, dried for 4 hours at 120 ℃ and roasted for 3 hours at 400 ℃, so as to obtain a heavy oil hydrogenation catalyst C2, and the composition of the C2 is shown in Table 3.
Example 3
200 g of carrier Z3 are taken and 220 ml of carrier Z3 containing MoO are used 3 80 g/l, coO 16 g/l of mixed solution of ammonium heptamolybdate and cobalt nitrate is immersed for 1 hour, dried for 4 hours at 120 ℃, and roasted for 3 hours at 400 ℃, so that a heavy oil hydrogenation catalyst CZ3 is obtained, and the composition of C3 is shown in Table 3.
Comparative example 1
200 g of carrier DZ1 are taken and 220 ml of carrier containing MoO 3 80 g/l, coO 16 g/l ammonium heptamolybdate and cobalt nitrate mixed solution impregnation for 1 hour, 120 ℃ drying for 4 hours, 400 ℃ roasting for 2 hours, and obtaining hydrogenation demetallization catalyst DC1, wherein the composition of DC1 is listed in Table 3.
Comparative example 2
200 g of DZ2 are taken and 220 ml of the mixture containing MoO is used 3 80 g/l of mixed solution of ammonium heptamolybdate and nickel nitrate, 16 g/l of NiO, was immersed for 1 hour, dried at 120 ℃ for 4 hours, and calcined at 400 ℃ for 2 hours to obtain a hydrodeasphaltene catalyst DC2, and the composition of DC2 is shown in Table 3.
Comparative example 3
200 g of carrier is takenBody DZ3, with 220 ml MoO 3 80 g/l, 16 g/l of NiO and nickel nitrate mixed solution is immersed for 1 hour, dried for 4 hours at 120 ℃ and roasted for 3 hours at 400 ℃ to obtain a hydrodemetallization catalyst DC3, wherein the composition of the DC3 is shown in Table 3.
Example 4
200 g of carrier Z4 are taken and 220 ml of carrier Z4 containing MoO are used 3 80 g/l, 16 g/l of NiO, and nickel nitrate mixed solution are immersed for 1 hour, dried for 4 hours at 120 ℃, and baked for 3 hours at 400 ℃, so as to obtain a heavy oil hydrogenation catalyst C4, wherein the composition of C4 is shown in Table 3.
Example 5
200 g of Z5 are taken and 220 ml of the mixture containing MoO 3 80 g/l, 16 g/l of NiO and nickel nitrate mixed solution is immersed for 1 hour, dried for 4 hours at 120 ℃, and roasted for 3 hours at 400 ℃, so as to obtain a heavy oil hydrogenation catalyst C5, and the composition of the C5 is shown in Table 3.
Example 6
200 g of Z6 are taken and 220 ml of the solution containing WO 3 59 g/l, coO 10 g/l ammonium tungstate and cobalt nitrate mixed solution is immersed for 1 hour, dried for 4 hours at 120 ℃, and baked for 3 hours at 400 ℃, so as to obtain a heavy oil hydrogenation catalyst C6, wherein the composition of the C6 is shown in Table 3.
Comparative example 4
200 g of DZ4 are taken and 220 ml of the mixture containing MoO is used 3 59 g/l, a mixed solution of ammonium heptamolybdate and nickel nitrate, niO 10 g/l, was immersed for 1 hour, dried at 120 ℃ for 4 hours, and calcined at 400 ℃ for 2 hours to obtain hydrodemetallization catalyst DC4, the composition of DC4 is shown in Table 3.
Comparative example 5
200 g of carrier DZ5 were taken and 220 ml of the solution containing WO 3 59 g/l, 10 g/l CoO ammonium tungstate and cobalt nitrate mixed solution is immersed for 1 hour, dried for 4 hours at 120 ℃ and roasted for 3 hours at 400 ℃ to obtain a hydrodemetallization catalyst DC5, wherein the composition of the DC5 is shown in table 3.
Comparative example 6
The procedure of example 6 was followed except that vector Z6 was replaced with vector DZ6.
Comparative example 7
The procedure of example 6 was followed except that vector Z6 was replaced with vector DZ7.
Comparative example 8
The procedure of example 6 was followed except that vector Z6 was replaced with vector DZ8.
Example 7
200 g of Z7 are taken and 220 ml of the solution containing WO 3 80 g/l, 16 g/l of NiO ammonium tungstate and nickel nitrate mixed solution is immersed for 1 hour, dried for 4 hours at 120 ℃ and roasted for 3 hours at 400 ℃ to obtain a heavy oil hydrogenation catalyst C7, and the composition of the C7 is shown in Table 3.
Example 8
200 g of Z8 are taken and 220 ml of the mixture containing MoO 3 58 g/l, 2 g/l of NiO, and nickel nitrate were impregnated for 1 hour, dried at 120℃for 4 hours, and calcined at 400℃for 3 hours to give a heavy oil hydrogenation catalyst C8, the composition of C8 being shown in Table 3.
Example 9
200 g of Z9 are taken and 220 ml of the solution containing WO 3 59 g/l, coO 10 g/l mixed solution of ammonium tungstate and cobalt nitrate is immersed for 1 hour, dried for 4 hours at 120 ℃, and baked for 3 hours at 400 ℃, so as to obtain a heavy oil hydrogenation catalyst C9, and the composition of the C9 is shown in Table 3.
TABLE 3 Table 3
Test case
The test example is used for explaining the heavy oil hydrogenation performance of the heavy oil hydrogenation catalyst provided by the invention.
The catalyst was evaluated on a 100 ml small fixed bed reactor using sand light slag as the starting material.
The catalyst was crushed into particles having a diameter of 2 to 3 mm, the catalyst was charged in an amount of 100 ml, and then presulfiding was carried out under the conditions including: the sulfide oil adopts Qingdao normal two-line diesel oil containing 5w percent of dimethyl disulfide, and the liquid hourly space velocity of the sulfide oil is 1.2h -1 The hydrogen partial pressure is 14.0MPa, the hydrogen oil volume ratio is 600, and the constant temperature is carried out for 3 hours at 360 ℃.
Raw oilThe properties are shown in Table 4, and the evaluation results are shown in Table 5. The reaction conditions are as follows: the reaction temperature is 380 ℃, the hydrogen partial pressure is 14 MPa, and the liquid hourly space velocity is 0.7 hour -1 The hydrogen-oil volume ratio was 1000, and samples were taken after 200 hours of reaction.
The specific calculation method of the demetallization rate and the desulfurization rate is as follows:
the nickel and vanadium contents in the oil sample were measured by inductively coupled plasma emission spectrometry (ICP-AES) (the apparatus used is PE-5300 type plasma light meter of PE company in America, and the specific method is RIPP 124-90). The content of asphaltene in the oil sample is measured by a petroleum asphaltene content measuring method, and the specific method is shown in a petrochemical analysis method SH 0266-1).
TABLE 4 Table 4
| Raw oil name | Sand light slag |
| Density (20 ℃ C.) kg/m 3 | 0.774 |
| Charcoal residue,% (m) | 11.9 |
| Four component,% (m) | |
| Saturation fraction | 30.2 |
| Aromatic components | 47.2 |
| Colloid | 19.5 |
| Asphaltenes | 3.0 |
| S，m％ | 3.5 |
| N，m％ | 0.21 |
| Ni，ppm | 11.7 |
| V，ppm | 31.7 |
TABLE 5
| Examples numbering | Catalyst numbering | Ni removal rate/% | V removal rate/% | Deasphalting Rate/% |
| 1 | C1 | 75 | 89 | 82 |
| 2 | C2 | 76 | 87 | 87 |
| 3 | C3 | 73 | 85 | 84 |
| Comparative example 1 | DC1 | 61 | 70 | 56 |
| Comparative example 2 | DC2 | 61 | 71 | 57 |
| Comparative example 3 | DC3 | 66 | 72 | 61 |
| 4 | C4 | 73 | 83 | 83 |
| 5 | C5 | 75 | 79 | 88 |
| 6 | C6 | 71 | 77 | 81 |
| Comparative example 4 | DC4 | 54 | 60 | 46 |
| Comparative example 5 | DC5 | 57 | 63 | 45 |
| Comparative example 6 | DC6 | 60 | 68 | 59 |
| Comparative example 7 | DC7 | 61 | 69 | 58 |
| Comparative example 8 | DC8 | 59 | 65 | 62 |
| 7 | C7 | 77 | 82 | 83 |
| 8 | C8 | 71 | 78 | 76 |
| 9 | C9 | 72 | 79 | 75 |
The results given in Table 5 are results after 200 hours of evaluation of the reaction, and it can be seen by comparison that the hydrodemetallization activity and the deasphalting activity of the heavy oil hydrogenation catalyst provided by the present invention are significantly higher than those of the comparative catalyst.
Claims (21)
1. A halogen-containing heavy oil hydrogenation catalyst contains alumina carrier with bimodal pore structure and hydrogenation active metal loaded on the carrierWherein the carrier contains phosphorus and halogen element, the halogen element is one or more selected from fluorine, chlorine, bromine, iodine and astatine, and based on the weight of the carrier, the carrier is P 2 O 5 The phosphorus content is 0.1-8.0 wt% and the halogen content is 0.1-6 wt% calculated as element; the hydrogenation active metal is at least one metal selected from the group consisting of VIB metals and optionally at least one metal selected from the group consisting of VIII metals, and the hydrogenation active metal content is 0.3-20 wt% based on the total catalyst and calculated on oxide; characterized by mercury intrusion, the first pores of the carrier are distributed as mesopores positioned at 3-100nm, and the pore volume V Middle hole 1.0-1.5 mL/g, the second pores are distributed as macropores at 100-5000nm, pore volume V Macropores are formed 1.0-1.8 mL/g, total pore volume V Total (S) 2.0-3.3 mL/g; the carrier is prepared from phosphorus-containing pseudo-boehmite, phosphorus-containing alumina obtained by roasting the phosphorus-containing pseudo-boehmite has a bimodal pore structure, and is characterized by mercury intrusion, wherein the distribution of pores of the phosphorus-containing alumina is positioned at a pore volume V of 3-100nm 1 1.0-2.0mL/g, a pore distribution of pore volume V between 100 and 5000nm 2 2.0-5.0mL/g, and the total pore volume V is 3.0-7.0mL/g; the roasting conditions include: the temperature is 350-950 ℃ and the time is 2-8 hours.
2. The hydrogenation catalyst according to claim 1, wherein the carrier is prepared from a phosphorus-containing pseudo-boehmite, the phosphorus-containing pseudo-boehmite having a bimodal pore structure, characterized by mercury intrusion, and the phosphorus-containing alumina has a pore distribution of pore volume V of 3-100nm 1 1.2-1.8mL/g, a pore distribution of pore volume V in the range of 100-5000nm 2 2.1-3.5mL/g and a total pore volume V of 3.3-5.3mL/g.
3. The hydrogenation catalyst according to claim 2, wherein the hydrogenation active metal is at least one group VIII metal selected from nickel or cobalt and at least one group VIB metal selected from molybdenum or tungsten, the group VIB metal content being 0.2-10 wt.% and the group VIII metal content being 0.2-5 wt.% based on the total catalyst and on oxide; the halogen content of the carrier is 0.3-4 wt% calculated by element.
4. The hydrogenation catalyst according to claim 3, wherein the halogen content in elemental form in the carrier is 0.5-2.5 wt%.
5. The hydrogenation catalyst according to any one of claims 1 to 4, wherein the phosphorus-containing alumina carrier contains magnesium promoter and optionally other promoters in an amount of 0.1 to 5.0 wt.% P, calculated as oxide, based on the total amount of the alumina carrier 2 O 5 0.1 to 5.0% by weight MgO; the other auxiliary agents comprise metal auxiliary agents and/or nonmetal auxiliary agents, and the content of the other auxiliary agents calculated by oxide is 0-10.0 wt%; the metal auxiliary agent is at least one of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, calcium, zirconium and titanium, and the non-metal auxiliary agent element is at least one of boron element, fluorine element and silicon element.
6. The process for preparing a halogen-containing heavy oil hydrogenation catalyst according to claim 1, comprising the steps of preparing an alumina carrier having a bimodal pore structure and introducing a hydrogenation active metal into the carrier, the hydrogenation active metal being one or more metals selected from the group consisting of a group VIII metal and a group VIB metal, the amount of hydrogenation active metal being such that the hydrogenation active metal content in terms of oxide in the final catalyst is from 0.3 to 20 wt.%; wherein, the steps for preparing the alumina carrier are as follows: (1) The gelling reaction is carried out in the presence of an aluminum-containing compound and a phosphorus-containing compound to obtain a slurry containing hydrated alumina containing phosphorus, the phosphorus-containing compound enables P to be contained in the finally obtained carrier 2 O 5 The phosphorus content is 0.1-8.0 wt%; (2) Regulating the pH value of the slurry containing the phosphorus-containing hydrated alumina obtained in the step (1) to 7-10.5, aging, filtering, washing and drying to obtain phosphorus-containing pseudo-boehmite; (3) Shaping, drying and roasting the phosphorus-containing pseudo-boehmite obtained in the step (2) and a compound containing halogen elements to obtain the alumina carrier, wherein the halogen elements areOne or more selected from the group consisting of fluorine, chlorine, bromine, iodine and astatine, said halogen-containing compound being used in such an amount that the halogen content in elemental form in the finally obtained carrier is 0.1 to 6% by weight; the gel forming reaction in the step (1) is carried out under the condition of pH value of 4-7.
7. The process according to claim 6, wherein the reactants in step (1) further comprise a magnesium-containing compound and optionally other auxiliary-containing compounds, the amounts of the magnesium-containing compound and the optional other auxiliary-containing compounds being such that the finally prepared alumina carrier contains 0.1 to 5.0 wt.% P, calculated as oxide 2 O 5 0.1-5.0 wt% MgO,0-10.0 wt% other auxiliary agent; the other auxiliary agents comprise metal auxiliary agents and/or nonmetal auxiliary agents, and the content of the other auxiliary agents calculated by oxide is 0-10.0 wt%; the metal auxiliary agent is at least one of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, calcium, zirconium and titanium, and the non-metal auxiliary agent element is at least one of boron element, fluorine element and silicon element.
8. The method of claim 6 or 7, wherein the gelling reaction in step (1) is any of the following: a. the aluminum-containing compound is an inorganic aluminum-containing compound, the phosphorus-containing compound, the magnesium-containing compound and the optional compound containing other auxiliary agents are independently prepared into a solution, or the solution is prepared into a mixed solution, then all the solutions are added into an acidic or alkaline solution, the pH value of the system is regulated to be 4-7, and precipitation reaction is carried out to obtain slurry containing phosphorus-containing hydrated alumina; b. preparing a phosphorus-containing compound, a magnesium-containing compound and optionally a compound containing other auxiliary agents into an aqueous solution, contacting an organic aluminum-containing compound or a solution thereof with the aqueous solution for hydrolysis reaction, and regulating the pH value of the system to 4-7 to obtain slurry containing phosphorus-containing hydrated alumina.
9. The method of claim 8, wherein the inorganic aluminum-containing compound is an aluminum salt and/or aluminate; the organic aluminum-containing compound is at least one of aluminum alkoxides which can generate hydrated aluminum oxide precipitation through hydrolysis reaction with water; in the step (1), acid and/or alkali are used for adjusting the pH value of the system in the process of the gel forming reaction, wherein the acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid and oxalic acid; the alkali is at least one of sodium metaaluminate, potassium metaaluminate, sodium hydroxide, potassium hydroxide and ammonia water.
10. The method of claim 9, wherein the gel forming reaction of step (1) has a pH of 5 to 7.
11. The method of claim 10, wherein the gel forming reaction of step (1) has a pH of 5-6.5.
12. The method according to claim 6 or 7, wherein the temperature of the gelling reaction is 30-90 ℃.
13. The method of claim 9, wherein the precipitation reaction conditions include: the reaction temperature is 40-90 ℃ and the reaction time is 10-60 minutes; the conditions of the hydrolysis reaction include: the reaction temperature is 40-90 ℃, and the reaction time is 2-30 hours.
14. The method of claim 13, wherein the precipitation reaction conditions include: the reaction temperature is 45-80 ℃ and the reaction time is 10-30 minutes; the conditions of the hydrolysis reaction include: the reaction temperature is 45-80 ℃ and the reaction time is 4-20 hours.
15. The method according to any one of claims 7, 9 to 11, 14, wherein the phosphorus-containing compound is at least one selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate and potassium phosphate, and the magnesium-containing compound is one or more of magnesium chloride, magnesium nitrate and magnesium sulfate.
16. The process according to any one of claims 6 to 7, 9 to 11, 14, wherein the halogen-containing compound in step (3) is used in such an amount that the halogen content in elemental form in the final support is 0.3 to 4% by weight.
17. The method according to claim 16, wherein the halogen-containing compound is used in the step (3) in such an amount that the halogen content in terms of elements in the finally obtained carrier is 0.5 to 2.5% by weight; the ageing in the step (2) is carried out under the condition that the pH value is 8-10; the aging temperature is 50-95 ℃; aging for 0.5-8 hours; the roasting conditions include: the temperature is 350-950 ℃ and the time is 2-8 hours.
18. The method of claim 17, wherein the aging temperature is 55-90 ℃; aging for 2-6 hours; the roasting conditions include: the temperature is 450-750 ℃.
19. The process according to any one of claims 6-7, 9-11, 14, wherein the hydrogenation active metals are at least one group VIII metal selected from nickel or cobalt and at least one group VIB metal selected from molybdenum or tungsten, the hydrogenation active metals being used in such amounts that the resulting catalyst has a group VIB metal content of 0.2-10 wt.% as oxide and a group VIII metal content of 0.2-5 wt.%.
20. A heavy oil hydrogenation catalyst prepared by the process of any one of claims 6-19.
21. A heavy oil hydroprocessing method comprising contacting a heavy oil feedstock with a heavy oil hydroprocessing catalyst under heavy oil hydroprocessing conditions, wherein the heavy oil hydroprocessing catalyst is the heavy oil hydroprocessing catalyst of any of claims 1-5, 20.
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| CN104226342A (en) * | 2013-06-13 | 2014-12-24 | 中国石油化工股份有限公司 | Heavy oil hydrotreating catalyst and preparation and application |
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| CN104226342A (en) * | 2013-06-13 | 2014-12-24 | 中国石油化工股份有限公司 | Heavy oil hydrotreating catalyst and preparation and application |
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