CN109926077A - A kind of inferior raw material hydrogenation conversion catalyst and preparation method thereof - Google Patents
A kind of inferior raw material hydrogenation conversion catalyst and preparation method thereof Download PDFInfo
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- CN109926077A CN109926077A CN201711353763.4A CN201711353763A CN109926077A CN 109926077 A CN109926077 A CN 109926077A CN 201711353763 A CN201711353763 A CN 201711353763A CN 109926077 A CN109926077 A CN 109926077A
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- conversion catalyst
- hydrogenation conversion
- solution
- catalyst described
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- 239000003054 catalyst Substances 0.000 title claims abstract description 147
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 129
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 88
- 239000002994 raw material Substances 0.000 title claims abstract description 17
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 34
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 68
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- 239000004411 aluminium Substances 0.000 claims description 16
- 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 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 150000004645 aluminates Chemical class 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- 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 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 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 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000005299 abrasion Methods 0.000 claims description 4
- 229940102253 isopropanolamine Drugs 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000001802 infusion Methods 0.000 claims description 3
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims 1
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 8
- 241000219782 Sesbania Species 0.000 description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 description 7
- 239000004575 stone Substances 0.000 description 7
- 229910018104 Ni-P Inorganic materials 0.000 description 6
- 229910018536 Ni—P Inorganic materials 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 238000005255 carburizing Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- -1 boehmite Aluminium oxide Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000136 polysorbate Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000000626 Daucus carota Species 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000005770 birds nest Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 125000005624 silicic acid group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- UDKYUQZDRMRDOR-UHFFFAOYSA-N tungsten Chemical compound [W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W][W] UDKYUQZDRMRDOR-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 235000005765 wild carrot Nutrition 0.000 description 1
Abstract
The present invention provides a kind of inferior raw material hydrogenation conversion catalysts and preparation method thereof, and the catalyst includes active component and carrier；Active component is group VIB and/or group VIII metal, and carrier is aluminium oxide.The preparation method is that preparing boehmite first, carrier, final load active metal component then are obtained through molding, drying, roasting.The catalyst of the method for the present invention preparation has biggish Kong Rong and specific surface area, and with higher plus hydrogen takes off impurity activity and conversion ratio.
Description
Technical field
The invention belongs to refining art, it is related to a kind of catalysis material and preparation method thereof, turns more particularly to one kind plus hydrogen
Change catalyst and preparation method thereof.
Background technique
In recent years, crude oil increasingly becomes weight, and fraction product demand constantly increases between city's field alignment, to residual fuel demand by
It is decrescence few, residuum hydroconversion production high quality of products is become more and more attractive.Boiling bed residual oil hydrogenation technique technology
With difunctional advantage, which both can achieve good hydrogenation capability, can also realize that the higher hydro-conversion of residual oil is horizontal.
Fluidized bed reactor should have good kinetic balance, to maintain catalyst bed to expand and fluidization uniformity,
Reach catalytic hydrogenation reaction balance.This requires catalyst should have certain special physicochemical properties, close to the accumulation of catalyst
Degree, grain shape, size distribution also have certain requirement, it is generally recognized that the ball more tiny for granularity than convenient grain shape
Shape.Spheric granules is readily flowed, and without the coarse corner for being easy to be crashed sharp in such as other shapes.
When ebullated bed processes inferior raw material, such as decompression residuum, reactant is mostly bigger molecule compound, and catalyst should have
There are sufficiently large Kong Rong and suitable pore-size distribution, so that reactant molecule is able to enter catalytic inner, it is living with inner surface
Property central contact, to improve diffusion and accommodate more impurity.If aperture is relatively small, catalyst aperture will be fast
Speed is blocked, and causes catalyst inactivation.If macropore is more, surface area is too low, and also difficulty reaches requirement to wear resistance.With it is solid
Fixed bed is slightly different, and since reaction temperature is higher, the viscosity of residual oil significantly reduces ebullated bed, to be easier to enter catalyst duct
It is inside reacted, so suitable pore-size distribution adds hydrogen extremely important boiling bed residual oil.The property of support material is directly determined
Determine the pore-size distribution of boiling bed residual oil hydrogenation catalyst, therefore, develops and the low cost of boiling bed residual oil hydrogenation catalyst is suitble to carry
Body raw material is the target of research.
CN201310495647.1 discloses a kind of preparation method of boiling-bed catalyst.The patent is prepared using carbonizatin method
Boehmite, reaction carry out in impact flow reactor, strengthen mass transfer.There is no solve for the standby boehmite of the patent system
Particle is uneven during plastic, and the boehmite raw material pore size distribution of preparation is not concentrated.
CN201510306899.4 discloses a kind of carburizing reagent synthesis system and its answering in terms of preparing boehmite
With and preparation method, including continuous carbonization reaction kettle prepares aluminum hydroxide precipitation, aging, washing filtering and dry, wherein continuous
Carburizing reagent kettle prepares aluminum hydroxide precipitation system and is connected in series by two or more tiny cells carburizing reagent kettles, is used for
The alkaline solution containing aluminium of boehmite preparation is in tiny cells carburizing reagent kettle because being formed baffling, back-mixing and CO by resistance2
Carburizing reagent occurs with the mixed gas of air, the slurries of generation flow into next tiny cells carburizing reagent kettle from outlet, so
Repeatedly, realize that carbonation reaction is continuous.Although the technique realizes that preparation process serialization, technical process are complex.
CN201010188611.5 discloses a kind of hydrated alumina and preparation method thereof.The hydrated alumina, which contains, intends thin water
Aluminium stone and aluminum carbonate basic ammonium.This method includes making sodium metaaluminate and/or sodium aluminate and acid solution haptoreaction, and will contact
The mixed serum obtained after reaction carries out aging in the presence of aging agent；The catalytic condition includes: that pH value in reaction is
4.5-9, reaction temperature are 15-75 DEG C；The condition of the aging includes: that temperature is 20-60 DEG C, and the time is 2-6 hours；It is described old
Agent is ammonium carbonate and/or ammonium hydrogen carbonate.The patent system is cumbersome for ageing process in alumina process.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of inferior raw material hydrogenation conversion catalyst and its systems
Preparation Method.In the method for hydrogenation conversion catalyst of the present invention, two-stage reaction is used when preparing boehmite and introduces processing
Agent, the boehmite made, which has, waits partial sizes crystal grain and high close-burning feature, prepares by precursor of this boehmite
Aluminium oxide be that catalyst prepared by carrier has Kong Rong great, pore distribution concentration wears away the advantages that low and Hydrogenation is good.
First aspect present invention provides a kind of hydrogenation conversion catalyst, the hydrogenation conversion catalyst include active component and
Carrier；Institute's active component is vib metals and/or group VIII metal, on the basis of catalyst weight, vib metals
Content is 8.0w%~18.0wt% in terms of oxide, preferably 9.0wt%~15.0wt%, and group VIII metal is contained in terms of oxide
Amount is 1.0wt%~8.0wt%, preferably 2.0wt%~5.0wt%.
In hydrogenation conversion catalyst of the present invention, the vib metals are W and/or Mo, the group VIII metal Co
And/or Ni.
In hydrogenation conversion catalyst of the present invention, the active component is Mo and Ni.
The property of hydrogenation conversion catalyst of the present invention is as follows: 0.55~0.70mL/g of Kong Rongwei, specific surface area be 150~
220m2/ g, preferably 150~200m2/g。
The pore size distribution of hydrogenation conversion catalyst of the present invention is as follows: the Kong Rong in the hole of bore dia < 8nm account for the 15% of total pore volume with
Under, preferably 10% hereinafter, the Kong Rong in hole that bore dia is 8~15nm accounts for the 60%~80% of total pore volume, preferably 70%~80%,
The Kong Rong in the hole of bore dia > 15nm accounts for the 15%~25% of total pore volume, preferably 18%~25%.
The catalyst surface hydroxy density mole of density of surface hydroxyl and SB the powder preparation of hydrogenation conversion catalyst of the present invention
Ratio is 1.1~1.6, preferably 1.2~1.5.The SB powder is the standard sample that Sasol company, Germany provides.The SB powder
Kong Rongwei 0.5mL/g.
The partial size of hydrogenation conversion catalyst of the present invention is 0.8~2.0mm, abrasion the < 1.5wt%, preferably < of catalyst
1.0wt%.In the present invention, abrasion are using fluidisation state tear strength tester measurement.Catalyst can be spherical shape, honeycomb, Bird's Nest
One or more of shape, tablet or bar shaped (clover, butterfly, cylinder etc.), it is preferably spherical.
Second aspect of the present invention provides a kind of preparation method of above-mentioned hydrogenation conversion catalyst, and the preparation method includes
Following content:
(1) water is added into first reactor, alkali aluminate soln and the first acidic aluminum are then added in a manner of continuous cocurrent
Acid salt solution, adjusting solution pH value is 3~6.5, preferably 4~6, obtains slurries after reaction；
(2) slurries, inorganic agent A are continually introduced into second reactor, then it is molten that alkaline solution, the second bialuminate is added in cocurrent
Liquid, adjusting solution pH value is 7~10, preferably 7.5~9, obtains suspension after reaction；
(3) step (2) resulting suspension obtains boehmite after being filtered, washed and dried drying；
(4) boehmite that step (3) obtains is obtained into carrier after molding, drying, roasting；
(5) the carrier loaded active component for obtaining step (4) obtains catalyst by dry and roasting.
In the preparation method of hydrogenation conversion catalyst of the present invention, the additional amount of water in first reactor described in step (1)
It is the 1/4~1/2 of first reactor volume, preferably 1/4~1/3.
In the preparation method of hydrogenation conversion catalyst of the present invention, basic aluminate described in step (1) is sodium metaaluminate, partially
One of potassium aluminate is a variety of, preferably sodium metaaluminate.
In the preparation method of hydrogenation conversion catalyst of the present invention, the concentration of alkali aluminate soln described in step (1) is
100~250 gAl2O3/ L, preferably 150~200gAl2O3/ L, 0.5~1L/h of flow velocity.
In the preparation method of hydrogenation conversion catalyst of the present invention, the first bialuminate as described in step (1) is sulfuric acid
One or more of aluminium, aluminum nitrate, aluminium chloride, preferably sulfuric acid aluminium.
In the preparation method of hydrogenation conversion catalyst of the present invention, the first bialuminate solution as described in step (1)
Concentration is 40~100 gAl2O3/ L, preferably 50~80gAl2O3/ L, 1~2L/h of coutroi velocity.
In the preparation method of hydrogenation conversion of the present invention, alkaline solution described in step (2) is sodium hydroxide, hydrogen-oxygen
Change one or more, the preferred sodium carbonate of potassium, sodium carbonate, sodium bicarbonate.
In the preparation method of hydrogenation conversion of the present invention, the concentration of alkaline solution described in step (2) is 0.5mol/
L~2.0mol/L, 1.0~2.0L/h of coutroi velocity.
In the preparation method of hydrogenation conversion catalyst of the present invention, the second bialuminate described in step (2) is sulfuric acid
The one or more of aluminium, aluminum nitrate, aluminium chloride etc., preferably sulfuric acid aluminium.
In the preparation method of hydrogenation conversion catalyst of the present invention, the second bialuminate solution described in step (2)
Concentration is 20~50gAl2O3/ L, preferably 20~40gAl2O3/ L, 0.4~1.0L/h of coutroi velocity.
In the preparation method of hydrogenation conversion catalyst of the present invention, the concentration of the first bialuminate solution is than the second acidic aluminum
High 20~the 80gAl of the concentration of acid salt solution2O3/ L, preferably high 40~60gAl2O3/L。
In the preparation method of hydrogenation conversion catalyst of the present invention, inorganic agent A described in step (2) is triethanolamine, different
Propanolamine, polyacrylamide, ammonium dodecyl ether sulfate, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride
One of and several, preferably one or more of triethanolamine, isopropanolamine, polyacrylamide, further preferably
Triethanolamine.
In the preparation method of hydrogenation conversion catalyst of the present invention, inorganic agent A concentration described in step (2) is 0.5~5wt%,
1.0~2.0L/h of coutroi velocity.
In the preparation method of hydrogenation conversion catalyst of the present invention, inorganic agent A described in step (2) is in alkaline solution and second
It is added before bialuminate solution cocurrent, the slurries preferably obtained with step (1) while introducing second reactor.
In the preparation method of hydrogenation conversion catalyst of the present invention, step (2) neutral and alkali solution, the second bialuminate solution
It is added simultaneously.
In the preparation method of hydrogenation conversion catalyst of the present invention, alkaline solution, the second acidic aluminum is added in cocurrent in step (2)
When acid salt solution, be preferably additionally added inorganic agent B, the inorganic agent B be one of polyethylene glycol, OP-20, Span, tween or
Several, the molecular weight of the polyethylene glycol is not less than 10000.
In the preparation method of hydrogenation conversion catalyst of the present invention, the additional amount of inorganic agent B described in step (2) is second
2~8wt% of alumina content, preferably 3~5wt% in bialuminate.
In the preparation method of hydrogenation conversion catalyst of the present invention, the acid aluminic acid of inorganic agent B described in step (2) and second
Salting liquid is added simultaneously.
In the preparation method of hydrogenation conversion catalyst of the present invention, reaction temperature described in step (1) is 50 DEG C~95 DEG C, excellent
It is selected as 60 DEG C~95 DEG C, further preferably 65 DEG C~85 DEG C.
In the preparation method of hydrogenation conversion catalyst of the present invention, reaction temperature described in step (2) is 50 DEG C~95 DEG C, excellent
It is selected as 60 DEG C~95 DEG C, further preferably 65 DEG C~85 DEG C.
In the preparation method of hydrogenation conversion catalyst of the present invention, washing described in step (3), can in temperature 50 C~70 DEG C
To be washed using water.Drying condition: 100~150 DEG C drying 2~6 hours, preferably 110~130 DEG C, dry 4~6 hours.
It, can also be according to reality in the preparation process of the boehmite in the preparation method of hydrogenation conversion catalyst of the present invention
Border needs to be added auxiliary agent, such as SiO2、P2O5、B2O3、TiO2One or more of predecessor, the predecessor is with water-soluble inorganic
The form of object is added, and can be added, can also be individually added into together with alkali aluminate soln.Auxiliary agent predecessor can be silicic acid
One of salt, phosphoric acid, boric acid, titanium sulfate, Titanium Nitrate are a variety of.Promoter addition can be added according to demand.
In the preparation method of hydrogenation conversion catalyst of the present invention, the forming process of step (4) described boehmite can be with
Shaping assistant is added to complete, shaping assistant is adhesive, peptizing agent or extrusion aid etc., as sesbania powder methylcellulose, silicon are molten
Glue, ammonium dihydrogen phosphate etc. it is one or more, additional amount be alumina content 2~8%, preferably 2~5%.Drying condition: 100
~150 DEG C drying 2~6 hours, preferably 110~130 DEG C, dry 4~6 hours.Roasting condition: 500~800 DEG C of roastings 2~6 are small
When, preferably 600~750 DEG C roast 3~6 hours.Hydrogenation conversion catalyst provided by the invention requires carrier therein depending on different
It can be made into various easily operated moldings, such as spherical shape, honeycomb, nest like, tablet or bar shaped (clover, butterfly, circle
Cylindricality etc.), it is preferably spherical.The molding carries out according to a conventional method, for example, squeezing out one of balling-up, tabletting and extruded moulding
The combination of method or several method.
In the preparation method of hydrogenation conversion catalyst of the present invention, in supported on carriers active component described in step (5)
Method can be using the existing any method in this field, in the premise that can guarantee to be carried on active component on carrier
Under, carrying method is not particularly limited, it is preferred to use infusion process.The dipping for specially preparing the compound containing the metal is molten
Liquid, the carrier described with solution dipping later, then catalyst is obtained through dry and roasting.The dipping method is routine side
Method, for example, it may be excessive liquid dipping, hole saturation infusion process.The active component is vib metals and/or Section VIII
Race's metal, one of described soluble compound of metal component compound in them contained selected from group vib or several
Kind, such as one or more of molybdenum oxide, molybdate, paramolybdate, molybdenum oxide, ammonium molybdate, ammonium paramolybdate preferably wherein；Tungsten
One or more of hydrochlorate, metatungstate, ethyl metatungstate, ammonium metatungstate, ethyl ammonium metatungstate preferably wherein.It is described
Be selected from their one or more of soluble compound containing the compound selected from group VIII metal component, as cobalt nitrate,
One or more of cobalt acetate, basic cobaltous carbonate, cobalt chloride and soluble complexes of cobalt, preferably cobalt nitrate, alkali formula carbon
Sour cobalt；One or more of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and soluble complexes of nickel, preferably nitre
Sour nickel, basic nickel carbonate.
In the preparation method of hydrogenation conversion catalyst of the present invention, drying condition described in step (5): 100~150 DEG C of dryings
2~6 hours, preferably 110~130 DEG C, it is 4~6 hours dry.Roasting condition: 400~600 DEG C roast 2~6 hours, preferably 450
~600 DEG C roast 3~6 hours.
Third aspect present invention provides a kind of inferior raw material method of hydrotreating, under the conditions of hydroconversion reactions, hydrocarbon ils is bad
Matter raw material and hydrogen are contacted with above-mentioned hydrogenation conversion catalyst to be reacted.It is not special to the reaction condition of the hydro-conversion
Limitation, the preferably described hydroconversion reactions condition are as follows: 380~450 DEG C of reaction temperature, preferably 400~440 DEG C, hydrogen partial pressure 4~
25MPa, preferably 13~20 MPa, liquid volume air speed (LHSV) are 0.3~5.0h-1, preferably 0.3~2.0h-1, hydrogen oil volume
Than 200~2500, preferably 500~1000.
In inferior raw material method of hydrotreating of the present invention, the inferior raw material can be reduced crude, decompression residuum, frivolous
One or more of coal tar, heavy deasphalted oil.
In inferior raw material method of hydrotreating of the present invention, the device for carrying out hydrogenation reaction can be fixed bed reaction
Device, one or more of moving-burden bed reactor, suspended-bed reactor or fluidized bed reactor, is particularly suitable for ebullating bed reactor
Device.
According to the conventional method in this field, the hydrogenation conversion catalyst carries out presulfurization before the use, this pre-
Vulcanization can carry out also In-situ sulphiding in device outside device, and the active metal component that it is loaded is converted into metal sulfide group
Point, the means for realizing presulfurization can be realized any hand to hydrotreating catalyst vulcanization using this field
Section, this operation and selection are to be easy determination to those skilled in the art.
Hydrogenation conversion catalyst provided by the invention can be used alone, and can also use with other catalyst combinations, should
Catalyst carries out hydro-conversion particularly suitable for heavy oil especially poor residuum, converts residual oil effectively.
Compared with prior art, hydrogenation conversion catalyst of the present invention and preparation method thereof has the advantages that
1, in the preparation method of hydrogenation conversion catalyst of the present invention, prepare first Kong Rong great, pore distribution concentration, apparent density it is low and
The good boehmite of cohesiveness has hole as the hydrogenation conversion catalyst of carrier using the aluminium oxide of this boehmite preparation
Rong great, pore-size distribution are concentrated, and hydrogenation activity is high, and wear-resisting property is good, and high density of surface hydroxyl catalyst can form more work
Property phase, hydrogenation activity is high.
2, the present invention adds in the preparation method of hydro-conversion, in the preparation of boehmite, by the way that two-step reaction is arranged,
Wherein first step reaction uses the first bialuminate solution of rather high concentration, continuous by liquid liquid with alkali aluminate soln
Cocurrent mode synthesizes pseudoboehmite slurry, and the slurries controlled by reaction condition, in acidity, slurries enter second
Inorganic agent A is introduced when reactor, in conjunction with the full die in slurries that inorganic agent A can be obtained with the first step, by full die
It protects, guarantees that more the reaction was continued on imperfect crystal grain for the relatively low intensity of second bialuminate solution introduced
Obtain product identical with full die.Preparation method of the present invention, which solves to prepare using conventional continuous cocurrent mode, intends thin water aluminium
Shi Shi causes the reaction mass residence time different due to liquid agitation back-mixing, thus the complete and imperfect crystal grain generated
It flows out together, subsequent plastic reaction causes imperfect crystal grain to become smaller or dissolve, to cause due to intergranular micro-environmental variation
The technical issues of obtained boehmite grain size is different, and cohesiveness is poor, influences subsequent oxidation aluminium product property.
3, in the preparation method of hydrogenation conversion catalyst of the present invention, the preparation of boehmite by using two-stage reaction,
Introduce different disposal agent, different reaction conditions, various concentration bialuminate solution multiple means collective effect under, can be with
The Aging Step in conventional preparation techniques is saved, process flow is shortened, entire preparation process is more energy saving, from economic angle
It is more suitable for large-scale industrial production on degree.
4, in the preparation method of hydrogenation conversion catalyst of the present invention, since there are nucleus generations for boehmite preparation process
With two stages of growth, the first step is reacted using the first bialuminate solution and sodium metaaluminate, quickly generates boehmite
There is complete or incomplete crystal grain, it is molten that inorganic agent A is added in second step due to material back-mixing in nucleus and slow growth
The concentration of liquid, the second bialuminate solution and alkaline solution, slurries reduces, and under alkaline condition, is more advantageous to imperfect crystalline substance
Grain growth, meanwhile, in the second reaction process, the second bialuminate is mixed with inorganic agent B, generates imperfect particle complete
Particle does not reassociate, grows up.
Specific embodiment
Technical solution of the present invention is further illustrated by the following examples, but is not limited to following embodiment.The present invention
In, specific surface area, Kong Rong and pore size distribution are using low temperature liquid nitrogen determination of adsorption method.
The measuring method of the density of surface hydroxyl of heretofore described catalyst: it weighs 0.5g catalyst sample and is ground
Mill, it is stand-by to be ground to sample of the granularity less than 1 micron.It weighs 10mg sample and carries out tabletting, be transferred to in-situ ft-ir instrument
It is 10 in vacuum degree in pond in situ-3Under conditions of Pa, the sample in pond in situ is heated, heating rate is 10 DEG C/min,
500 DEG C are warming up to, then under vacuum conditions constant temperature 2h is down to room temperature.Spectrum is acquired with in-situ ft-ir instrument, wherein peak
3600~3850cm of position-1For the peak of the surface hydroxyl of sample, by catalyst prepared by the present invention and pass through SB powder in the same terms
The catalyst of lower preparation measures the area at surface hydroxyl peak respectively, and the ratio between two figure peak areas are two kinds of catalyst sample tables
Face hydroxy density molar ratio, the SB powder are provided by German Sasol company, Kong Rongwei 0.5mL/g.
Embodiment 1
To 150mL water is added in first reactor (volume 500mL), then sodium aluminate solution is added in continuous cocurrent
(180gAl2O3/ L), flow velocity is acid aluminum sulfate solution (80 gAl of 1.1L/h and first2O3/ L), flow velocity 1.8L/h is adjusted
Solution pH value is 6.5, controls 75 DEG C of first reactor gelling temperature.Slurries are obtained after reaction, and 0.7% triethanolamine liquid is added,
Flow velocity is 1.8L/h, into second reactor (volume 500mL).Then 1.5mol/L sodium carbonate liquor is added in cocurrent, and flow velocity is
Acid aluminum sulfate (30 gAl of 0.6L/h and second2O3/ L) solution, flow velocity 0.7L/h and polyethylene glycol (molecular weight 20000)
0.75g/h, adjusting solution pH value is 8.0, controls 55 DEG C of second reactor gelling temperature.Suspension is obtained after reaction to wash at 60 DEG C
Underwater washing is washed, it is 4 hours dry at 120 DEG C, obtain boehmite A.
Weigh 200g preparation boehmite A, be added sesbania powder 4.2g and 200g water purification after be uniformly mixed, balling-up at
Type, sample obtain the ball type carrier that granularity is 0.8~1.0mm by 120 DEG C of dry 3,700 DEG C of roastings 3h.Ball type carrier is soaked
Stain Mo-Ni-P(12-3.0-1.3%) solution, it is 4 hours dry at 120 DEG C, it is roasted 3 hours through 480 DEG C and obtains catalyst S-A,
Catalyst property is shown in Table 1, and evaluating catalyst the results are shown in Table 4.
When measuring catalyst surface hydroxy density, reference catalyst is prepared according to above-mentioned preparation method, will only intend thin water
Aluminium stone A replaces with 200gSB powder, and the SB powder is provided by German Sasol company, Kong Rongwei 0.5mL/g.Latter embodiments and
The density of surface hydroxyl of catalyst described in comparative example is tested using identical method, exactly by embodiment and is compared
Boehmite in example replaces with SB powder.
Embodiment 2
Other conditions are prepared with embodiment 1, first reactor solution pH value are only adjusted to 6, first reactor gelling temperature
80 DEG C, the concentration of inorganic agent A is 0.9%, and boehmite B and catalyst S-B is prepared in flow velocity 1.0L/h.Catalyst property
It is shown in Table 1, evaluating catalyst the results are shown in Table 4.
Embodiment 3
Other conditions are prepared with embodiment 1, only inorganic agent A is changed to polyacrylamide liquid, by second reactor solution pH value
10 are adjusted to, 40 DEG C of second reactor gelling temperature, boehmite C is prepared.The microsphere supported dipping Mo-Ni of preparation
(15-3.5-1.5%) solution, it is 3 hours dry at 120 DEG C, it is roasted 3 hours through 550 DEG C and obtains catalyst S-C, catalyst property
It is shown in Table 1, evaluating catalyst the results are shown in Table 4.
Embodiment 4
Other conditions are prepared with embodiment 1, only inorganic agent B is changed to tween, additional amount 2.5g/h, the second acid aluminum sulfate
(40 gAl2O3/ L) solution, second reactor solution pH value is adjusted to 8, second reactor gelling temperature 70 by flow velocity 0.8L/h
DEG C, boehmite D is prepared, methylcellulose 2g and ammonium dihydrogen phosphate 2.4g is added in carrier preparation process, prepares grain
Degree is the ball type carrier of 1.0~1.5mm, is finally prepared into catalyst S-D.Catalyst property is shown in Table 1, and evaluating catalyst result is shown in
Table 4.
Embodiment 5
Other conditions are prepared with embodiment 1, only untreated dose of B, is prepared boehmite E and catalyst S-E.
Embodiment 6
To 200mL water is added in first reactor (volume 500mL), then sodium aluminate solution is added in continuous cocurrent
(150gAl2O3/ L), flow velocity is 1.0L/h and the first acidic nitric aluminum solutions (60 gAl2O3/ L), flow velocity 1.5L/h is adjusted
Solution pH value is 5.5, controls 80 DEG C of first reactor gelling temperature.Slurries are obtained after reaction, and 0.5% isopropanolamine liquid is added,
Flow velocity is 1.0L/h, into second reactor (volume 500mL).Then 0.7mol/L sodium carbonate liquor is added in cocurrent, and flow velocity is
Acid aluminum sulfate (20 gAl of 0.9L/h and second2O3/ L), flow velocity 0.8L/h and OP-20 solution 0.64g/h adjusts solution pH value
It is 9.0, controls 50 DEG C of second reactor gelling temperature.Suspension is obtained after reaction to wash under 60 DEG C of washing waters, it is dry at 130 DEG C
Dry 4 hours, obtain boehmite F.
Weigh 200g preparation intends thin aluminium stone F, mixes after sesbania powder 1g, methylcellulose 1g and 190g water purification is added
Even, at ball forming, sample is 4 hours dry by 110 DEG C, and 750 DEG C of roasting 4h obtain the ball type carrier that granularity is 1.6~2.0mm.
Ball type carrier is impregnated into Mo-Ni-P(12-3.0-1.3%) solution, it is 6 hours dry at 120 DEG C, it is roasted 3 hours through 580 DEG C
To catalyst S-F, catalyst property is shown in Table 1, and evaluating catalyst the results are shown in Table 4.
Comparative example 1
To 150mL water is added in first reactor (volume 500mL), then sodium aluminate solution is added in continuous cocurrent
(180gAl2O3/ L), flow velocity is acid aluminum sulfate solution (80 gAl of 1.1L/h and first2O3/ L), flow velocity 1.8L/h is adjusted
Solution pH value is 6.5, controls 75 DEG C of first reactor gelling temperature.Slurries are obtained after reaction enters second reactor (volume
500mL).Then 1.5mol/L sodium carbonate liquor is added in cocurrent, and flow velocity is acid aluminum sulfate (30 gAl of 0.6L/h and second2O3/
L) solution, flow velocity 0.7L/h, adjusting solution pH value is 8.0, controls 55 DEG C of second reactor gelling temperature.It is obtained after reaction suspended
Liquid washs under 60 DEG C of washing waters, 4 hours dry at 120 DEG C, obtains boehmite G.
Weigh 200g preparation intends thin aluminium stone G, is uniformly mixed after sesbania powder 4.2g and 200g water purification is added, at ball forming,
Sample obtains the ball type carrier that granularity is 0.8~1.0mm by 120 DEG C of dry 3,700 DEG C of roastings 3h.Ball type carrier is impregnated
Mo-Ni-P(12-3.0-1.3%) solution, it is 4 hours dry at 120 DEG C, it is roasted 3 hours through 480 DEG C and obtains catalyst S-A, urged
Agent property is shown in Table 1, and evaluating catalyst the results are shown in Table 4.
Comparative example 2
To 150mL water is added in first reactor (volume 500mL), then sodium aluminate solution is added in continuous cocurrent
(180gAl2O3/ L), flow velocity is acid aluminum sulfate solution (80 gAl of 1.1L/h and first2O3/ L), flow velocity 1.8L/h is adjusted
Solution pH value is 6.5, controls 75 DEG C of first reactor gelling temperature.Slurries are obtained after reaction enters second reactor (volume
500mL).Then 1.5mol/L sodium carbonate liquor is added in cocurrent, and flow velocity is acid aluminum sulfate (30 gAl of 0.6L/h and second2O3/
L) solution, flow velocity 0.7L/h and polyethylene glycol (molecular weight 20000) 0.75g/h, adjusting solution pH value is 8.0, control second
55 DEG C of reactor gelling temperature.Suspension is obtained after reaction to wash under 60 DEG C of washing waters, it is 4 hours dry at 120 DEG C, intended
Boehmite H.
Weigh 200g preparation intends thin aluminium stone A, is uniformly mixed after sesbania powder 4.2g and 200g water purification is added, at ball forming,
Sample obtains the ball type carrier that granularity is 0.8~1.0mm by 120 DEG C of dry 3,700 DEG C of roastings 3h.Ball type carrier is impregnated
Mo-Ni-P(12-3.0-1.3%) solution, it is 4 hours dry at 120 DEG C, it is roasted 3 hours through 480 DEG C and obtains catalyst S-H, urged
Agent property is shown in Table 1, and evaluating catalyst the results are shown in Table 4.
Comparative example 3
To 150mL water is added in first reactor (volume 500mL), then sodium aluminate solution is added in continuous cocurrent
(180gAl2O3/ L), flow velocity is acid aluminum sulfate solution (80 gAl of 1.1L/h and first2O3/ L), flow velocity 1.8L/h is adjusted
Solution pH value is 6.5, controls 75 DEG C of first reactor gelling temperature.Slurries are obtained after reaction, and 0.7% triethanolamine liquid is added,
Flow velocity is 1.8L/h, into second reactor (volume 500mL).Then 1.5mol/L sodium carbonate liquor is added in cocurrent, and flow velocity is
Acid aluminum sulfate (80 gAl of 0.6L/h and second2O3/ L) solution, flow velocity 0.7L/h and polyethylene glycol (molecular weight 20000)
0.75g/h, adjusting solution pH value is 8.0, controls 55 DEG C of second reactor gelling temperature.Suspension is obtained after reaction to wash at 60 DEG C
Underwater washing is washed, it is 4 hours dry at 120 DEG C, obtain boehmite I.
Weigh 200g preparation intends thin aluminium stone A, is uniformly mixed after sesbania powder 4.2g and 200g water purification is added, at ball forming,
Sample obtains the ball type carrier that granularity is 0.8~1.0mm by 120 DEG C of dry 3,700 DEG C of roastings 3h.Ball type carrier is impregnated
Mo-Ni-P(12-3.0-1.3%) solution, it is 4 hours dry at 120 DEG C, it is roasted 3 hours through 480 DEG C and obtains catalyst S-I, urged
Agent property is shown in Table 1, and evaluating catalyst the results are shown in Table 4.
Comparative example 4
To 150mL water is added in first reactor (volume 500mL), then sodium aluminate solution is added in continuous cocurrent
(180gAl2O3/ L), flow velocity is acid aluminum sulfate solution (30 gAl of 1.1L/h and first2O3/ L), flow velocity 1.8L/h is adjusted
Solution pH value is 6.5, controls 75 DEG C of first reactor gelling temperature.Slurries are obtained after reaction, and 0.7% triethanolamine liquid is added,
Flow velocity is 1.8L/h, into second reactor (volume 500mL).Then 1.5mol/L sodium carbonate liquor is added in cocurrent, and flow velocity is
Acid aluminum sulfate (30 gAl of 0.6L/h and second2O3/ L) solution, flow velocity 0.7L/h and polyethylene glycol (molecular weight 20000)
0.75g/h, adjusting solution pH value is 8.0, controls 55 DEG C of second reactor gelling temperature.Suspension is obtained after reaction to wash at 60 DEG C
Underwater washing is washed, it is 4 hours dry at 120 DEG C, obtain boehmite J.
Weigh 200g preparation intends thin aluminium stone A, is uniformly mixed after sesbania powder 4.2g and 200g water purification is added, at ball forming,
Sample obtains the ball type carrier that granularity is 0.8~1.0mm by 120 DEG C of dry 3,700 DEG C of roastings 3h.Ball type carrier is impregnated
Mo-Ni-P(12-3.0-1.3%) solution, it is 4 hours dry at 120 DEG C, it is roasted 3 hours through 480 DEG C and obtains catalyst S-J, urged
Agent property is shown in Table 1, and evaluating catalyst the results are shown in Table 4.
The property of 1 catalyst of table
As can be seen from the table: being concentrated using hydrotreating catalyst Kong Rong great prepared by the present invention, pore-size distribution, abrasion
Low, surface hydroxyl molar ratio is high.
Above-mentioned catalyst is measured into 200mL respectively, activity rating, the property of residual oil raw material used are carried out on autoclave
2 are shown in Table, evaluation condition is shown in Table 3, and evaluation result is shown in Table 4.
2 raw material oil nature of table
Table 3 evaluates process conditions
The evaluation result of 4 different catalysts of table
From evaluation result it can be seen that processing decompression residuum inferior using inferior raw material hydrogenation conversion catalyst prepared by the present invention
When, it shows higher plus hydrogen and takes off impurity activity, residual oil is effectively converted.
Claims (31)
1. a kind of hydrogenation conversion catalyst, the hydrogenation conversion catalyst includes active component and carrier；Institute's active component is the
Group vib metal and/or group VIII metal, on the basis of catalyst weight, vib metals content in terms of oxide is
8.0w%~18.0wt%, group VIII metal content in terms of oxide are 1.0wt%~8.0wt%, the table of hydrogenation conversion catalyst
Face hydroxy density and the catalyst surface hydroxy density molar ratio of SB powder preparation are 1.1~1.6.
2. hydrogenation conversion catalyst described in accordance with the claim 1, it is characterised in that: on the basis of catalyst weight, group VIB
Metal content in terms of oxide is 9.0wt%~15.0wt%, group VIII metal in terms of oxide content for 2.0wt%~
5.0wt%。
3. hydrogenation conversion catalyst described in accordance with the claim 1, it is characterised in that: the vib metals are W and/or Mo,
Group VIII the metal Co and/or Ni.
4. hydrogenation conversion catalyst described in accordance with the claim 1, it is characterised in that: the active component is Mo and Ni.
5. hydrogenation conversion catalyst described in accordance with the claim 1, it is characterised in that: 0.55~0.70mL/g of Kong Rongwei compares table
Area is 150~220m2/ g, preferably 150~200m2/g。
6. hydrogenation conversion catalyst described in accordance with the claim 1, it is characterised in that: the pore size distribution of hydrogenation conversion catalyst is such as
Under: the Kong Rong in the hole of bore dia < 8nm accounts for the 15% of total pore volume hereinafter, preferably 10% hereinafter, bore dia is the hole of 8~15nm
Kong Rong accounts for the 60%~80% of total pore volume, preferably 70%~80%, the Kong Rong in the hole of bore dia > 15nm account for total pore volume 15%~
25%, preferably 18%~25%.
7. hydrogenation conversion catalyst described in accordance with the claim 1, it is characterised in that: the surface hydroxyl of hydrogenation conversion catalyst is close
Degree and the catalyst surface hydroxy density molar ratio of SB powder preparation are 1.2~1.5.
8. hydrogenation conversion catalyst described in accordance with the claim 1, it is characterised in that: the partial size of hydrogenation conversion catalyst is 0.8
~2.0mm, the abrasion < 1.5wt% of catalyst, preferably < 1.0wt%.
9. the preparation method of hydrogenation conversion catalyst described in any claim in claim 1-8, the preparation method include
Following content:
(1) water is added into first reactor, alkali aluminate soln and the first acidic aluminum are then added in a manner of continuous cocurrent
Acid salt solution, adjusting solution pH value is 3~6.5, preferably 4~6, obtains slurries after reaction；
(2) slurries, inorganic agent A are continually introduced into second reactor, then it is molten that alkaline solution, the second bialuminate is added in cocurrent
Liquid, adjusting solution pH value is 7~10, preferably 7.5~9, obtains suspension after reaction；
(3) step (2) resulting suspension obtains boehmite after being filtered, washed and dried drying；
(4) boehmite that step (3) obtains is obtained into carrier after molding, drying, roasting；
(5) the carrier loaded active component for obtaining step (4) obtains catalyst by dry and roasting.
10. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: first described in step (1)
The additional amount of water is 1/4~1/2, preferably the 1/4~1/3 of first reactor volume in reactor.
11. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: alkalinity described in step (1)
Aluminate is one of sodium metaaluminate, potassium metaaluminate or a variety of, preferably sodium metaaluminate.
12. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: alkalinity described in step (1)
The concentration of aluminate solution is 100~250gAl2O3/ L, preferably 150~200gAl2O3/L。
13. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: as described in step (1)
One bialuminate is one or more of aluminum sulfate, aluminum nitrate, aluminium chloride, preferably sulfuric acid aluminium.
14. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: as described in step (1)
The concentration of one bialuminate solution is 40~100gAl2O3/ L, preferably 50~80gAl2O3/L。
15. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: alkali described in step (2)
Property solution be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate one or more, preferred sodium carbonate.
16. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: alkali described in step (2)
Property solution concentration be 0.5mol/L~2.0mol/L.
17. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: described in step (2)
Two bialuminates are the one or more of aluminum sulfate, aluminum nitrate, aluminium chloride etc., preferably sulfuric acid aluminium.
18. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: described in step (2)
The concentration of two acid aluminate solutions is 20~50gAl2O3/ L, preferably 20~40gAl2O3/L。
19. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: the first bialuminate is molten
The concentration of liquid is 20~80gAl higher than the concentration of the second bialuminate solution2O3/ L, preferably high 40~60gAl2O3/L。
20. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: place described in step (2)
Reason agent A is triethanolamine, isopropanolamine, polyacrylamide, ammonium dodecyl ether sulfate, hexadecyltrimethylammonium chloride, ten
One of eight alkyl trimethyl ammonium chlorides and several, preferably one of triethanolamine, isopropanolamine, polyacrylamide or
It is several, further preferably triethanolamine.
21. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: handled described in step (2)
Agent A concentration is 0.5~5wt%.
22. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: cocurrent is added in step (2)
When alkaline solution, the second bialuminate solution, inorganic agent B is added, the inorganic agent B is polyethylene glycol, OP-20, Span, spits
The molecular weight of one or more of temperature, the polyethylene glycol is not less than 10000.
23. according to the preparation method of hydrogenation conversion catalyst described in claim 22, it is characterised in that: described in step (2)
The additional amount of inorganic agent B is the 2~8wt%, preferably 3~5wt% of alumina content in the second bialuminate.
24. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: reacted described in step (1)
Temperature is 50 DEG C~95 DEG C, preferably 60 DEG C~95 DEG C, further preferably 65 DEG C~85 DEG C.
25. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: reacted described in step (2)
Temperature is 50 DEG C~95 DEG C, preferably 60 DEG C~95 DEG C, further preferably 65 DEG C~85 DEG C.
26. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: washed described in step (3)
In temperature 50 C~70 DEG C, washed using water；Drying condition: 100~150 DEG C of dryings 2~6 hours, preferably 110~130
DEG C, it is 4~6 hours dry.
27. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: step is carrying described in (5)
The method of load active component uses infusion process on body, the dipping solution including preparing the compound containing the active component, it
The carrier described with solution dipping afterwards, then catalyst is obtained through dry and roasting.
28. according to the preparation method of hydrogenation conversion catalyst described in claim 27, it is characterised in that: the active component is the
Group vib metal and/or group VIII metal, the soluble chemical combination containing the metal component compound selected from group vib in them
One or more of object, containing the compound selected from group VIII metal component be selected from they one of soluble compound or
It is several.
29. according to the preparation method of hydrogenation conversion catalyst described in claim 9, it is characterised in that: dry described in step (5)
Condition: 100~150 DEG C drying 2~6 hours, preferably 110~130 DEG C, dry 4~6 hours；Roasting condition: 400~600 DEG C of roastings
It burns 2~6 hours, preferably 450~600 DEG C roast 3~6 hours.
30. a kind of inferior raw material method of hydrotreating, it is characterised in that: urged using described in any claim in claim 1-8
Agent reacts hydrocarbon ils inferior raw material and hydrogen contact under the conditions of hydroconversion reactions.
31. according to the method for claim 30, it is characterised in that: hydroconversion reactions condition are as follows: reaction temperature 380~
450 DEG C, preferably 400~440 DEG C, 4~25MPa of hydrogen partial pressure, preferably 13~20 MPa, liquid volume air speed are 0.3~5.0h-1,
It is preferred that 0.3~2.0h-1, hydrogen to oil volume ratio 200~2500, preferably 500~1000.
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Effective date of registration: 20231011 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |