CN115254083B - Preparation method of aluminum-zirconium composite carrier and distillate oil hydrofining catalyst containing carrier - Google Patents
Preparation method of aluminum-zirconium composite carrier and distillate oil hydrofining catalyst containing carrier Download PDFInfo
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- CN115254083B CN115254083B CN202110487926.8A CN202110487926A CN115254083B CN 115254083 B CN115254083 B CN 115254083B CN 202110487926 A CN202110487926 A CN 202110487926A CN 115254083 B CN115254083 B CN 115254083B
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- zirconium
- aluminum
- composite carrier
- carrier
- solution
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- 239000002131 composite material Substances 0.000 title claims abstract description 123
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 41
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 21
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 19
- 239000000017 hydrogel Substances 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 239000000499 gel Substances 0.000 claims abstract description 17
- 238000000967 suction filtration Methods 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 15
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 13
- 239000001923 methylcellulose Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 235000010981 methylcellulose Nutrition 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 57
- 238000005984 hydrogenation reaction Methods 0.000 description 15
- 239000003921 oil Substances 0.000 description 12
- 239000002283 diesel fuel Substances 0.000 description 10
- 241000219782 Sesbania Species 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- 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 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention relates to a preparation method of an aluminum-zirconium composite carrier, which comprises the following steps: adding ammonia water into the zirconium-containing solution, adjusting the pH value, stirring, and aging to obtain zirconium-containing hydrosol; filtering the zirconium-containing hydrosol to obtain a solid, and washing with deionized water to remove Cl ‑ in the solid to obtain zirconium-containing hydrogel; adding pseudo-boehmite and methylcellulose into the zirconium-containing hydrogel to prepare zirconium-aluminum sol; adjusting the pH value of the aluminum zirconium sol to form gel, aging, washing with water, carrying out suction filtration and drying to obtain a zirconium aluminum composite material, adding a binder and a lubricant into the composite material, uniformly mixing, extruding and molding, drying, and roasting to obtain the ZrO 2/γ-Al2O3 composite carrier. The composite carrier has the advantages of high specific surface area, large pore volume, high mechanical strength and good stability, and zirconia contained in the composite carrier is enriched on the surface of the carrier, so that the co-catalysis effect of the zirconia is effectively exerted. The invention also relates to a distillate oil hydrofining catalyst.
Description
Technical Field
The invention relates to the field of petroleum refining hydrofining, in particular to a preparation method of an aluminum-zirconium composite carrier and a middle distillate hydrofining catalyst taking the composite carrier as a carrier.
Background
The construction resource saving and environment friendly oil refining industry becomes one of important key problems to be solved urgently in the sustainable development of national economy and society in China, and the production of ultralow-sulfur and high-combustion-efficiency vehicle fuel plays a key role in promoting the coordinated development of energy, economy and environment. In order to solve the problem of serious air pollution in large and medium cities caused by rapid increase of the holding capacity of automobiles, china speeds up the upgrading of the oil quality. National VI clean diesel standard has been fully implemented on 1 month 1 2019.
With the increase of the heavy and inferior degree of crude oil, the processing difficulty of diesel oil is continuously increased. Meanwhile, the annual demand of diesel oil is approximately 1.8 hundred million tons, the quality upgrading of the diesel oil is quickened, and the production of high-quality clean diesel oil becomes one of the key works of the current refining enterprises. The quality upgrading method aims at the existing diesel hydrogenation device, and the currently available means mainly comprise the steps of reducing the device throughput, improving the reaction severity of the device, reducing the diesel end point and using a high-activity diesel hydrogenation catalyst. Measures such as reducing the processing capacity of the device, improving the reaction severity of the device, reducing the end point of diesel oil and the like have adverse effects on the production cost and the production efficiency of the device. To solve the above problems, foreign Criterion, exxon Mobil, IFP, akzo Nobel, UOP, haldorThe companies respectively develop high-activity hydrogenation catalysts suitable for deep hydrodesulfurization reaction of diesel oil, and realize wide application. Therefore, the research and development of the high-activity diesel hydrogenation catalyst is the most effective measure for upgrading the quality of diesel by a diesel hydrogenation device, and accords with the development trend of the world oil refining technology.
In order to develop a novel high-activity hydrogenation catalyst, research institutions at home and abroad mainly improve the performance of the hydrogenation catalyst by adopting novel catalytic materials, optimizing a catalyst preparation method and other means. The development of novel catalytic materials can change and promote the activity of hydrogenation catalysts essentially, and is an effective way for developing high-activity hydrogenation catalysts.
The main starting point for improving the efficiency of hydrodesulfurization is to improve the supporting technology, modify the catalyst and develop a novel catalyst. The development of the novel catalyst is easier than the former two. Alumina is used as the carrier of the traditional hydrodesulfurization catalyst, has the characteristics of high specific surface area, high thermal stability and the like, but the alumina is an inert carrier, and the activity and the toxicity resistance of the alumina are still to be improved. Zirconium dioxide is used as an important structural functional material, has the characteristics of high temperature resistance, high hardness, good chemical stability and thermal stability and the like, and is widely applied to the fields of structural ceramics, sensors, solar cells, heat insulation materials and the like. Zirconium dioxide is prone to oxygen vacancies and can interact uniquely with the active component and is therefore also a very characteristic catalyst support. The zirconia-supported catalysts exhibit unique advantages over conventional supports, such as good sulfur resistance, easy reduction of the supported metal, and the like. However, the conventional zirconium dioxide carrier has small specific surface, less developed pores, irregular pore size change and the like, and limits the exertion of the excellent performance of the zirconium dioxide carrier.
Patent ZL00123133.2 discloses a zirconium-containing aluminum oxide carrier and a preparation method thereof, wherein the zirconium-containing aluminum oxide carrier is prepared by adding a zirconium-containing compound in a wet Fresnel mode in the forming process of the carrier; the side pressure intensity of the carrier is 12-24N/mm, and the infrared acidity is 0.25-0.30 mmol/g. The method has the main defects that the composite carrier prepared in a wet Fresnel mode has strong randomness, and the zirconium-containing compound is introduced into the alumina through a wet kneading process, so that the uniform dispersion of the zirconium-containing compound is not facilitated, and the hydrodesulfurization activity of the catalyst is adversely affected.
Patent ZL201310524738.3 discloses a diesel hydrodesulfurization denitrification catalyst and a preparation method thereof, wherein the catalyst comprises a carrier, an auxiliary agent and active metal; the carrier is an Al 2O3-ZrO2-TiO2-SiO2 multi-element oxide composite carrier; the auxiliary agent is phosphorus; nickel, cobalt, molybdenum and tungsten are used as active components; the weight percentage content of each component based on the catalyst is as follows: 1 to 6 weight percent of cobalt oxide calculated by oxide; 1 to 15 weight percent of nickel oxide, 2 to 12 weight percent of molybdenum oxide, 12 to 35 weight percent of tungsten oxide and 1.5 to 5 weight percent of auxiliary agent phosphorus pentoxide; kong Rong 0.2.2 ml/g of catalyst, the specific surface area is not less than 140m 2/g, and the mechanical strength is not less than 15N/mm; the specific weight of each component in the composite carrier in the carrier is as follows: 2 to 15 weight percent of titanium oxide, 2 to 20 weight percent of silicon oxide and 5 to 15 weight percent of zirconium oxide; the balance being alumina. The preparation method of the composite carrier comprises the steps of uniformly mixing pseudo-boehmite, zirconyl nitrate, meta-titanic acid (or nano-titanium dioxide or tetra-n-propyl titanate) and silica sol, adding a peptizing agent, an extrusion aid and a pore-expanding agent, kneading, extruding strips for molding, and drying and roasting to obtain the Al 2O3-ZrO2-TiO2-SiO2 multi-element oxide composite carrier. The same wet kneading method is adopted for preparing the composite carrier, and the same problems still exist.
Patent ZL 201010514168.6 discloses a preparation method of a zirconia-alumina composite oxide carrier, which adopts a method of preparing aluminum hydroxide sol and zirconium-containing sol in advance, introduces silicon when aluminum hydroxide forms gel, and adds a surfactant or an organic solvent into the zirconium-containing sol; after the PH values of the two colloids are respectively regulated, the two colloids are mixed and aged, and then washed, filtered and dried to obtain the zirconia-silica-alumina composite oxide dry adhesive. And adding an adhesive, an extrusion aid, a peptizing agent and an auxiliary agent into the composite oxide dry gel, kneading, extruding strips, drying and roasting to obtain the composite oxide carrier. Wherein the binder is small-pore alumina, and the dosage is 5-30wt% of the weight of the composite oxide carrier. The preparation process is complex, and in order to improve the dispersibility of the sol, a surfactant or an organic solvent is added into the zirconium-containing sol, so that the preparation process has more influence factors. In addition, small-pore alumina is added as a binder in the process of forming the composite oxide carrier, so that the physical properties of the carrier are affected, and the hydrodesulfurization activity of the catalyst is adversely affected.
The patent ZL201710329054.6 discloses a zirconia-containing composite catalyst carrier and a preparation method and application thereof, wherein the composite carrier consists of 10-60% of zirconia, 15-55% of zinc oxide and 15-55% of manganese oxide by 100% of carrier mass. The composite carrier is prepared by adopting a coprecipitation method, and the precipitate mixed solution is aged for 30min at 80-140 ℃, and is obtained by filtering, drying and roasting. The catalyst prepared by soaking K and Pd on the composite carrier is used in the reaction of preparing isobutanol from synthesis gas.
Patent ZL201110134042.0 discloses an alumina-zirconia composite carrier and a preparation method thereof. The carrier comprises 1-95% of alumina and 5-99% of zirconia by 100% of the mass of the carrier, and has the following physical properties: bulk density 0.8-1.1 g/ml, pore volume 0.3-0.6 ml/g, specific surface area 5-60 m 2/g, average pore diameter 80-350 nm, preferably 100-250 nm; the carrier shows double peaks at 90-140 nm and 250-500 nm. The patent also discloses a preparation method of the carrier and a hydrogenation catalyst containing the carrier.
Patent ZL201110267805.9 discloses an alumina-zirconia-titania composite carrier and a preparation method thereof. The carrier comprises 1-95% of alumina, 5-60% of zirconia and 5-60% of titanium oxide by 100% of carrier mass, and has the following physical properties: bulk density is 0.7-1.1 g/ml, pore volume is 0.2-0.6 ml/g, specific surface area is 3-60 m 2/g, average pore diameter is 50-300 nm; the carrier shows double peaks at 40-120 nm and 200-400 nm. The patent also discloses a preparation method of the carrier and a hydrogenation catalyst containing the carrier. The catalyst prepared by the two zirconium-containing composite carriers is used in the reaction of the carbon two-front hydrogenation.
Disclosure of Invention
Based on the above, the invention aims to provide a preparation method of a ZrO 2/γ-Al2O3 composite carrier, which has the advantages of larger specific surface area and pore volume, good stability and high mechanical strength, and zirconia contained in the composite carrier is enriched on the carrier surface, so that the co-catalysis effect of the zirconia is more effectively exerted.
The invention also provides a preparation method of the hydrofining catalyst taking the composite carrier as a carrier. Compared with the prior art, the catalyst can more effectively play the role of zirconia, and cooperatively adjust the physicochemical property and pore structure of the surface of the carrier, so that the catalyst has higher hydrodesulfurization activity and aromatic saturation performance.
In order to achieve the above purpose, the invention provides a preparation method of an aluminum-zirconium composite carrier, which comprises the following steps:
Step 1, adding zirconium oxychloride into water, and stirring until the zirconium oxychloride is fully dissolved to obtain a zirconium-containing solution;
step 2, dropwise adding the zirconium-containing solution into ammonia water, adjusting the pH value to 9-10, stirring for 0.5-2 h, and aging for 2-8 h;
Step 3, carrying out suction filtration on the material obtained in the step 2 to obtain a solid, and washing with deionized water to remove Cl - in the solid to obtain zirconium-containing hydrogel;
step 4, adding methyl cellulose, pseudo-boehmite and the zirconium-containing hydrogel into water, stirring and uniformly mixing the mixture according to the mass ratio of 1:5-20, heating the mixture to 80-85 ℃, stirring and simultaneously dropwise adding inorganic acid, regulating the pH value of the system to 2-3, and carrying out acidolysis at constant temperature for 4-8 hours to form aluminum-zirconium sol;
And 5, adjusting the pH of the aluminum-zirconium sol to 9-10 to form gel, aging for 2-10 h, washing to neutrality, carrying out suction filtration, and drying to obtain a zirconium-aluminum composite material, adding a binder and a lubricant into the zirconium-aluminum composite material, uniformly mixing, extruding and molding, wherein the total addition amount of the binder and the lubricant is 1-5wt% of the zirconium-aluminum composite material, and drying and roasting to obtain the ZrO 2/γ-Al2O3 composite carrier.
The preparation method of the aluminum-zirconium composite carrier provided by the invention is characterized in that the preferable content of zirconia in the composite carrier is 5-20wt% and the preferable content of alumina is 80-95wt%.
The preparation method of the aluminum-zirconium composite carrier is characterized in that the composite carrier is preferably clover-shaped, tooth-shaped, clover-shaped or granular, the specific surface area of the composite carrier is 260-400 m 2/g, the pore volume is 0.6-0.9 cm 3/g, and the mechanical strength is 180-270N/cm.
The preparation method of the aluminum-zirconium composite carrier provided by the invention is characterized in that the concentration of the zirconium-containing solution is preferably 0.18-0.24 mol/L.
The preparation method of the aluminum-zirconium composite carrier provided by the invention is characterized in that the addition amount of the methylcellulose is preferably 0.5-5 wt% of the weight of the aluminum-zirconium composite carrier.
The preparation method of the aluminum-zirconium composite carrier is characterized in that the inorganic acid is preferably one or more of hydrochloric acid, sulfuric acid and nitric acid.
The preparation method of the aluminum-zirconium composite carrier provided by the invention is characterized in that the binder is preferably one or more selected from nitric acid, citric acid, oxalic acid and tartaric acid; the lubricant is one or more selected from sesbania powder, dry starch, graphite and paraffin.
The preparation method of the aluminum-zirconium composite carrier provided by the invention is characterized in that the mass ratio of the binder to the lubricant is preferably 1:1-3:2.
The preparation method of the aluminum-zirconium composite carrier provided by the invention is characterized in that the roasting temperature in the step 5 is preferably 400-600 ℃ and the time is preferably 2-6 h.
The invention also provides a distillate oil hydrofining catalyst, which is prepared by taking the composite carrier prepared by the preparation method as a carrier, dipping active components, drying and roasting, wherein the active components comprise one or more of MoO 3、WO3, niO and CoO; preferably, the impregnation is an equal volume negative pressure impregnation.
The distillate oil hydrofining catalyst of the present invention, wherein preferably, the precursor solution of the active component is selected from at least two of an ammonium molybdate solution, a nickel nitrate solution, an ammonium phosphomolybdate solution, a nickel chloride solution, an ammonium meta-tungstate solution, a tungsten chloride solution, a cobalt nitrate solution, a cobalt chloride solution, a cobalt acetate solution and a nickel acetate solution.
The distillate oil hydrofining catalyst of the present invention, wherein the solvent of the precursor solution of the active component is preferably selected from one or more of water, ethanol and ammonia water.
Specifically, the preparation method of the ZrO 2/γ-Al2O3 composite carrier and the preparation method of the middle distillate hydrofining catalyst taking the composite carrier as the carrier provided by the invention comprise the following steps:
step 1, adding zirconium oxychloride into a container filled with water, and stirring until the zirconium oxychloride is fully dissolved;
step 2, slowly dripping the solution obtained in the step 1 into diluted ammonia water, regulating the pH value to 9-10, stirring for 0.5-2 h, and aging for 2-8 h;
Step 3, filtering the material obtained in the step 2, and washing off Cl - in the obtained solid by using deionized water to obtain zirconium-containing hydrogel;
step 4, adding methyl cellulose, pseudo-boehmite and the zirconium-containing hydrogel obtained in the step 3 into water, stirring and uniformly mixing the mixture, heating the mixture to 80-85 ℃, stirring and slowly dropwise adding inorganic acid, regulating the pH value of the system to 2-3, and carrying out constant-temperature acidolysis for 4-8 hours to form aluminum-zirconium sol;
Step 5, regulating the pH of the aluminum zirconium sol to 9-10 to form gel, aging for 2-10 h, washing to neutrality, carrying out suction filtration and drying to obtain a zirconium aluminum composite material, adding 1-5wt% of binder and lubricant based on the zirconium aluminum composite material into the zirconium aluminum composite material, uniformly mixing, extruding and molding, and drying and roasting to obtain the ZrO 2/γ-Al2O3 composite carrier;
And 6, soaking the ZrO 2/γ-Al2O3 composite carrier in a precursor solution of an active component, drying and roasting to obtain the middle distillate hydrofining catalyst, wherein the active component comprises one or more of MoO 3、WO3, niO and CoO.
Specifically, in the ZrO 2/γ-Al2O3 composite carrier, the content of zirconia is 5-20wt% and the content of alumina is 80-95wt%.
Specifically, the ZrO 2/γ-Al2O3 composite carrier is clover-shaped, tooth-shaped, clover-shaped or granular, the specific surface area of the composite carrier is 260-400 m 2/g, the pore volume is 0.6-0.9 cm 3/g, and the mechanical strength is 180-270N/cm.
Specifically, in the step 1 of the preparation method of the ZrO 2/γ-Al2O3 composite carrier, the concentration of ZrOCl 2·8H2 O is preferably 0.18-0.24 mol/L.
Specifically, in step 4 of the preparation method of the ZrO 2/γ-Al2O3 composite carrier, the adding amount of the methylcellulose is 0.5-5 wt% of the weight of the composite carrier.
Specifically, in step 4 of the preparation method of the ZrO 2/γ-Al2O3 composite carrier, the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid.
Specifically, in step 5 of the preparation method of the ZrO 2/γ-Al2O3 composite carrier, the binder is one or more selected from nitric acid, citric acid, oxalic acid and tartaric acid.
Specifically, in step 5 of the preparation method of the ZrO 2/γ-Al2O3 composite carrier, the lubricant is one or more selected from sesbania powder, dry starch, graphite and paraffin.
Specifically, in step 5 of the preparation method of the ZrO 2/γ-Al2O3 composite carrier, the roasting temperature is preferably 400-600 ℃, and the roasting time is preferably 2-6 h.
The precursor solution of the active component is preferably two or more of ammonium molybdate solution, nickel nitrate solution, ammonium phosphomolybdate solution, nickel chloride solution, ammonium metatungstate solution, tungsten chloride solution, cobalt nitrate solution, cobalt chloride solution, cobalt acetate solution and nickel acetate solution.
The invention relates to a preparation method of a middle distillate hydrofining catalyst, wherein the solvent in the precursor solution of the active component is preferably one or more of water, ethanol and ammonia water.
The preparation method of the intermediate distillate hydrofining catalyst provided by the invention is characterized in that the impregnation is preferably equal-volume negative pressure impregnation.
The composite carrier and the catalyst prepared by the invention have the advantages that:
(1) The composite carrier has high specific surface area, large pore volume, good stability and high mechanical strength, and is suitable for being used as a middle distillate oil hydrofining catalyst carrier.
(2) The zirconia in the composite carrier can weaken the strong interaction between the active component and the carrier, so that the active metal is easy to reduce, and the advantages of the zirconia active carrier are fully exerted.
(3) The preparation process and the conditions are simple and easy to control, the cost is low, and the preparation method is beneficial to industrial large-scale preparation.
(4) The catalyst prepared by the invention has high hydrodesulfurization and aromatic hydrocarbon saturation activities, can remove sulfur in diesel oil with the sulfur content of 5162ppm and the polycyclic aromatic hydrocarbon content of 26.5wt% to less than 10ppm, and has the polycyclic aromatic hydrocarbon content of less than 7wt%, so that the product meets the clean diesel oil standard of China VI. The catalyst has good stability, and can provide technical support for the hydrogenation device to realize the long-period operation target of 'five years of repair'.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The preparation method of the aluminum-zirconium composite carrier provided by the invention comprises the following steps:
Step 1, adding zirconium oxychloride into water, and stirring until the zirconium oxychloride is fully dissolved to obtain a zirconium-containing solution;
step 2, dropwise adding the zirconium-containing solution into ammonia water, adjusting the pH value to 9-10, stirring for 0.5-2 h, and aging for 2-8 h;
Step 3, carrying out suction filtration on the material obtained in the step 2 to obtain a solid, and washing with deionized water to remove Cl - in the solid to obtain zirconium-containing hydrogel;
step 4, adding methyl cellulose, pseudo-boehmite and the zirconium-containing hydrogel into water, stirring and uniformly mixing the mixture according to the mass ratio of 1:5-20, heating the mixture to 80-85 ℃, stirring and simultaneously dropwise adding inorganic acid, regulating the pH value of the system to 2-3, and carrying out acidolysis at constant temperature for 4-8 hours to form aluminum-zirconium sol;
And 5, adjusting the pH of the aluminum-zirconium sol to 9-10 to form gel, aging for 2-10 h, washing to neutrality, carrying out suction filtration, and drying to obtain a zirconium-aluminum composite material, adding a binder and a lubricant into the zirconium-aluminum composite material, uniformly mixing, extruding and molding, wherein the total addition amount of the binder and the lubricant is 1-5wt% of the zirconium-aluminum composite material, and drying and roasting to obtain the ZrO 2/γ-Al2O3 composite carrier.
In some embodiments, it is preferred that the zirconia content of the composite support is 5 to 20wt% and the alumina content is 80 to 95wt%.
In some embodiments, it is preferred that the composite carrier is clover-shaped, tooth-shaped, clover-shaped or granular, the specific surface area of the composite carrier is 260-400 m 2/g, the pore volume is 0.6-0.9 cm 3/g, and the mechanical strength is 180-270N/cm.
In some embodiments, it is preferred that the concentration of the zirconium-containing solution is from 0.18 to 0.24mol/L.
In some embodiments, it is preferred that the methylcellulose is added in an amount of 0.5 to 5wt% based on the weight of the aluminum zirconium composite carrier.
In some embodiments, it is preferred that the mineral acid is one or more of hydrochloric acid, sulfuric acid, and nitric acid.
In some embodiments, it is preferable that the binder is selected from one or more of nitric acid, citric acid, oxalic acid, tartaric acid; the lubricant is one or more selected from sesbania powder, dry starch, graphite and paraffin.
In some embodiments it is preferred that the mass ratio of the binder to the lubricant is 1:1-3:2.
In some embodiments, it is preferable that the temperature of the calcination in the step 5 is 400 to 600 ℃ for 2 to 6 hours.
The distillate oil hydrofining catalyst provided by the invention is prepared by taking the composite carrier prepared by the preparation method as a carrier, dipping active components, drying and roasting, wherein the active components comprise one or more of MoO 3、WO3, niO and CoO; preferably, the impregnation is an equal volume negative pressure impregnation.
In some embodiments it is preferred that the precursor solution of the active component is selected from at least two of an ammonium molybdate solution, a nickel nitrate solution, an ammonium phosphomolybdate solution, a nickel chloride solution, an ammonium metatungstate solution, a tungsten chloride solution, a cobalt nitrate solution, a cobalt chloride solution, a cobalt acetate solution, and a nickel acetate solution.
In some embodiments it is preferred that the solvent of the precursor solution of the active component is selected from one or more of water, ethanol and ammonia.
Example 1
Adding ZrOCl 2·8H2 O58 g into a container containing 1000ml of deionized water, stirring until the ZrOCl 2·8H2 O is fully dissolved, slowly dripping the solution into diluted ammonia water, adjusting the pH value to 9, stirring for 1h, aging for 6h, carrying out suction filtration, and washing Cl - in the obtained solid by using deionized water to obtain the zirconium-containing hydrogel.
Adding 5g of methylcellulose, 126g of pseudo-boehmite and the obtained zirconium-containing hydrogel into deionized water, stirring and uniformly mixing, heating the mixed material to 80 ℃, stirring while slowly dropwise adding nitric acid, regulating the pH value of the system to 2, and carrying out constant-temperature acidolysis for 4 hours to form aluminum zirconium sol; then, an appropriate amount of ammonia water is slowly added dropwise to adjust the pH of the aluminum zirconium sol to 9.5, gel is formed, the gel is aged for 10 hours, deionized water is used for washing until the pH=7, suction filtration and drying are carried out, the zirconium aluminum composite material is obtained, the composite material is ground and filtered through a 180-mesh sieve, 2.5wt% (based on the zirconium aluminum composite material) sesbania powder and 2.5wt% (based on the zirconium aluminum composite material) nitric acid are added, the mixture is uniformly mixed and extruded to be molded, and then the mixture is dried at 110 ℃ for 2 hours and baked at 500 ℃ for 4 hours, so that the ZrO 2/γ-Al2O3 composite carrier is obtained, and the main properties of the ZrO 2/γ-Al2O3 composite carrier are shown in table 1.
On the basis of completing the preparation of the carrier, preparing the nickel-molybdenum supported catalyst by adopting an isovolumetric impregnation method under the absolute pressure of 0.085MPa, wherein the precursor solution is an ammonium molybdate solution and a nickel nitrate solution, and the MoO 3 and NiO loadings are respectively 26wt% and 3.5wt%.
Example 2
Adding ZrOCl 2·8H2 O39 g into a container containing 500ml deionized water, stirring until the ZrOCl 2·8H2 O39 g is fully dissolved, slowly dropwise adding the solution into diluted ammonia water, adjusting the pH value to 10, stirring for 2 hours, aging for 6 hours, carrying out suction filtration, and washing Cl - in the obtained solid by using deionized water to obtain the zirconium-containing hydrogel. Adding 7.5g of methylcellulose, 193g of pseudo-boehmite and the obtained zirconium-containing hydrogel into deionized water, stirring and uniformly mixing, heating the mixed material to 85 ℃, stirring while slowly dropwise adding nitric acid, regulating the pH value of the system to 2.5, and carrying out acidolysis at constant temperature for 4 hours; then, an appropriate amount of ammonia water is slowly added dropwise to adjust the pH of the aluminum zirconium sol to 9 to form gel, the gel is aged for 9 hours, deionized water is used for washing until the pH=7, the zirconium aluminum composite material is obtained through suction filtration and drying, the composite material is ground, a 180-mesh sieve is adopted, 2 weight percent sesbania powder and 3 weight percent nitric acid are added, the mixture is uniformly mixed and extruded to form, and the mixture is dried at 110 ℃ for 2 hours and baked at 500 ℃ for 4 hours to obtain the ZrO 2/γ-Al2O3 composite carrier, wherein the main properties of the ZrO 2/γ-Al2O3 composite carrier are shown in table 1. The catalyst preparation was as in example 1.
Example 3
Adding ZrOCl 2·8H2 O32 g into a container containing 500ml of deionized water, stirring until the ZrOCl 2·8H2 O32 g is fully dissolved, slowly dropwise adding the solution into diluted ammonia water, adjusting the pH value to 9, stirring for 1.5h, aging for 4h, performing suction filtration, and washing Cl - in the obtained solid with deionized water to obtain the zirconium-containing hydrogel. Adding 7.5g of methylcellulose, 334g of pseudo-boehmite and the obtained zirconium-containing hydrogel into deionized water, stirring and uniformly mixing, heating the mixed material to 80 ℃, stirring while slowly dropwise adding nitric acid, adjusting the pH of the system to 3, and carrying out acidolysis at constant temperature for 4 hours; then, an appropriate amount of ammonia water is slowly added dropwise to adjust the pH of the aluminum zirconium sol to 9 to form gel, the gel is aged for 6 hours, deionized water is used for washing until the pH=7, suction filtration and drying are carried out, the zirconium aluminum composite material is obtained, the composite material is ground, a 180-mesh sieve is adopted, 2.5 weight percent sesbania powder and 2.5 weight percent nitric acid are added, the mixture is uniformly mixed and extruded to form, and then the mixture is dried at 110 ℃ for 2 hours and baked at 500 ℃ for 4 hours to obtain the ZrO 2/γ-Al2O3 composite carrier, wherein the main properties are shown in table 1. The catalyst preparation was as in example 1.
Example 4
Adding ZrOCl 2·8H2 O71 g into a container containing 1000ml of deionized water, stirring until the ZrOCl 2·8H2 O71 g is fully dissolved, slowly dropwise adding the solution into diluted ammonia water, adjusting the pH value to 10, stirring for 2 hours, aging for 5 hours, carrying out suction filtration, and washing Cl - in the obtained solid by using deionized water to obtain the zirconium-containing hydrogel. Adding 6.8g of methylcellulose, 203g of pseudo-boehmite and the obtained zirconium-containing hydrogel into deionized water, stirring and uniformly mixing, heating the mixed material to 85 ℃, stirring while slowly dropwise adding nitric acid, regulating the pH value of the system to 3, and carrying out acidolysis at constant temperature for 6 hours; then, an appropriate amount of ammonia water is slowly added dropwise to adjust the pH of the aluminum zirconium sol to 9.5, gel is formed, the gel is aged for 8 hours, deionized water is used for washing until the pH=7, suction filtration and drying are carried out, the zirconium aluminum composite material is obtained, the composite material is ground, a 180-mesh sieve is adopted, 2 weight percent sesbania powder and 3 weight percent nitric acid are added, the mixture is uniformly mixed and extruded to form, and then the mixture is dried at 110 ℃ for 2 hours and baked at 500 ℃ for 4 hours, so that the ZrO 2/γ-Al2O3 composite carrier is obtained, and the main properties are shown in table 1. The catalyst preparation was as in example 1.
Comparative example 1
To 100ml of an aluminum nitrate (2 mol/L) solution, 20ml of silica gel (SiO 2 content 25 wt%) was added, and the mixture was uniformly mixed, the solution was heated to 60℃and aqueous ammonia was added dropwise to adjust the pH of the solution to 7, to obtain an aluminum sol. Preparing a 0.1mol/L zirconium nitrate solution, heating to 95 ℃, dropwise adding oxalic acid into the solution, adjusting the pH value of the solution to 5.5, and keeping the temperature for 2 hours to obtain zirconium sol. Mixing zirconium sol, aluminum sol and deionized water according to a volume ratio of 1:2, stirring for 2 hours, heating to 50 ℃, aging for 2 hours at constant temperature, adding 200ml of ethanol, filtering, washing with deionized water, and drying to obtain the composite oxide dry gel. The composite oxide dry gel is ground, screened by a 180-mesh sieve, added with 2 weight percent sesbania powder and 3 weight percent nitric acid, uniformly mixed, extruded and molded, and then dried at 110 ℃ for 2 hours and baked at 500 ℃ for 4 hours to obtain the ZrO 2/γ-Al2O3 composite carrier, wherein the main properties are shown in table 1. The catalyst preparation was as in example 1.
Test example 1
The catalyst was subjected to hydrofining performance evaluation on a 200ml fixed bed reactor, the raw materials treated by the catalyst (the properties are shown in Table 2) are the same as the experimental conditions, the reaction temperature is 340 ℃, the hydrogen partial pressure is 6.0MPa, the space velocity is 1.8h -1, the hydrogen-oil ratio is 500:1, and the catalyst activity evaluation data are shown in Table 3.
Table 1 shows the structural characteristics and strength characteristic data of the composite carriers obtained in examples 1 to 4 and comparative example 1.
TABLE 1 physical Properties of composite Carrier
As can be seen from Table 1, the specific surface area and pore volume of the composite supports obtained in examples 1 to 4 were larger than those of the composite support obtained in comparative example 1, and the mechanical strength of the composite supports obtained in examples 1 to 4 was also higher than that of comparative example 1.
TABLE 2 oil Properties of raw materials
TABLE 3 evaluation results of catalyst hydrogenation
As can be seen from Table 3, the catalysts of examples 1 to 4 of the present invention were higher in both hydrodesulfurization activity and aromatic hydrocarbon saturation performance than the catalyst of comparative example 1.
In summary, the composite carrier and the catalyst prepared by the invention have the following advantages:
(1) The composite carrier has high specific surface area, large pore volume, good stability and high mechanical strength, and is suitable for being used as a middle distillate oil hydrofining catalyst carrier.
(2) The zirconia in the composite carrier can weaken the strong interaction between the active component and the carrier, so that the active metal is easy to reduce, and the advantages of the zirconia active carrier are fully exerted.
(3) The preparation process and the conditions are simple and easy to control, the cost is low, and the preparation method is beneficial to industrial large-scale preparation.
(4) The catalyst prepared by the invention has high hydrodesulfurization and aromatic hydrocarbon saturation activities, can remove sulfur in diesel oil with the sulfur content of 5162ppm and the polycyclic aromatic hydrocarbon content of 26.5wt% to less than 10ppm, and has the polycyclic aromatic hydrocarbon content of less than 7wt%, so that the product meets the clean diesel oil standard of China VI. The catalyst has good stability, and can provide technical support for the hydrogenation device to realize the long-period operation target of 'five years of repair'.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.
Claims (11)
1. The preparation method of the aluminum-zirconium composite carrier is characterized by comprising the following steps of:
Step 1, adding zirconium oxychloride into water, and stirring until the zirconium oxychloride is fully dissolved to obtain a zirconium-containing solution;
step 2, dropwise adding the zirconium-containing solution into ammonia water, adjusting the pH value to 9-10, stirring for 0.5-2 h, and aging for 2-8 h;
Step 3, carrying out suction filtration on the material obtained in the step 2 to obtain a solid, and washing with deionized water to remove Cl - in the solid to obtain zirconium-containing hydrogel;
step 4, adding methyl cellulose, pseudo-boehmite and the zirconium-containing hydrogel into water, stirring and uniformly mixing the mixture according to the mass ratio of 1:5-20, heating the mixture to 80-85 ℃, stirring and simultaneously dropwise adding inorganic acid, regulating the pH value of the system to 2-3, and carrying out acidolysis at constant temperature for 4-8 hours to form aluminum-zirconium sol;
Step 5, regulating the pH of the aluminum-zirconium sol to 9-10, aging for 2-10 hours after forming gel, washing to neutrality, carrying out suction filtration and drying to obtain a zirconium-aluminum composite material, adding a binder and a lubricant into the zirconium-aluminum composite material, uniformly mixing, extruding and molding, wherein the total addition amount of the binder and the lubricant is 1-5wt% of the zirconium-aluminum composite material, and drying and roasting to obtain a ZrO 2/γ-Al2O3 composite carrier;
wherein the content of zirconia in the composite carrier is 5-20wt% and the content of alumina is 80-95wt%;
The binder is one or more selected from nitric acid, citric acid, oxalic acid and tartaric acid; the lubricant is one or more selected from sesbania powder, dry starch, graphite and paraffin.
2. The method for preparing an aluminum-zirconium composite carrier according to claim 1, wherein the composite carrier is clover-shaped, tooth-shaped, clover-shaped or granular, the specific surface area of the composite carrier is 260-400 m 2/g, the pore volume is 0.6-0.9 cm 3/g, and the mechanical strength is 180-270N/cm.
3. The method for producing an aluminum zirconium composite carrier according to claim 1, wherein the concentration of the zirconium-containing solution is 0.18 to 0.24mol/L.
4. The method for preparing an aluminum zirconium composite carrier according to claim 1, wherein the addition amount of the methyl cellulose is 0.5 to 5wt% of the weight of the aluminum zirconium composite carrier.
5. The method for preparing an aluminum-zirconium composite carrier according to claim 1, wherein the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid.
6. The method of preparing an aluminum zirconium composite carrier according to claim 1, wherein the mass ratio of the binder to the lubricant is 1:1 to 3:2.
7. The method for preparing an aluminum zirconium composite carrier according to claim 1, wherein the roasting temperature in the step 5 is 400-600 ℃ and the time is 2-6 h.
8. A distillate oil hydrofining catalyst is characterized in that a composite carrier prepared by the preparation method of any one of claims 1-7 is used as a carrier, an active component is impregnated, then the active component is dried and roasted, and the active component comprises one or more of MoO 3、WO3, niO and CoO.
9. The distillate hydrofinishing catalyst of claim 8, wherein the impregnation is an equal volume negative pressure impregnation.
10. The distillate hydrofining catalyst according to claim 8, wherein the precursor solution of the active component is selected from at least two of an ammonium molybdate solution, a nickel nitrate solution, an ammonium phosphomolybdate solution, a nickel chloride solution, an ammonium meta-tungstate solution, a tungsten chloride solution, a cobalt nitrate solution, a cobalt chloride solution, a cobalt acetate solution, and a nickel acetate solution.
11. The distillate hydrofining catalyst according to claim 10, wherein the solvent of the precursor solution of the active component is selected from one or more of water, ethanol and ammonia water.
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