CN115254083A - 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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- CN115254083A CN115254083A CN202110487926.8A CN202110487926A CN115254083A CN 115254083 A CN115254083 A CN 115254083A CN 202110487926 A CN202110487926 A CN 202110487926A CN 115254083 A CN115254083 A CN 115254083A
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- Prior art keywords
- zirconium
- aluminum
- composite carrier
- carrier
- solution
- Prior art date
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- 239000002131 composite material Substances 0.000 title claims abstract description 123
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 84
- 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
- 238000003756 stirring Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 24
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 21
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 230000032683 aging Effects 0.000 claims abstract description 18
- 239000000017 hydrogel Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 239000000314 lubricant Substances 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
- 235000010981 methylcellulose Nutrition 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000000499 gel Substances 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 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
- 239000002243 precursor Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 239000007788 liquid Substances 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-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
- 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-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 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
- 238000004821 distillation Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 53
- 239000003921 oil Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 239000002283 diesel fuel Substances 0.000 description 10
- 241000219782 Sesbania Species 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000004898 kneading Methods 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
- 238000007873 sieving Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 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
- 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
- 230000003993 interaction Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 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
- 239000011787 zinc oxide Substances 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
- 239000002253 acid Substances 0.000 description 1
- 238000003915 air pollution Methods 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012050 conventional carrier Substances 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
- 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
- 230000006872 improvement Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011259 mixed solution Substances 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
- 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
- 238000012545 processing Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 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
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 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
- 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
-
- B01J35/615—
-
- B01J35/635—
-
- 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
-
- 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
-
- 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
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, washing the solid with deionized water to remove Cl in the solid‑Obtaining zirconium-containing hydrogel; to containAdding pseudo-boehmite and methyl cellulose into the zirconium hydrogel to prepare zirconium-aluminum sol; adjusting the pH value of the aluminum zirconium sol to form gel, aging, washing, filtering, drying to obtain a zirconium aluminum composite material, adding a binder and a lubricant into the composite material, uniformly mixing, extruding, molding, drying, and roasting to obtain ZrO2/γ‑Al2O3And (3) a composite carrier. The composite carrier has the advantages of high specific surface area, large pore volume, high mechanical strength and good stability, and the zirconia contained in the composite carrier is enriched on the surface of the carrier, thereby effectively playing the catalysis promoting role of the zirconia. The invention also relates to a distillate oil hydrofining catalyst.
Description
Technical Field
The invention relates to the field of petroleum refining and hydrorefining, in particular to a preparation method of an aluminum-zirconium composite carrier and a middle distillate oil hydrorefining catalyst taking the composite carrier as a carrier.
Background
The construction of resource-saving and environment-friendly oil refining industry becomes one of the major key problems to be solved urgently in national economy and social sustainable development in China, and the production of the vehicle fuel with ultra-low sulfur and high combustion efficiency plays a key role in promoting the coordinated development of energy, economy and environment. In order to solve the increasingly serious problem of air pollution in large and medium-sized cities caused by the rapid increase of the automobile holding amount, china accelerates the pace of oil quality upgrading. National VI clean diesel standard has been fully implemented in 2019, 1 month and 1 day.
Along with the aggravation of the heavy and inferior degree of crude oil, the difficulty of diesel oil processing is continuously increased. Meanwhile, the annual demand of diesel oil is about 1.8 hundred million tons, the quality upgrade of the diesel oil is accelerated, and the production of high-quality clean diesel oil becomes one of key work of the current refining and chemical enterprises. Aiming at upgrading the quality of the existing diesel hydrogenation device, the measures which can be adopted at present mainly comprise reducing the treatment capacity of the device, improving the reaction severity of the device, reducing the final distillation point of the diesel and using a high-activity diesel hydrogenation catalyst. The measures of reducing the treatment capacity of the device, improving the reaction severity of the device, reducing the final distillation point of the diesel oil and the like have adverse effects on the production cost and the production efficiency of the device. To solve the above problems, criterion, exxon Mobile, IFP, akzo Nobel, UOP, haldor abroad
Companies and the like respectively research and 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 are the most effective measures for upgrading the diesel quality of the diesel hydrogenation device, and accord 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 the novel catalytic material can substantially change and improve the activity of the hydrogenation catalyst, and is an effective way for developing the high-activity hydrogenation catalyst.
The main current starting points for increasing the efficiency of hydrodesulphurisation are the improvement of the loading technology, the modification of the catalyst and the development of new catalysts. Compared with the former two catalysts, the development of the novel catalyst is easier. Alumina is used as a traditional hydrodesulfurization catalyst carrier and 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 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 also a very characteristic catalyst support because it tends to generate oxygen vacancies that allow for unique interactions with the active components. Compared with the conventional carrier, the catalyst taking zirconia as the carrier has unique advantages, such as good sulfur resistance, easy reduction of supported metal and the like. However, the conventional zirconium dioxide carrier has small specific surface, less developed pores, irregular change of pore size and the like, and the exertion of the excellent performance of the zirconium dioxide carrier is limited.
Patent ZL00123133.2 discloses a zirconium-containing alumina carrier and a preparation method thereof, wherein the zirconium-containing alumina carrier is prepared by adding a zirconium-containing compound in a wet mode in the forming process of the carrier; the lateral pressure strength 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 randomness of the composite carrier prepared in a wet kneading mode is high, and the zirconium-containing compound is introduced into the alumina in a wet kneading process, so that the zirconium-containing compound is not favorably and uniformly dispersed, and the hydrodesulfurization activity of the catalyst is adversely affected.
Patent ZL201310524738.3 discloses a diesel hydrodesulfurization and denitrification catalyst and a preparation method thereof, wherein the catalyst comprises a carrier, an auxiliary agent and an active metal; the carrier being Al2O3-ZrO2-TiO2-SiO2A multi-oxide composite support; the auxiliary agent is phosphorus; taking nickel, cobalt, molybdenum and tungsten as active components; the catalyst comprises the following components in percentage by weight based on the weight of the catalyst: 1-6 wt% of cobalt oxide calculated by oxide; 1-15 wt% of nickel oxide, 2-12 wt% of molybdenum oxide, 12-35 wt% of tungsten oxide and 1.5-5 wt% of auxiliary agent phosphorus pentoxide; the pore volume of the catalyst is not less than 0.2ml/g, and the specific surface area is not less than 140m2(ii)/g, mechanical strength is not less than 15N/mm; the composite carrier comprises the following components in percentage by weight: titanium oxide accounts for 2 to 15 weight percent, silicon oxide accounts for 2 to 20 weight percent, and zirconium oxide accounts for 5 to 15 weight percent; the balance being alumina. The composite carrier is prepared through mixing pseudoboehmite, zirconyl nitrate, metatitanic acid (or nano level titania or tetra-n-propyl titanate) and silica sol, adding peptizing agent, extrusion assistant and pore-enlarging agent, kneading, extruding to form, drying and roasting to obtain Al2O3-ZrO2-TiO2-SiO2A multi-oxide composite carrier. The preparation of the composite carrier adopts wet kneading, and the same problems as above still exist.
Patent ZL 201010514168.6 discloses a preparation method of a zirconia-alumina composite oxide carrier, which adopts a method for preparing aluminum hydroxide sol and zirconium-containing sol in advance, silicon is introduced when aluminum hydroxide is gelatinized, and a surfactant or an organic solvent is added into the zirconium-containing sol; after the pH values of the two colloids are respectively adjusted, the two colloids are mixed and aged, and then the mixture is washed, filtered and dried to obtain the zirconia-silica-alumina composite oxide dry glue. And then adding an adhesive, an extrusion aid, a peptizing agent and an auxiliary agent into the composite oxide dry glue, kneading, extruding into strips, drying and roasting to obtain the composite oxide carrier. Wherein, the adhesive is microporous alumina, and the dosage is 5-30 wt% of the weight of the composite oxide carrier. The method has complex preparation process, and needs to add a surfactant or an organic solvent into the zirconium-containing sol in order to improve the dispersibility of the sol, and the preparation process has more influencing factors. In addition, the 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 influenced, and the hydrodesulfurization activity of the catalyst is adversely affected.
Patent ZL201710329054.6 discloses a composite catalyst carrier containing zirconia, and a preparation method and application thereof, wherein the composite catalyst carrier consists of zirconia, zinc oxide and manganese oxide, and comprises, by mass of 100%, 10-60% of zirconia, 15-55% of zinc oxide and 15-55% of manganese oxide. The composite carrier is prepared by a coprecipitation method, and the precipitate mixed solution is aged for 30min at the temperature of 80-140 ℃, filtered, dried and roasted to obtain the composite carrier. The composite carrier is soaked with K and Pd to prepare the catalyst for the reaction of preparing isobutanol by using 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 the carrier has the following physical properties: the bulk density is 0.8-1.1 g/ml, the pore volume is 0.3-0.6 ml/g, and the specific surface area is 5-60 m2Per g, average poreThe diameter is 80-350 nm, preferably 100-250 nm; the carrier has 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 the mass of the carrier, and the carrier has the following physical properties: the bulk density is 0.7-1.1 g/ml, the pore volume is 0.2-0.6 ml/g, and the specific surface area is 3-60 m2Per g, the average pore diameter is 50-300 nm; the carrier has 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 catalysts prepared by the two zirconium-containing composite carriers are both used in the hydrogenation reaction before carbon dioxide generation.
Disclosure of Invention
Based on the above, an object of the present invention is to provide ZrO2/γ-Al2O3The composite carrier has relatively large specific surface area and pore volume, high stability and high mechanical strength, and the zirconia contained in the composite carrier is enriched on the surface of the carrier, so that the co-catalysis of the zirconia is exerted more efficiently.
The invention also provides a preparation method of the hydrofining catalyst with the composite carrier as the carrier. Compared with the prior art, the method can more effectively play the role of the zirconia, and can synergistically regulate the surface physicochemical property and the pore structure of the carrier, so that the catalyst has higher hydrodesulfurization activity and aromatic hydrocarbon saturation performance.
In order to achieve the above object, the present invention provides a method for preparing an aluminum zirconium composite carrier, comprising the 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, filtering the material obtained in the step 2 to obtain a solid, washing the solid with deionized water to remove the solidCl of-Obtaining the zirconium-containing hydrogel;
step 4, adding methyl cellulose, pseudo-boehmite and the zirconium-containing hydrogel into water, wherein the solid-liquid mass ratio is 1-20, stirring and uniformly mixing, then heating the mixed material to 80-85 ℃, stirring and simultaneously dripping inorganic acid, adjusting the pH of the system to 2-3, and carrying out acidolysis at constant temperature for 4-8 h to form aluminum-zirconium sol;
step 5, adjusting the pH value of the aluminum zirconium sol to 9-10, forming gel, aging for 2-10 h, washing to be neutral, filtering, 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 adding amount of the binder and the lubricant is 1-5 wt% of the zirconium aluminum composite material, drying and roasting to obtain ZrO2/γ-Al2O3And (3) a composite carrier.
In the preparation method of the aluminum zirconium composite carrier, the content of zirconia in the composite carrier is preferably 5-20 wt%, and the content of alumina in the composite carrier is preferably 80-95 wt%.
The preparation method of the aluminum-zirconium composite carrier is preferably that the composite carrier is clover-shaped, dentate sphere-shaped, clover-shaped or granular, and the specific surface area of the composite carrier is 260-400 m2Per g, pore volume of 0.6-0.9 cm3(ii) g, the mechanical strength is 180-270N/cm.
In the method for preparing the aluminum-zirconium composite carrier, the concentration of the zirconium-containing solution is preferably 0.18 to 0.24mol/L.
In the preparation method of the aluminum zirconium composite carrier, the addition amount of the methyl cellulose is preferably 0.5 to 5wt% of the weight of the aluminum zirconium composite carrier.
In the preparation method of the aluminum zirconium composite carrier, the inorganic acid is preferably one or more of hydrochloric acid, sulfuric acid and nitric acid.
In the preparation method of the aluminum-zirconium composite carrier, the binder is preferably one or more selected from nitric acid, citric acid, oxalic acid and tartaric acid; the lubricant is selected from one or more of sesbania powder, dry starch, graphite and paraffin.
In the preparation method of the aluminum zirconium composite carrier, the mass ratio of the binder to the lubricant is preferably 1.
The preparation method of the aluminum zirconium composite carrier is preferably characterized in that the roasting temperature in the step 5 is 400-600 ℃, and the roasting time is 2-6 h.
Therefore, 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, impregnating the carrier with an active component, drying and roasting the impregnated carrier, wherein the active component comprises MoO3、WO3One or more of NiO and CoO; preferably, the impregnation is an equal volume negative pressure impregnation.
In the distillate oil hydrorefining catalyst of the present invention, it is preferable that the precursor solution of the active component is at least two selected from 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 distillate oil hydrorefining catalyst of the invention is preferably characterized in that the solvent of the precursor solution of the active component is one or more selected from water, ethanol and ammonia water.
Specifically, the invention provides ZrO2/γ-Al2O3The preparation method of the composite carrier and the preparation method of the intermediate distillate oil hydrofining catalyst taking the composite carrier as the carrier 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, adjusting the pH value to 9-10, stirring for 0.5-2 h, and aging for 2-8 h;
step 3, performing suction filtration on the material obtained in the step 2, and washing Cl in the obtained solid by deionized water-Obtaining the zirconium-containing hydrogel;
step 4, adding methyl cellulose, pseudo-boehmite and the zirconium-containing hydrogel obtained in the step 3 into water, wherein the solid-liquid mass ratio is 1-20, stirring and uniformly mixing, then heating the mixed material to 80-85 ℃, stirring while slowly dripping inorganic acid, adjusting the pH of the system to 2-3, and carrying out acidolysis at constant temperature for 4-8 h to form aluminum-zirconium sol;
step 5, adjusting the pH value of the aluminum zirconium sol to 9-10 to form gel, aging for 2-10 h, washing with water to be neutral, performing suction filtration and drying to obtain a zirconium-aluminum composite material, adding 1-5 wt% of a binder and a lubricant in terms of the zirconium-aluminum composite material into the zirconium-aluminum composite material, uniformly mixing, performing extrusion molding, drying and roasting to obtain ZrO2/γ-Al2O3A composite carrier;
step 6, zrO is subjected to2/γ-Al2O3The composite carrier is impregnated with precursor solution of active component, dried and roasted to obtain the intermediate distillate oil hydrofining catalyst, wherein the active component comprises MoO3、WO3One or more of NiO and CoO.
Specifically, the ZrO2/γ-Al2O3In the composite carrier, the content of zirconia is 5-20 wt%, and the content of alumina is 80-95 wt%.
Specifically, the ZrO2/γ-Al2O3The composite carrier is clover-shaped, dentate sphere-shaped, clover-shaped or granular, and the specific surface area of the composite carrier is 260-400 m2G, pore volume of 0.6-0.9 cm3The mechanical strength is 180-270N/cm.
Specifically, the ZrO2/γ-Al2O3In step 1 of the method for preparing the composite carrier, zrOCl2·8H2The O concentration is preferably 0.18 to 0.24mol/L.
Specifically, the ZrO2/γ-Al2O3In step 4 of the preparation method of the composite carrier, the addition amount of the methyl cellulose is 0.5-5 wt% of the weight of the composite carrier.
Specifically, the ZrO2/γ-Al2O3In step 4 of the preparation method of the composite carrier, the inorganic acid is one of hydrochloric acid, sulfuric acid and nitric acidOne or more of them.
Specifically, the ZrO2/γ-Al2O3In step 5 of the preparation method of the composite carrier, the binder is selected from one or more of nitric acid, citric acid, oxalic acid and tartaric acid.
Specifically, the ZrO2/γ-Al2O3In step 5 of the preparation method of the composite carrier, the lubricant is selected from one or more of sesbania powder, dry starch, graphite and paraffin.
Specifically, the ZrO2/γ-Al2O3In step 5 of the preparation method of the composite carrier, the roasting temperature is preferably 400-600 ℃, and the roasting time is preferably 2-6 h.
The preparation method of the catalyst for hydrorefining of middle distillate oil comprises the following steps of preparing a precursor solution of an active component, and preferably selecting the precursor solution of the active component from two or more of the group consisting 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.
The preparation method of the middle distillate oil hydrofining catalyst is characterized in that the solvent in the precursor solution of the active component is preferably one or more of the group consisting of water, ethanol and ammonia water.
The preparation method of the middle distillate oil hydrofining catalyst 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 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 carrier of a hydrofining catalyst for middle distillate oil.
(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 conditions are simple and easy to control, the cost is low, and the industrial large-scale preparation is facilitated.
(4) The catalyst prepared by the invention has high hydrodesulfurization and aromatic hydrocarbon saturation activity, can remove sulfur in diesel oil with the sulfur content of 5162ppm and the polycyclic aromatic hydrocarbon content of 26.5wt% to below 10ppm, and remove the polycyclic aromatic hydrocarbon content to below 7wt%, and the product meets the national VI clean diesel oil standard. The catalyst has good stability, and can provide technical support for realizing the long-period operation goal of 'five years and one repair'.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed 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, filtering the material obtained in the step 2 to obtain a solid, washing the solid with deionized water to remove Cl in the solid-Obtaining zirconium-containing hydrogel;
step 4, adding methyl cellulose, pseudo-boehmite and the zirconium-containing hydrogel into water, wherein the solid-liquid mass ratio is 1-20, stirring and uniformly mixing, then heating the mixed material to 80-85 ℃, stirring and simultaneously dripping inorganic acid, adjusting the pH of the system to 2-3, and carrying out acidolysis at constant temperature for 4-8 h to form aluminum-zirconium sol;
step 5, adjusting the pH value of the aluminum zirconium sol to 9-10, forming gel, aging for 2-10 h, washing to be neutral, filtering, 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 adding amount of the binder and the lubricant is 1-5 wt% of the zirconium aluminum composite material, drying and roasting to obtain ZrO2/γ-Al2O3And (3) compounding a carrier.
In some embodiments, it is preferred that the composite support has a zirconia content of 5 to 20wt% and an alumina content of 80 to 95wt%.
In some embodiments, the composite carrier is cloverleaf-shaped, dentate sphere-shaped, clover-shaped or granular, and the specific surface area of the composite carrier is 260-400 m2Per g, pore volume of 0.6-0.9 cm3(ii) g, the mechanical strength is 180-270N/cm.
In some embodiments, it is preferred that the concentration of the zirconium-containing solution is 0.18 to 0.24mol/L.
In some embodiments, it is preferable 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 preferable that the inorganic 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, and tartaric acid; the lubricant is selected from one or more of sesbania powder, dry starch, graphite and paraffin.
It is preferred in some embodiments that the ratio of the mass of the binder to the mass of the lubricant is 1.
In some embodiments, the roasting temperature in the step 5 is 400-600 ℃ and the roasting time is 2-6 h.
The distillate oil hydrorefining catalyst provided by the invention is prepared by taking the composite carrier prepared by the preparation method as a carrier, impregnating an active component, drying and roasting, wherein the active component comprises MoO3、WO3One or more of NiO and CoO; preferably, the impregnation is an equal volume negative pressure impregnation.
In some embodiments, it is preferable 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 preferable that the solvent of the precursor solution of the active component is selected from one or more of water, ethanol and ammonia.
Example 1
ZrOCl is added into a container containing 1000ml of deionized water2·8H2Stirring and fully dissolving 58g of O, slowly dripping into diluted ammonia water, adjusting the pH value to 9, stirring for 1h, aging for 6h, filtering, and washing Cl in the obtained solid by deionized water-And obtaining the zirconium-containing hydrogel.
Adding 5g of methyl cellulose, 126g of pseudo-boehmite and the obtained zirconium-containing hydrogel into deionized water, uniformly stirring and mixing, heating the mixed material to 80 ℃, slowly dropwise adding nitric acid while stirring, adjusting the pH of the system to 2, and carrying out acidolysis at constant temperature for 4 hours to form aluminum-zirconium sol, wherein the solid-liquid mass ratio is 1; then slowly adding a proper amount of ammonia water dropwise to adjust the pH value of the aluminum zirconium sol to 9.5 to form gel, aging for 10h, washing with deionized water until the pH value is =7, performing suction filtration and drying to obtain a zirconium aluminum composite material, grinding the composite material, sieving with a 180-mesh sieve, adding 2.5wt% (based on 100 percent of the zirconium aluminum composite material) of sesbania powder and 2.5wt% (based on 100 percent of the zirconium aluminum composite material) of nitric acid, uniformly mixing, performing extrusion molding, drying at 110 ℃ for 2h, and roasting at 500 ℃ for 4h to obtain ZrO2/γ-Al2O3The main properties of the composite carrier are shown in Table 1.
Preparing nickel-molybdenum supported catalyst by adopting an isovolumetric impregnation method under the absolute pressure of 0.085MPa on the basis of completing the preparation of the carrier, wherein precursor solutions are ammonium molybdate solution and nickel nitrate solution, and MoO is3And NiO loadings of 26wt% and 3.5wt%, respectively.
Example 2
ZrOCl is added into a container containing 500ml of deionized water2·8H2Stirring to fully dissolve O39 g, slowly dripping into diluted ammonia water, adjusting pH value to 10, stirring for 2h, aging for 6h, filtering, washing Cl in the obtained solid by deionized water-And obtaining the zirconium-containing hydrogel. 7.5g of methyl cellulose, 193g of pseudo-boehmite and the obtained zirconium-containing hydrogel are added into deionized water, and the solid-liquid mass ratio is1, uniformly stirring, heating the mixed material to 85 ℃, slowly dropwise adding nitric acid while stirring, adjusting the pH of the system to 2.5, and carrying out acidolysis at constant temperature for 4 hours; then slowly adding a proper amount of ammonia water dropwise to adjust the pH value of the aluminum zirconium sol to 9 to form a gel, aging for 9h, washing with deionized water until the pH value is =7, performing suction filtration and drying to obtain a zirconium aluminum composite material, grinding the composite material, sieving with a 180-mesh sieve, adding 2wt% of sesbania powder and 3wt% of nitric acid, uniformly mixing, performing extrusion molding, drying at 110 ℃ for 2h, and roasting at 500 ℃ for 4h to obtain ZrO2/γ-Al2O3The main properties of the composite carrier are shown in Table 1. The catalyst preparation was the same as in example 1.
Example 3
ZrOCl is added into a container containing 500ml of deionized water2·8H2Stirring and fully dissolving 32g of O, slowly dripping into diluted ammonia water, adjusting the pH value to 9, stirring for 1.5h, aging for 4h, filtering, and washing Cl in the obtained solid by deionized water-And obtaining 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 ℃, slowly adding dropwise nitric acid while stirring, adjusting the pH of the system to 3, and carrying out acidolysis at constant temperature for 4 hours, wherein the solid-liquid mass ratio is 1; then slowly adding a proper amount of ammonia water dropwise to adjust the pH value of the aluminum zirconium sol to 9 to form gel, aging for 6h, washing with deionized water until the pH value is =7, performing suction filtration and drying to obtain a zirconium aluminum composite material, grinding the composite material, sieving with a 180-mesh sieve, adding 2.5wt% of sesbania powder and 2.5wt% of nitric acid, uniformly mixing, performing extrusion molding, drying at 110 ℃ for 2h, and roasting at 500 ℃ for 4h to obtain ZrO2/γ-Al2O3The main properties of the composite carrier are shown in Table 1. The catalyst preparation was the same as in example 1.
Example 4
ZrOCl is added into a container containing 1000ml of deionized water2·8H2Stirring to fully dissolve O71 g, slowly dripping into diluted ammonia water, adjusting the pH value to 10, stirring for 2h, aging for 5h, performing suction filtration, and washing Cl in the obtained solid by deionized water-And obtaining the zirconium-containing hydrogel. 6.8g of methylcellulose, 203g of pseudo-boehmite and the resulting zirconium-containing hydrogel were added to deionized waterIn the method, the solid-liquid mass ratio is 1; then slowly adding a proper amount of ammonia water dropwise to adjust the pH value of the aluminum zirconium sol to 9.5 to form gel, aging for 8h, washing with deionized water until the pH value is =7, performing suction filtration and drying to obtain a zirconium aluminum composite material, grinding the composite material, sieving with a 180-mesh sieve, adding 2wt% of sesbania powder and 3wt% of nitric acid, uniformly mixing, performing extrusion molding, drying at 110 ℃ for 2h, and roasting at 500 ℃ for 4h to obtain ZrO2/γ-Al2O3The main properties of the composite carrier are shown in Table 1. The catalyst preparation was the same as in example 1.
Comparative example 1
To 100ml of an aluminum nitrate (2 mol/L) solution was added 20ml of silica gel (SiO)2Content 25 wt%), mixing, heating the solution to 60 deg.C, and adding ammonia water to adjust pH to 7 to obtain aluminum sol. Preparing a zirconium nitrate solution with the concentration of 0.1mol/L, 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 and stirring zirconium sol, aluminum sol and deionized water according to a volume ratio of 1. Grinding the dry glue of the composite oxide, sieving the ground dry glue with a 180-mesh sieve, adding 2wt% of sesbania powder and 3wt% of nitric acid, uniformly mixing, extruding and molding, drying the mixture at 110 ℃ for 2 hours, and roasting the mixture at 500 ℃ for 4 hours to obtain ZrO2/γ-Al2O3The main properties of the composite carrier are shown in Table 1. The catalyst preparation was the same as in example 1.
Test example 1
The catalyst is subjected to hydrofining performance evaluation on a 200ml fixed bed reactor, the raw materials (properties are shown in Table 2) treated by the catalyst are the same as the experimental conditions, the reaction temperature is 340 ℃, the hydrogen partial pressure is 6.0MPa, and the space velocity is 1.8h-1Hydrogen-oil ratio 500, and the catalyst activity evaluation data are shown in table 3.
Table 1 shows structural characteristics and strength characteristic data of the composite supports 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 areas and the pore volumes 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 strengths of the composite supports obtained in examples 1 to 4 were also higher than those of comparative example 1.
TABLE 2 Properties of the feed oils
TABLE 3 catalyst hydrogenation evaluation results
As can be seen from Table 3, the hydrodesulfurization activity and the aromatic saturation performance of the catalysts provided in examples 1 to 4 of the present invention are higher than those of the catalyst of comparative example 1.
In conclusion, 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, high stability and high mechanical strength, and is suitable for use as the carrier of middle distillate oil hydrorefining catalyst.
(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 conditions are simple and easy to control, the cost is low, and the industrial large-scale preparation is facilitated.
(4) The catalyst prepared by the invention has high hydrodesulfurization and aromatic hydrocarbon saturation activity, can remove sulfur in diesel oil with the sulfur content of 5162ppm and the polycyclic aromatic hydrocarbon content of 26.5wt% to below 10ppm, and remove the polycyclic aromatic hydrocarbon content to below 7wt%, and the product meets the national VI clean diesel oil standard. The catalyst has good stability, and can provide technical support for realizing the long-period operation goal of 'five years and one repair'.
The present invention is capable of other embodiments, and various changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the invention.
Claims (12)
1. The preparation method of the aluminum-zirconium composite carrier is characterized by comprising 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, then stirring for 0.5-2 h, and aging for 2-8 h;
step 3, filtering the material obtained in the step 2 to obtain a solid, washing the solid with deionized water to remove Cl in the solid-Obtaining the zirconium-containing hydrogel;
step 4, adding methyl cellulose, pseudo-boehmite and the zirconium-containing hydrogel into water, wherein the solid-liquid mass ratio is 1-20, stirring and uniformly mixing, then heating the mixed material to 80-85 ℃, stirring and simultaneously dripping inorganic acid, adjusting the pH of the system to 2-3, and carrying out acidolysis at constant temperature for 4-8 h to form aluminum-zirconium sol;
step 5, adjusting the pH value of the aluminum zirconium sol to 9-10, aging for 2-10 h after gel formation, then washing to be neutral, filtering, drying to obtain a zirconium aluminum composite material, adding a binder and a lubricant into the zirconium aluminum composite material, uniformly mixing, then extruding and molding, wherein the total adding amount of the binder and the lubricant is 1-5 wt% of the zirconium aluminum composite material, drying and roasting to obtain ZrO2/γ-Al2O3And (3) a composite carrier.
2. The method for preparing an aluminum zirconium composite carrier according to claim 1, wherein the composite carrier contains 5 to 20wt% of zirconia and 80 to 95wt% of alumina.
3. The method for preparing the aluminum-zirconium composite carrier according to claim 1, wherein the composite carrier is clover-shaped, dentate sphere-shaped, clover-shaped or granular, and the specific surface area of the composite carrier is 260-400 m2Per g, pore volume of 0.6-0.9 cm3(ii) g, the mechanical strength is 180-270N/cm.
4. 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.
5. The method for preparing an aluminum zirconium composite carrier according to claim 1, wherein the methylcellulose is added in an amount of 0.5 to 5wt% based on the weight of the aluminum zirconium composite carrier.
6. The method for preparing the aluminum-zirconium composite carrier according to claim 1, wherein the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid.
7. The method for preparing the aluminum-zirconium composite carrier according to claim 1, wherein the binder is one or more selected from nitric acid, citric acid, oxalic acid and tartaric acid; the lubricant is selected from one or more of sesbania powder, dry starch, graphite and paraffin.
8. The method for preparing an aluminum zirconium composite carrier according to claim 1, wherein the mass ratio of the binder to the lubricant is 1.
9. The method for preparing the aluminum-zirconium composite carrier according to claim 1, wherein the calcination temperature in the step 5 is 400 to 600 ℃ and the calcination time is 2 to 6 hours.
10. Distillation deviceThe oil separation hydrofining catalyst is characterized in that the composite carrier prepared by the preparation method of any one of claims 1 to 9 is used as a carrier, and the catalyst is prepared by impregnating an active component, drying and roasting, wherein the active component comprises MoO3、WO3One or more of NiO and CoO; preferably, the impregnation is an equal volume negative pressure impregnation.
11. The distillate hydrofinishing catalyst according to claim 10, wherein the precursor solution of the active component is selected from at least two 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.
12. The distillate hydrofinishing catalyst according to claim 11, characterized in that the solvent of the precursor solution of the active component is selected from one or more of water, ethanol and ammonia.
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| CN116273035A (en) * | 2023-03-10 | 2023-06-23 | 绍兴绿奕化工有限公司 | Solid acid forming catalyst and preparation method and application thereof |
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| CN102451764A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing zirconia-alumina composite oxide carrier |
| CN102527397A (en) * | 2010-12-10 | 2012-07-04 | 中国石油天然气股份有限公司 | Preparation method for pretreating catalyst by hydrocracking |
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| CN102451764A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing zirconia-alumina composite oxide carrier |
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