CN106955746A - A kind of complex carrier of the aluminum oxide containing zinc oxide and preparation method thereof - Google Patents
A kind of complex carrier of the aluminum oxide containing zinc oxide and preparation method thereof Download PDFInfo
- Publication number
- CN106955746A CN106955746A CN201710158372.0A CN201710158372A CN106955746A CN 106955746 A CN106955746 A CN 106955746A CN 201710158372 A CN201710158372 A CN 201710158372A CN 106955746 A CN106955746 A CN 106955746A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- complex carrier
- zinc
- alumina
- potassium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 229910001676 gahnite Inorganic materials 0.000 claims abstract description 42
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011591 potassium Substances 0.000 claims abstract description 41
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 41
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 37
- 239000011777 magnesium Substances 0.000 claims abstract description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000002671 adjuvant Substances 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims description 86
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 84
- 229910052725 zinc Inorganic materials 0.000 claims description 84
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 37
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- 239000004411 aluminium Substances 0.000 claims description 28
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 20
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 17
- 239000000395 magnesium oxide Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 15
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 13
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000004448 titration Methods 0.000 claims description 11
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000004323 potassium nitrate Substances 0.000 claims description 9
- 235000010333 potassium nitrate Nutrition 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001593 boehmite Inorganic materials 0.000 claims description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 241000219782 Sesbania Species 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 abstract description 16
- 229910000611 Zinc aluminium Inorganic materials 0.000 abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 abstract description 15
- 239000011593 sulfur Substances 0.000 abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 230000033228 biological regulation Effects 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000002803 maceration Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 5
- 238000001935 peptisation Methods 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 238000009938 salting Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- QDWGRSGGOUPRJF-UHFFFAOYSA-N O.O.[O--].[Zn++] Chemical compound O.O.[O--].[Zn++] QDWGRSGGOUPRJF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000012687 aluminium precursor Substances 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000000185 sucrose group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1808—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with zinc, cadmium or mercury
-
- 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
-
- 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
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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Abstract
The invention discloses complex carrier of a kind of aluminum oxide containing zinc oxide and preparation method thereof, the complex carrier includes the zinc oxide containing gahnite, aluminum oxide, adjuvant component phosphorus, potassium and magnesium, the complex carrier zinc-aluminium is uniformly dispersed, specific surface area high, the carrier available for FCC catalyst sulfur prodegradant, FCC hydrodesulfurizations or hydrogenation catalyst.
Description
Technical field
The invention belongs to Hydrobon catalyst technical field, more particularly to a kind of compound load containing zinc oxide-alumina
Body and preparation method thereof, the complex carrier can be used for FCC catalyst sulfur prodegradant and FCC hydrodesulfurization carriers.
Background technology
With Law on Environmental Protection require it is increasingly strict, the sulfur content in gasoline product receives stricter limitation.
More than 80% is catalytically cracked gasoline in current China gasoline product, because the general sulfur content of catalytically cracked gasoline is in 100-
500v%, or even also high-sulfur, high olefin feedstock oil, sulfur content is in more than 500mg/kg, and olefin(e) centent is also above 40%.Selection
Property hydrodesulfurization technology inevitably cause hydrocarbon fraction saturation when carrying out deep hydrodesulfurizationof and reduce octane number, this
Requiring to try one's best while Hydrobon catalyst desulfurization avoids loss of octane number excessive.
In existing Hydrobon catalyst, ZnO/A12O3It is its main active component, ZnO is in hydro-thermal spinel-type
Composite oxides are the up-and-coming Inorganic Non-metallic Materials of a class, and the composite of zinc oxide and aluminum oxide is urged frequently as desulfurization
Changing material is used to adsorb desulfurization and hydrodesulfurization field.It is mixed that the conventional preparation method of the domestic and international material includes infusion process, machinery
Legal, coprecipitation and peptisation.Wherein, because infusion process and mechanical mixing use alumina material as predecessor, lead to
The specific surface area of adjustment alumina material is crossed, both approaches can prepare the composite of high specific surface area, but be due to
Aluminum oxide and zinc oxide interaction in composite is weaker, and the loss of zinc oxide is easily produced during use, is typically
Promote the two to form spinelle to avoid the loss of zinc oxide using the method for high-temperature roasting；And coprecipitation and peptisation are used
Compound containing aluminum and zinc prepares zinc-aluminium precursor by precipitation or peptization, aluminum and zinc in preparation process by react produce compared with
Strong interaction can avoid the zinc oxide during use from being lost in, but the specific surface area that peptisation prepares material is minimum,
It is set to be restricted when being used as catalysis material.
CN200710045746.4 disclose it is a kind of reduce the assistant for calalytic cracking of content of sulfur in gasoline, the auxiliary agent include zinc
The composite oxides of aluminate and dispersed zinc oxide and optionally at least one rare earth metal oxide, by
The mixture of zinc-aluminium bedded substance and optional rare earth hydrous oxide with hydrotalcite-like compound is fired and obtained, chemistry
Formula is ZnAl2O4·(1-9)ZnO·(0-0.5)RE2O3；Its preparation method is by NaOH and the dropwise addition of soluble inorganic sodium salt
Into the mixed solution of zinc salt, aluminium salt and rare earth ion, the pH value of solution is 8-11, and 1-4h is calcined at 500-1000 DEG C.This is helped
Blend and be applied in catalytic cracking process with conventional FCC catalyst and/or active enhanced aid after agent shaping, with reduction gasoline
Sulfur content function simultaneously has excellent hydrothermal stability.To obtain gahnite structure, the material is needed in higher temperature roasting
Burn, specific surface area is 120m to the maximum after roasting2/g。
CN201210178395.5 (CN103449503A) discloses a kind of preparation method of nano zinc aluminum spinelle, and it is made
Preparation Method is that zinc salt is added to the water into dissolving, adds silicon source, is stirred 10-30 minutes, adds expanding agent, stirring, at 20-100 DEG C
Aging 30-60 minutes, is dried, 500-1200 DEG C of roasting；Feed molar proportioning is Zn：Al：Water=1：2：16-35；With zinc oxide
Quality calculated for 100%, the addition of expanding agent is 0.5-30%；Expanding agent is sucrose, glycerine, ammonium carbonate, bicarbonate
One or more in ammonium, polystyrene emulsion, polyethylene glycol.The specific surface area of synthesized gahnite from 60 to
300m2/g.The zinc-aluminium proportioning that this method feeds intake is relatively low and preparation process adds expanding agent, only obtains gahnite, does not wrap
Containing dispersed zinc oxide.CN201310625314.6 (CN103691441) discloses a kind of strong absorption, high visible degraded
The preparation method of performance catalysis material, it is presoma with ternary houghite that the invention, which is related to one kind, is obtained by high-temperature roasting
High-specific-surface mesoporous structure gahnite and zinc oxide, nickel oxide nano composite photocatalyst material for obtaining and preparation method thereof,
The material is used for absorption and degraded to organic pollution.The invention utilizes zinc nitrate, nickel nitrate, aluminum nitrate, sodium carbonate and hydrogen
It is raw material that oxidation, which is received and waited, and salting liquid and aqueous slkali are configured to respectively, simultaneously under magnetic agitation, is mixed at 80 DEG C with constant flow pump；
Reaction mixture is transferred in hydrothermal reaction kettle, in hydro-thermal process 5-10h at 130-180 DEG C；Suction filtration, wash, be drying to obtain before
Body is driven, forerunner is put into Muffle furnace and is calcined 2-6 hours at 400-600 DEG C, product is produced, zinc, nickel, aluminium ion mol ratio are
1-3:1-3:1-3, specific surface area is more than 150m2/g.Need to carry out during this method synthesis of ternary houghite presoma
Hydro-thermal process, and treatment time is longer.
CN200310121344.X discloses a kind of preparation method of the Nano-class zinc oxide conductive powder body of adulterated al.The party
Method is by the soluble-salt of zinc and doped chemical aluminium, gallium, indium, yttrium, scandium, tin, germanium, the mixing salt solution of the soluble-salt of silicon and heavy
Shallow lake agent is added drop-wise in water simultaneously, is produced altogether under conditions of 40-75 DEG C of the temperature and pH value 7.0-7.5 of whole reaction system is controlled
The zinc oxide precursor basic zinc carbonate of precipitation generation doping, by the roasting under the mixed atmosphere of hydrogen and argon gas, is made
The super fine zinc oxide conductive powder material of doping is obtained, but material prepared by this method is to be applied to conductive material, doping
The addition mole of element is only the 0.1-10% of zinc and doped chemical integral molar quantity.
CN200510028233.3 discloses a kind of preparation method of high-performance sulfur transfer agent for catalytic cracking flue gas, this method with
Zinc, magnesium and aluminium are active component, using cerium and vanadium as auxiliary agent, under the conditions of 60-80 DEG C, pH value 8-10, by zinc salt, magnesium salts, aluminium salt
In the mixed solution that NaOH and sodium carbonate are added drop-wise to the mixed solution of cerium salt, obtained coprecipitated product is in 400-600
DEG C roasting 6-8h, prepares zinc mangnesium-aluminium-cerium houghite, zinc, magnesium, the mol ratio of three kinds of metals of aluminium are 1.0 by coprecipitation:
1.0-4.5:1.0-2.0, the sulfur transfer additive prepared using the material has efficient SOx absorption and desorption performance and good machine
Tool intensity.
CN200910087590.5 discloses a kind of desulfurizing agent for reforming stock oil and preparation method thereof, method for preparing catalyst
It is related to blending method, eutectic method and coprecipitation, it is characterised in that its weight, which is constituted, is：ZnO：10%-40%, NiO：15%-
22%th, Al2O3：10%-17%, SiO2：5%-22%, surplus is the impurity that can not exempt from.
CN201310089762.9 (CN 103159238) disclose a kind of nano-scale stratiform complex hydroxide and its
Fractional precipitation preparation method, be the soluble-salt and alkali for using metal for raw material, by fractional precipitation reaction make composition LDH laminates
Metal ion precipitate respectively, and produce LDH in second step precipitation process, specific surface area is 140-280m2/g.Relative to altogether
The precipitation method, although the invention employs is precipitated twice, but the LDH material specific surface areas prepared are higher, but the invention is reacted
Time is longer, and the reaction time provided in embodiment is more than 10 hours.The purpose of the invention is that the stratiform for preparing Gao Bibiao is answered
Hydroxide (LDH) is closed, the layered double hydroxide structural formula is complicated, may relate to various metals or its combination, prepare
Process needs two steps to precipitate respectively, and the reaction time is longer.《Research-zinc-aluminium the point for reducing sulfur content of catalytic cracking gasoline auxiliary agent is brilliant
The synthesis of stone and its cracking desulfurization performance》(author：Wang Peng；Sinopec Group,《(oil adds petroleum journal
Work)》2 phases of volume 19 in 2003)：A kind of preparation method of gahnite is disclosed：Sodium aluminate solution and zinc nitrate solution are pressed into m
(Al2O3)/m (ZnO)=9 ratio, is added drop-wise in 40 DEG C of distilled water with identical speed respectively, is added after being well mixed
16% sodium hydroxide solution, the pH value of regulation solution is 8.6, and the sediment of generation adds a small amount of hydrogen after aging 15min
Sodium hydroxide solution, regulation pH value is 9.0.Sediment is filtered through the repetition of more than 3 times, washing, to remove Na+.Finally will precipitation
Thing dries 4h at 120 DEG C, and 2h is calcined at 700 DEG C.The specific surface area of sample is substantially all in 160m2/ g or so.
The content of the invention
It is an object of the invention to provide a kind of complex carrier containing zinc oxide-alumina.By by the solubility containing aluminium
Salting liquid and zinc-containing solution are alternately titrated by non-constant pH, prepare the zinc oxide stratified material containing gahnite, the oxygen
Change zinc stratified material again with the kneading such as the soluble-salt of boehmite, adjuvant component phosphorus, potassium and magnesium, obtain containing zinc oxide-oxygen
Change the complex carrier of aluminium.The complex carrier zinc-aluminium is uniformly dispersed, specific surface area is high, be mainly used in FCC catalyst sulfur prodegradant and
FCC hydrodesulfurization carriers.
A kind of complex carrier containing zinc oxide-alumina of the present invention, including the zinc oxide containing gahnite, oxygen
Change aluminium, adjuvant component phosphorus, potassium and magnesium, the composition of complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite
For 5.0-40.0wt%, alumina content is 60.0-95.0wt%, and the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality
Percentage composition is respectively P2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 0.2-2.5wt%, complex carrier compare surface
Product 200-300m2/g。
It is preferred that, the composition of described complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is
10.0-35.0wt%, alumina content is 65.0-90.0wt%, and the content of adjuvant component phosphorus, potassium and magnesium accounts for the hundred of carrier quality
Point content is respectively P2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 0.2-2.5wt%, complex carrier specific surface area
200-300m2/g。
A kind of preparation method of complex carrier containing zinc oxide-alumina of the present invention, comprises the following steps：
Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, prepared containing gahnite
Zinc oxide stratified material；Zinc oxide and boehmite containing gahnite are well mixed, sesbania powder, nitric acid is added
The acid solution containing Sodium Polyacrylate after acidification, and phosphoric acid, potassium nitrate and magnesium nitrate the aqueous solution, kneading, after shaping,
Drying process, calcination process obtains containing zinc oxide-alumina composite carrier.
Zinc oxide of the present invention containing gahnite, in terms of oxide, the content of zinc oxide is 60-90wt%,
It is preferred that 65-75wt%；Specific surface area is 160-220m2/ g, preferably 190-220m2/g.The content of zinc oxide is being controlled in 65-
When 80%, specific surface area 170-200m2/g；When controlling the content of zinc oxide in 70-80wt%, specific surface area 190-220m2/
g。
The described zinc oxide stratified material prepared containing gahnite, is preferably prepared by the following preparation method：Will
Soluble Zn salting liquid is divided into 2-4 parts, under the conditions of 40-80 DEG C, and sodium metaaluminate and sodium carbonate are added in a zinc solution
Mixed solution containing aluminium, stops that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；Be further continued for be added dropwise another zinc salt it is molten
Liquid；After zinc solution is dripped, continue that mixed solution containing aluminium is added dropwise, stop being added dropwise containing aluminium mixing when pH value reaches 8.5-9.5
Solution；It will contain aluminium mixed solution according to the above method and replace titration with zinc solution, until the whole completion of dropping of zinc solution, finally
Mixed solution containing aluminium is once added dropwise, when pH value reaches 8.5-9.5, the alternating titration process of non-constant pH value terminates, control drop
Determine process to complete in 1-6h；After 80-95 DEG C of aging 2-8h, cooling washing is to neutrality, in 80-140 DEG C of dry 4-10h,
450-550 DEG C of roasting 4-10h, obtains the dispersed zinc oxide stratified material containing gahnite.
The described zinc oxide stratified material containing gahnite or the zinc oxide material containing gahnite, can be abbreviated
For zinc oxide or zinc oxide containing gahnite.
Soluble zinc salt of the present invention is zinc nitrate or zinc chloride.
The acid solution containing Sodium Polyacrylate after described nitric acid acidification, is preferably prepared by the following preparation method：
Deionized water is heated to 30-90 DEG C, then nitric acid is dissolved into deionized water, Sodium Polyacrylate is added, and dissolved
Entirely, the acid solution containing Sodium Polyacrylate is obtained.The addition of described Sodium Polyacrylate is preferably the 0.6- of boehmite
12wt%.The Sodium Polyacrylate of acidified processing, its is uniformly dispersed more preferably, and zinc oxide, alumina powder mixing are more equal
It is even.
The addition of the sesbania powder is preferably the 0.2-7wt% of boehmite.
Described drying, roasting obtains Hydrobon catalyst, is dried 4-6 hours, 550-650 DEG C at 110-140 DEG C
Lower roasting 6-8 hours, obtains Hydrobon catalyst；At described drying process, calcination process, preferably 110-150 DEG C drying
Reason calcination process 4.5-8 hours at 4-8 hours, 550 DEG C -700 DEG C.
The complex carrier containing zinc oxide-alumina obtained using preparation method of the present invention, can also using potassium and
Magnesium is modified to the complex carrier surface containing zinc oxide-alumina, and the concentration of potassium and magnesium is unsuitable too high, preferably configuration concentration
Carrier surface is sprayed less than the potassium nitrate and magnesium nitrate aqueous solution when preparing complex carrier, carrier is preferably carried out as follows
Surface is modified：Complex carrier of the aqueous solution spray containing zinc oxide-alumina containing potassium nitrate and magnesium nitrate is configured, through drying, roasting
The zinc oxide-alumina complex carrier for obtaining used additives potassium and magnesium progress surface modification is burnt, control zinc oxide-alumina is compound to be carried
Potassium oxide and content of magnesia are respectively in the range of 0.2-2.5wt% and 0.2-2.5wt%, and aoxidize carrier surface in body
The content of potassium and magnesia is 1.05-1.6 times of internal oxidation potassium and content of magnesia.
Compared with prior art, the present invention has advantages below：
1st, the zinc oxide containing gahnite of the invention is that alternately prepared by titration by non-constant pH, i.e., in non-constant pH
Prepared by the alternating titration of sodium carbonate liquor and zinc-containing solution under the conditions of value, containing aluminium, accordingly, it would be desirable to which zinc-containing solution is divided into number
Part, the sodium carbonate liquor containing aluminium is strong alkali solution, and the strong acid weak base salting liquid containing zinc is between acid solution, aluminium zinc solution
Repeatedly alternately titration pH value is swung between soda acid, be conducive to aluminium zinc precursor thing can orderly accumulation be layer structure, through straight
Connect that low-temperature bake can be uniformly dispersed and specific surface area can be in 150-220m2The point containing zinc-aluminium regulated and controled between/g is brilliant
The zinc oxide material of stone, it is to avoid the precursor obtained using the step of alkaline solution one titration zinc-aluminium mixed solution needs high-temperature roasting
The problem of fixed zinc oxide, decrease hydrothermal treatment process.The material has larger specific surface area, it is adaptable to be catalyzed material
Material, is particularly suitable for use in FCC catalyst sulfur prodegradant and hydrodesulfurization carrier material.
2nd, the present invention can also introduce phosphorus, potassium, magnesium and Sodium Polyacrylate, poly- third in zinc oxide-alumina complex carrier
Olefin(e) acid sodium can repair that to improve diffusion effect in catalytic inner pore passage structure, catalyst good.The carrier is prepared into hydrodesulfurization
Catalyst, the catalyst such as cobalt molybdenum or nickel molybdenum can suppress alkene saturated activity, and catalyst desulfurizing rate is high, alkene saturation factor
(HYD) it is low, with good hydrodesulfurization selectivity.
What the 3rd, the present invention was obtained contains zinc oxide-alumina composite carrier, using potassium and magnesium to being answered containing zinc oxide-alumina
Close carrier surface to be modified, and make the content of carrier surface potassium oxide and magnesia be internal oxidation potassium and content of magnesia
1.05-1.6 times.Complex carrier surface is modified by the way of spray, is capable of the portion on effective peptization complex carrier surface
Divide micropore, so advantageously reduce the micropore ratio on complex carrier surface, improve complex carrier surface Jie-macropore ratio, promote
Complex carrier surface produces more active sites load centres, effectively improves catalyst desulfurizing activity.Carrier surface is changed
Enter to use dipping method, impregnated carrier surface can make large quantity of moisture enter carrier, and intensity is deteriorated, and does not reach raising carrier surface
The purpose of Jie-macropore ratio.
4th, carrier surface of the present invention is through potassium and magnesium-modified effect, and the complex carrier containing zinc oxide-alumina can be made
To be used for the hydrodesulfurization of gasoline after the carrier loaded active component of Hydrobon catalyst.
Embodiment
By the following examples with comparative example to the present invention is containing zinc oxide-alumina composite carrier and preparation method thereof and answers
With being described in further detail.But these embodiments are not regarded as limiting of the invention.
Analysis method and standard：Sulfur content in oil products is analyzed：SH/T 0689-2000
Primary raw material used by catalyst is prepared to originate：Reagent of the present invention is commercially available prod.
Feedstock oil is catalytically cracked gasoline, and sulfur content is 300mg/kg, and RON is 92.0, and alkene is 41.2%vol.
Embodiment 1
1.2kg zinc nitrates are dissolved in 6L water and are made into zinc-containing solution, by 0.24kg sodium metaaluminates and 0.30kg sodium carbonate
It is dissolved in 4L water and is made into containing aluminum solutions.Zinc-containing solution is divided into 3 parts, every part of 2L.2L zinc-containing solutions are taken, temperature keeps 80
DEG C, mixed solution containing aluminium to pH value is added dropwise thereto and reaches 9.0；Stop that mixed solution containing aluminium is added dropwise, then 2L zinc-containing solutions are added dropwise
Into hybrid system, continue dropwise addition mixed solution containing aluminium to pH value and reach 9.0；Mixed solution containing aluminium and zinc-containing solution alternately drip
Fixed, until zinc-containing solution is all added, last time is added dropwise mixed solution containing aluminium and reaches 9.0 to pH, and titration time amounts to 3h.
The mixture arrived is after 80 DEG C of aging 4h, and cooling washing dries 3h to neutrality in 135 DEG C of air atmospheres, in 500 DEG C of roastings
9h, obtains the dispersed zinc oxide stratified material containing gahnite, in terms of oxide, and the content of zinc oxide is 65%；
Specific surface area is 196m2/g。
Phosphatase 11 .04g, potassium nitrate 1.03g are weighed respectively, and magnesium nitrate 8.88g, which is dissolved completely in be made into 60g distilled water, to be contained
Phosphorus, potassium, the aqueous solution of magnesium.6.0g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.8g mass concentrations are 65%
Acid.Zinc oxide of the 40g containing gahnite and 164.3g boehmites ground and mixed is uniform, 6.0g sesbania powders are added,
Sodium Polyacrylate acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading after shaping, is roasted at 125 DEG C of drying process 7 hours, 580 DEG C
Burn processing and obtain the complex carrier containing zinc oxide-alumina in 7 hours.Complex carrier specific surface area 276m2/g.Complex carrier includes
Zinc oxide 25wt% containing gahnite, aluminum oxide is 71.9wt%, and adjuvant component phosphorus, potassium, content of magnesium are respectively P2O5
0.4wt%, K2O 1.2wt%, MgO 1.5wt%.
Take 28.1g ammonium molybdates, 13.3g cobalt nitrates to be added in 30ml distilled water, add after ammoniacal liquor regulation pH value, then spend
Ionized water dilutes, and is made into complex carrier of the maceration extract dipping containing zinc oxide-alumina, obtained catalyst precursor is at 120 DEG C
6h is calcined at 550 DEG C after drying, catalyst 1 is obtained.Catalyst 1 is mainly constituted：Cobalt oxide 4wt%, molybdenum oxide 12wt%, it is oxygen-containing
Change the complex carrier 84wt% of zinc-aluminum oxide.
Comparative example 1
Zinc nitrate solution, sodium metaaluminate and the sodium carbonate liquor of amount same as Example 1 are well mixed by blending method, with reality
Apply the zinc-aluminium mol ratio of example 1 identical, similarity condition aging, washing, drying, roasting obtain the oxide material containing zinc-aluminium.Zinc oxide
Content be 65%；Specific surface area is 141m2/g.Compared with comparative example 1, embodiment 1 is using pH swing methods zinc, the friendship of aluminum solutions
For titration, zinc-aluminium stratified material can be obtained, in two kinds of material zinc-aluminium mol ratios under the same conditions, embodiment 1 is containing zinc-aluminium point
The specific surface area of the zinc oxide stratified material of spar is higher.
Phosphatase 11 .04g, potassium nitrate 1.03g are weighed respectively, and magnesium nitrate 8.88g, which is dissolved completely in be made into 60g distilled water, to be contained
Phosphorus, potassium, the aqueous solution of magnesium.6.0g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.8g mass concentrations are 65%
Acid.Oxide materials of the 40g containing zinc-aluminium and 164.3g boehmites ground and mixed is uniform, 6.0g sesbania powders are added, are gathered
PAA acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading after shaping, is calcined at 125 DEG C of drying process 7 hours, 580 DEG C
Processing obtains carrier in 7 hours.Take 28.1g ammonium molybdates, 13.3g cobalt nitrates to be added in 30ml distilled water, add ammoniacal liquor regulation pH
After value, then diluted with deionized water, be made into maceration extract impregnated carrier, obtained catalyst precursor dried at 120 DEG C after 550
DEG C roasting 6h, obtain comparative catalyst 1.
Embodiment 2
The preparation method and step be the same as Example 1 of complex carrier containing zinc oxide-alumina, are prepared containing gahnite
Zinc oxide, pH value is adjusted to 8.7.In terms of oxide, the content of zinc oxide is 70%；Specific surface area is 191m2/g。
Complex carrier includes the zinc oxide 25wt% containing gahnite, and aluminum oxide is 71.9wt%, adjuvant component phosphorus,
Potassium, content of magnesium are respectively P2O50.4wt%, K2O 0.8wt%, MgO 0.6wt%.
Except that obtaining after complex carrier, table is carried out to the complex carrier containing zinc oxide-alumina using potassium and magnesium
Face is modified, and detailed process comprises the following steps：Configuration, as spray liquid, weighs nitric acid respectively containing potassium nitrate and magnesium nitrate aqueous solution
Potassium 1.5g, magnesium nitrate 11.9g, are dissolved completely in 30ml distilled water, then are diluted with deionized water, spray zinc oxide-alumina
Complex carrier so that the content of potassium and magnesium is 1.1 times of the content of internal potassium and magnesium outside carrier.Obtained through drying, roasting
Used additives potassium and magnesium carry out the zinc oxide-alumina complex carrier of surface modification.Complex carrier specific surface area 238m2/g。
Ammonium molybdate, cobalt nitrate are made into maceration extract, dipping used additives potassium and magnesium carry out the zinc oxide-alumina of surface modification
Complex carrier, specific steps be the same as Example 1.It is calcined 6.5 hours at being dried 6 hours, 550 DEG C at 120 DEG C, obtains hydrodesulfurization
Catalyst 2.Catalyst 2 is mainly constituted：Cobalt oxide 3.5wt%, molybdenum oxide 11wt%, used additives potassium and magnesium carry out surface modification
Zinc oxide-alumina complex carrier 85.5wt%.
Embodiment 3
The preparation method and step be the same as Example 1 of complex carrier containing zinc oxide-alumina.Prepare containing gahnite
Zinc oxide, pH value is adjusted to 9.3.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 63%；Compare table
Area is 214m2/g。
Complex carrier includes the zinc oxide 18.3wt% containing gahnite, and aluminum oxide is 79wt%, adjuvant component phosphorus,
Potassium, content of magnesium are respectively P2O50.9wt%, K2O 0.8wt%, MgO 1.0wt%.Complex carrier specific surface area 242m2/g。
Ammonium molybdate, cobalt nitrate are made into maceration extract, the complex carrier containing zinc oxide-alumina is impregnated, specific steps are with real
Apply example 1.It is calcined 6 hours at being dried 4 hours, 600 DEG C at 130 DEG C, obtains Hydrobon catalyst 3.Main group of catalyst 3
Into：Cobalt oxide 6wt%, molybdenum oxide 9wt%, the complex carrier 85wt% containing zinc oxide-alumina.
Embodiment 4
The preparation method and step be the same as Example 1 of complex carrier containing zinc oxide-alumina, are prepared containing gahnite
Zinc oxide, pH value is adjusted to 8.6.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 75%；Compare table
Area is 213m2/g。
Complex carrier includes the zinc oxide 22.9wt% containing gahnite, and aluminum oxide is 75wt%, adjuvant component phosphorus,
Potassium, content of magnesium are respectively P2O51.1wt%, K2O 0.4wt%, MgO 0.6wt%.Complex carrier specific surface area 256m2/g。
Ammonium molybdate, cobalt nitrate are made into maceration extract, add ammoniacal liquor regulation pH value make salt all after dissolving dipping containing zinc oxide-
The complex carrier of aluminum oxide, specific steps be the same as Example 1.It is calcined 7 hours, is added at being dried 5 hours, 550 DEG C at 120 DEG C
Hydrogen desulphurization catalyst 4.Catalyst 4 is mainly constituted：Cobalt oxide 2.5wt%, molybdenum oxide 10wt%, answering containing zinc oxide-alumina
Close carrier 87.5wt%.
Embodiment 5
The preparation method and step be the same as Example 1 of complex carrier containing zinc oxide-alumina, are prepared containing gahnite
Zinc oxide, pH value is adjusted to 8.7.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 67%；Compare table
Area is 191m2/g。
Complex carrier includes the zinc oxide 30wt% containing gahnite, and aluminum oxide is 68wt%, adjuvant component phosphorus, potassium,
Content of magnesium is respectively P2O50.6wt%, K2O 1.0wt%, MgO 0.4wt%.Complex carrier specific surface area 279m2/g。
The present embodiment and example 2 are similar, except that obtaining after complex carrier, using potassium and magnesium to containing zinc oxide-oxidation
The complex carrier of aluminium carries out surface modification, and detailed process comprises the following steps：Configuration contains potassium nitrate and magnesium nitrate aqueous solution, spray
Zinc oxide-alumina complex carrier so that the content of carrier outside potassium and magnesium is 1.4 times of the content of internal potassium and magnesium.Through dry
Dry, roasting obtains used additives potassium and magnesium carries out the zinc oxide-alumina complex carrier of surface modification.
Ammonium molybdate, cobalt nitrate are made into maceration extract, adding ammoniacal liquor regulation pH value makes salt impregnate used additives potassium after all dissolving
The zinc oxide-alumina complex carrier of surface modification, specific steps be the same as Example 2 are carried out with magnesium.Dried 5 hours at 130 DEG C,
It is calcined 6 hours at 600 DEG C, obtains Hydrobon catalyst 5.Catalyst 5 is mainly constituted：Cobalt oxide 5wt%, molybdenum oxide 7wt%,
Complex carrier 88wt% containing zinc oxide-alumina.
By catalyst 1-5, comparative catalyst 1 is respectively charged into 10ml fixed bed reactors, carries out evaluation catalyst reaction
Performance.Presulfurization is carried out to catalyst with sulfurized oil, sulfurized oil is direct steaming gasoline, and vulcanizing agent is CS2, its concentration is 1.0wt%；
Sulfide stress is 2.8MPa, and hydrogen to oil volume ratio is 300, and sulfurized oil volume space velocity is 3.0h-1, vulcanization program for respectively 220 DEG C,
280 DEG C of vulcanizing treatment 6h.After vulcanizing treatment terminates, full cut FCC gasoline replacement Treatment 8h is switched to, treats that pre-vulcanization process terminates
Afterwards, reaction process condition is adjusted to, enters catalytically cracked gasoline reaction.Reaction process condition is：240 DEG C of temperature of reactor, reaction
Pressure 1.6MPa, volume space velocity 2.4h-1, hydrogen to oil volume ratio 240.React sampling analysis after about 55h, catalyst and contrast medium reaction
Product property is shown in Table 1.As can be seen from Table 1, Hydrobon catalyst loss of octane number is low, and desulfurization degree is high, good catalyst activity.
In the case where desulfurization degree is not less than 77%, alkene saturation factor (HYD) is only 9% or so, is selected with good hydrodesulfurization
Property.Study on the stability, reaction operation 500h, Hydrobon catalyst 1,2 and 5 product desulfurization degrees point are carried out to catalyst 1,2,5
Not Wei 80.0%, 81.1% and 83.2%, loss of octane number is respectively 0.4 unit, 0.3 unit and 0.3 unit, HYD
Respectively 10,10 and 9.The complex carrier surface of catalyst 2 and 5 produces more active sites load centres, effectively improves and urges
Agent is desulphurizing activated, and catalyst reaction performance is stable.
The catalyst of table 1 and contrast medium reactor product property
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
Protection scope of the present invention should all be belonged to.
Claims (10)
1. a kind of complex carrier containing zinc oxide-alumina, it is characterised in that：
Including the zinc oxide containing gahnite, aluminum oxide, adjuvant component phosphorus, potassium and magnesium, the composition of complex carrier is with oxide
Quality meter：Zinc oxide content containing gahnite is 5.0-40.0wt%, and alumina content is 60.0-95.0wt%, auxiliary agent
The content of component phosphorus, potassium and magnesium accounts for the percentage composition respectively P of carrier quality2O50.2-1.2wt%, K2O 0.2-2.5wt%,
MgO 0.2-2.5wt%, complex carrier specific surface area 200-300m2/g。
2. a kind of complex carrier containing zinc oxide-alumina according to claim 1, it is characterised in that：
The composition of described complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite is 10.0-
35.0wt%, alumina content is 65.0-90.0wt%, and the percentage that the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality contains
Amount is respectively P2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 0.2-2.5wt%, complex carrier specific surface area 200-
300m2/g。
3. a kind of preparation method of the complex carrier containing zinc oxide-alumina described in claim 1 or 2, it is characterised in that including
Following steps：
Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, the oxygen containing gahnite is prepared
Change zinc stratified material；Zinc oxide and boehmite containing gahnite are well mixed, sesbania powder, nitric acid acidifying is added
The acid solution containing Sodium Polyacrylate after processing, and phosphoric acid, potassium nitrate and magnesium nitrate the aqueous solution, kneading, after shaping, dry
Processing, calcination process obtains containing zinc oxide-alumina composite carrier.
4. a kind of preparation method of complex carrier containing zinc oxide-alumina according to claim 3, it is characterised in that：
The described zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 60-90wt%, and specific surface area is 160-
220m2/ g, when controlling the content of zinc oxide in 65-80%, specific surface area 170-200m2/g；Exist in the content of control zinc oxide
During 70-80wt%, specific surface area 190-220m2/g。
5. a kind of preparation method of complex carrier containing zinc oxide-alumina according to claim 3, it is characterised in that：
The described zinc oxide stratified material prepared containing gahnite, is prepared by the following preparation method：Soluble zinc salt is molten
Liquid is divided into 2-4 parts, under the conditions of 40-80 DEG C, and the mixed solution containing aluminium of sodium metaaluminate and sodium carbonate is added in a zinc solution,
Stop that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；It is further continued for that another zinc solution is added dropwise；Zinc solution is added dropwise
After complete, continue that mixed solution containing aluminium is added dropwise, stop that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；According to the above method
Aluminium mixed solution will be contained and replace titration with zinc solution, until the whole completion of dropping of zinc solution, last time is added dropwise mixed containing aluminium
Solution is closed, when pH value reaches 8.5-9.5, the alternating titration process of non-constant pH value terminates, control titration process is in 1-6h
Complete；After 80-95 DEG C of aging 2-8h, cooling washing to neutrality, in 80-140 DEG C of dry 4-10h, 450-550 DEG C of roasting 4-
10h, obtains the dispersed zinc oxide stratified material containing gahnite.
6. a kind of preparation method of complex carrier containing zinc oxide-alumina according to claim 5, it is characterised in that：
The soluble zinc salt is zinc nitrate or zinc chloride.
7. a kind of preparation method of complex carrier containing zinc oxide-alumina according to claim 3, it is characterised in that：
The acid solution containing Sodium Polyacrylate after described nitric acid acidification, is prepared by the following preparation method：By deionized water plus
Heat arrives 30-90 DEG C, and then nitric acid is dissolved into deionized water, adds Sodium Polyacrylate, and dissolves complete, obtains containing poly- third
The acid solution of olefin(e) acid sodium.The Sodium Polyacrylate of acidified processing, the addition of described Sodium Polyacrylate is boehmite
0.6-12wt%.
8. a kind of preparation method of complex carrier containing zinc oxide-alumina according to claim 3, it is characterised in that：
The addition of the sesbania powder is the 0.2-7wt% of boehmite.
9. a kind of preparation method of complex carrier containing zinc oxide-alumina according to claim 3, it is characterised in that：
Described drying, roasting obtains Hydrobon catalyst, refers to roast at drying 4-6 hours, 550-650 DEG C at 110-140 DEG C
Burning obtains Hydrobon catalyst in 6-8 hours；Described drying process, calcination process refers to 110-150 DEG C of drying process 4-8
Hour, calcination process 4.5-8 hours at 550 DEG C -700 DEG C.
10. a kind of preparation method of complex carrier containing zinc oxide-alumina according to claim 3, it is characterised in that：
The complex carrier containing zinc oxide-alumina obtained to claim 3, using potassium and magnesium to being combined containing zinc oxide-alumina
Carrier surface is modified, and carrier surface modification is carried out as follows：Configure the aqueous solution spray containing potassium nitrate and magnesium nitrate
Drench the complex carrier containing zinc oxide-alumina, through drying, roasting obtain used additives potassium and magnesium carry out the zinc oxide of surface modification-
Potassium oxide and content of magnesia are respectively in 0.2-2.5wt% in alumina composite carrier, control zinc oxide-alumina complex carrier
In the range of 0.2-2.5wt%, and the content of carrier surface potassium oxide and magnesia is set to be that internal oxidation potassium and magnesia contain
1.05-1.6 times of amount.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108031431A (en) * | 2017-12-26 | 2018-05-15 | 大连全净科技有限公司 | The composite reactive Al that a kind of surface is modified2O3The preparation method of-ZnO carrier spheric granules |
| CN110142044A (en) * | 2019-06-03 | 2019-08-20 | 北京柯通科技有限公司 | A kind of hydrogenation of petroleum resin catalyst and its preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5525210A (en) * | 1993-01-27 | 1996-06-11 | W. R. Grace & Co. Conn. | Sulfur reduction in FCC gasoline |
| CN1164563A (en) * | 1996-05-02 | 1997-11-12 | 中国科学院山西煤炭化学研究所 | Method for preparing alumina as catalyst carrier |
| CN1533363A (en) * | 2001-07-27 | 2004-09-29 | ǧ���ﻯ��������ʽ���� | Porous 4 group metal oxide and method for preparation thereof |
| CN101439291A (en) * | 2007-11-19 | 2009-05-27 | 中国石油大学(北京) | Multiple-addition agent modified selective hydrodesulfurization catalyst and preparation method thereof |
| CN104971706A (en) * | 2014-04-09 | 2015-10-14 | 中国石油化工股份有限公司 | Method of preparing titanium oxide-aluminum oxide composition and application thereof |
-
2017
- 2017-03-17 CN CN201710158372.0A patent/CN106955746A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5525210A (en) * | 1993-01-27 | 1996-06-11 | W. R. Grace & Co. Conn. | Sulfur reduction in FCC gasoline |
| CN1164563A (en) * | 1996-05-02 | 1997-11-12 | 中国科学院山西煤炭化学研究所 | Method for preparing alumina as catalyst carrier |
| CN1533363A (en) * | 2001-07-27 | 2004-09-29 | ǧ���ﻯ��������ʽ���� | Porous 4 group metal oxide and method for preparation thereof |
| CN101439291A (en) * | 2007-11-19 | 2009-05-27 | 中国石油大学(北京) | Multiple-addition agent modified selective hydrodesulfurization catalyst and preparation method thereof |
| CN104971706A (en) * | 2014-04-09 | 2015-10-14 | 中国石油化工股份有限公司 | Method of preparing titanium oxide-aluminum oxide composition and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王鹏等: ""降低催化裂化汽油硫含量助剂的研究———锌铝尖晶石的合成及其裂化脱硫性能"", 《石油学报(石油加工)》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108031431A (en) * | 2017-12-26 | 2018-05-15 | 大连全净科技有限公司 | The composite reactive Al that a kind of surface is modified2O3The preparation method of-ZnO carrier spheric granules |
| CN110142044A (en) * | 2019-06-03 | 2019-08-20 | 北京柯通科技有限公司 | A kind of hydrogenation of petroleum resin catalyst and its preparation method and application |
| CN110142044B (en) * | 2019-06-03 | 2022-07-26 | 北京柯通科技有限公司 | Petroleum resin hydrogenation catalyst, and preparation method and application thereof |
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