CN112742381B - Shell-layer distributed catalyst and preparation method and application thereof - Google Patents
Shell-layer distributed catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN112742381B CN112742381B CN201911037358.0A CN201911037358A CN112742381B CN 112742381 B CN112742381 B CN 112742381B CN 201911037358 A CN201911037358 A CN 201911037358A CN 112742381 B CN112742381 B CN 112742381B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- active component
- film
- forming polymer
- shell
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 238000005507 spraying Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 23
- 238000003786 synthesis reaction Methods 0.000 claims description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001038 ethylene copolymer Polymers 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- -1 polyethylene terephthalate Polymers 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 102000008186 Collagen Human genes 0.000 claims description 2
- 108010035532 Collagen Proteins 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 229920001436 collagen Polymers 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 44
- 230000000694 effects Effects 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 14
- 238000005470 impregnation Methods 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 102000002322 Egg Proteins Human genes 0.000 description 3
- 108010000912 Egg Proteins Proteins 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 210000003278 egg shell Anatomy 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000009495 sugar coating Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004126 brilliant black BN Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004334 oxygen containing inorganic group Chemical group 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052720 vanadium 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B01J35/397—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
-
- 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
- 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
- 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 the field of catalyst preparation, and discloses a shell-distributed catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Spraying a porous carrier with a solution containing a film-forming polymer, wherein the spraying amount of the solution is V L1 The pore volume of the porous carrier is V C ，V L1 /V C =0.01-0.6; (2) Spraying the product obtained in step (1) with a solvent, the solvent beingSpraying amount is V L2 ，V L2 /V C =0.01-0.6; (3) drying the product obtained in the step (2); (4) Dipping the product obtained in the step (3) by using a solution containing a catalytic active component; and (5) roasting the product obtained in the step (4). The preparation method of the shell-distributed catalyst provided by the invention is simple to operate and good in repeatability, and the prepared catalyst has good catalytic performance when being used in catalytic reaction.
Description
Technical Field
The invention relates to the field of catalyst preparation, in particular to a shell-distributed catalyst and a preparation method and application thereof.
Background
If the product molecules generated by the reaction at the deep part of the catalyst pore channel can not be diffused out in time to further react, the selectivity of the catalyst is influenced on one hand, and the service life of the catalyst is influenced on the other hand. Particularly reactions in which internal diffusion is a controlled step, it is desirable that the reaction occur at a site that facilitates diffusion of the reactants and products, and generally at the surface of the catalyst. In addition, in the cost of the catalyst, the proportion of the cost of the active component is larger, and if the component which is not high in utilization rate and distributed in the deep part of the pore channel is moved to the area close to the surface layer of the catalyst, the cost of the catalyst is undoubtedly reduced, and the activity and the selectivity of the catalyst are favorably improved.
US5545674A discloses a process for preparing a shell-type catalyst by spreading the support over a wire, heating the wire to above 140 ℃ in a heating furnace and removing it from the furnace. Spraying the solution containing the supported component on a heat carrier on a metal wire mesh, evaporating the solution containing the supported component on the surface of the hot carrier, and then putting the metal wire mesh with the catalyst back into the heating furnace for reheating. This is repeated a number of times until sufficient loading component is loaded.
CN101318133A discloses a shell catalyst for preparing naphtha and diesel oil, which uses active carbon as carrier, and adopts a spraying method to spray the solution onto the rolling carrier, and then the catalyst is dried or calcined in inert gas. However, the catalyst prepared by this method has a low shell fraction.
CN102451722A discloses a preparation method of an eggshell type hydrogenation catalyst. The method comprises the steps of impregnating a carrier with an active metal aqueous solution containing a thickening agent and an active metal dispersing agent, wherein the carrier is impregnated under the condition of introducing air bubbles, and then drying and roasting are carried out to obtain the eggshell type hydrogenation catalyst. The method can effectively adjust the surface activity of the eggshell type hydrogenation catalyst, the thickness of the metal shell layer and the dispersion degree of the active metal, stabilize the active metal component on the hydrogenation catalyst, reduce the loss of the active metal component and reduce the production cost of the catalyst. However, the preparation method has strict requirements on time, is complicated to operate and is not easy to realize large-scale production.
US4599481A discloses a process for the production of hydrocarbons by the catalytic reaction of carbon monoxide with hydrogen which comprises contacting carbon monoxide and hydrogen with a catalyst comprising a support and cobalt supported on the support, the distribution of the cobalt on the support satisfying (Σ Vp/Σ Vc) < 0.85 at a temperature of 125 to 350 ℃ and a pressure of 5 to 100 bar (bar), wherein Σ Vc represents the total volume of the catalyst particles and Vp is the volume of the catalyst mid-shell. The catalyst has high activity and selectivity when the cobalt content in the shell is about 90%. The preparation method of the catalyst comprises the steps of firstly treating the carrier with water, then soaking the carrier in cobalt nitrate solution, and then drying and roasting the carrier. The preparation method has strict requirements on time, is complicated to operate and is not easy to realize large-scale production.
Therefore, the method for preparing the shell-distributed catalyst is complex, and the method for preparing the shell-distributed catalyst still needs to be continuously explored.
Disclosure of Invention
The invention aims to provide a preparation method of a novel shell-distributed catalyst, the shell-distributed catalyst prepared by the method and application of the shell-distributed catalyst. The preparation method of the shell-distributed catalyst provided by the invention is simple to operate and good in repeatability, and the prepared catalyst has good catalytic performance when being used in catalytic reaction.
In order to achieve the above object, the present invention provides, in one aspect, a method for preparing a shell-distributed catalyst, the method comprising:
(1) Spraying a porous carrier with a solution containing a film-forming polymer, the amount of said solution sprayed being V L1 The pore volume of the porous carrier is V C ，V L1 /V C ＝0.01-0.6；
(2) Spraying the product obtained in the step (1) by using a solvent, wherein the spraying amount of the solvent is V L2 ，V L2 /V C ＝0.01-0.6；
(3) Drying the product obtained in the step (2);
(4) Impregnating the product obtained in the step (3) with a solution containing a catalytic active component;
(5) And (5) roasting the product obtained in the step (4).
Preferably, the concentration of the solution containing the film-forming polymer is 0.1 to 15 wt%, preferably 0.3 to 10 wt%, more preferably 0.5 to 8 wt%, and still more preferably 1 to 5 wt%.
Preferably, the film-forming polymer is polyvinyl alcohol and/or a vinyl alcohol-olefin copolymer, more preferably a vinyl alcohol-olefin copolymer, most preferably a vinyl alcohol-ethylene copolymer.
In a second aspect, the present invention provides a shell distributed catalyst prepared by the process of the present invention.
In a third aspect, the invention provides the use of the shell distributed catalyst of the invention in fischer-tropsch synthesis or hydrofinishing reactions.
The preparation method of the shell-distributed catalyst has the advantages of simple and easily-controlled operation process and good repeatability, and is particularly suitable for large-scale implementation. The shell-distributed catalyst prepared by the method of the invention is used as the catalyst of the Fischer-Tropsch synthesis reaction, and can obtain higher catalytic activity and C 5+ Hydrocarbon selectivity. The shell-distributed catalyst prepared by the method is used as a catalyst for hydrofining reaction, and can obtain higher hydrodesulfurization activity and hydrodenitrogenation activity.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The "shell-distributed catalyst" of the present invention is also referred to as an eggshell-type non-uniformly distributed catalyst, which is abbreviated as an eggshell-type catalyst, and is defined by those skilled in the art, for example, as defined in pages 199 to 200 (page 1, 5.2002 of oil industry press) in the book "preparation and application of catalyst support", which is edited by zhuhong law.
The invention provides a preparation method of a shell-distributed catalyst, which comprises the following steps:
(1) Spraying a porous carrier with a solution containing a film-forming polymer, wherein the spraying amount of the solution is V L1 The pore volume of the porous carrier is V C ，V L1 /V C ＝0.01-0.6；
(2) Spraying the product obtained in the step (1) by using a solvent, wherein the spraying amount of the solvent is V L2 ，V L2 /V C ＝0.01-0.6；
(3) Drying the product obtained in the step (2);
(4) Impregnating the product obtained in the step (3) with a solution containing a catalytic active component;
(5) And (4) roasting the product obtained in the step (4).
According to the method of the present invention, preferably, the film-forming polymer is selected from at least one of polyvinyl alcohol, a vinyl alcohol-olefin copolymer, partially hydrolyzed polyvinyl alcohol, a partially hydrolyzed vinyl alcohol-olefin copolymer, polyvinyl acetate, polyethylene glycol, collagen, polyethylene terephthalate, polyethylene naphthalate, polyamide, polysaccharide, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyacrylate resin, and a copolymer containing an acrylate ester unit.
The degree of hydrolysis of the partially hydrolyzed polyvinyl alcohol and partially hydrolyzed vinyl alcohol-olefin copolymer of the present invention is selected from a wide range and can be selected by conventional techniques in the art, and the present invention is not described herein again.
According to the invention, preferably, the polysaccharide is selected from cellulose and derivatives thereof and/or starch, for example C1-C4 alkyl cellulose and/or modified starch.
According to the invention, the olefin units in the vinyl alcohol-olefin copolymer are preferably ethylene.
According to a preferred embodiment of the invention, the film-forming polymer is polyvinyl alcohol and/or a vinyl alcohol-olefin copolymer, more preferably a vinyl alcohol-olefin copolymer, most preferably a vinyl alcohol-ethylene copolymer. By adopting the preferred embodiment, the catalytic performance of the prepared catalyst is improved.
The molecular weight of the film-forming polymer is selected from a wide range, and preferably, the weight average molecular weight of the film-forming polymer is 16000-130000.
The concentration of the film-forming polymer in the solution containing the film-forming polymer can be selected from a wide range, and preferably, the concentration of the solution containing the film-forming polymer is 0.1 to 15% by weight, preferably 0.3 to 10% by weight, more preferably 0.5 to 8% by weight, and still more preferably 1 to 5% by weight.
The solvent of the solution of the film-forming polymer is selected from a wide range and can be water and/or an organic solvent.
The solvent used in the step (2) of the invention has a wide selection range, and can be water and/or an organic solvent.
According to a preferred embodiment of the present invention, the solvent of the solution containing the film-forming polymer and the solvent of step (2) are each independently selected from at least one of water, methanol, ethanol, propanol, acetone, ethyl acetate, furfural, benzene, toluene, and cyclohexane, and further preferably water. In the present invention, the solvent of the solution containing the film-forming polymer may be the same as or different from the solvent described in the step (2), and preferably, the solvent of the solution containing the film-forming polymer is the same as the solvent described in the step (2). With this preferred embodiment it is easier to distribute the film-forming polymer uniformly on the support, so that the depth of the solution into the support is comparable during impregnation of the solution containing the catalytically active component, and the shell thickness is uniform.
According to a preferred embodiment of the present invention, in step (1), V L1 /V C =0.05-0.45, preferably V L1 /V C ＝0.1-0.3。
According to a preferred embodiment of the present invention, in step (2), V L2 /V C =0.05-0.45, further preferably V L2 /V C ＝0.1-0.3。
In the present invention, V C Is equal to the mass of the porous support (in grams) multiplied by the water absorption of the porous support (density of water 1 g/cm) 3 ) The water absorption is the amount of water absorbed (e.g., ml/g) per unit weight of the carrier. Specifically, the water absorption can be measured by the following method: the carrier (by weight) may be mixed with water in a ratio of carrier (by weight) to water (by volume) of 1:3 immersion for 2 hours, after filtration, the solids were drained and the carrier water absorption volume was calculated, absorption = carrier water absorption volume/carrier weight.
According to the method of the present invention, the spraying in step (1) can be carried out by various methods. Specifically, the porous support may be placed in a rotating vessel and the solution containing the film-forming polymer then sprayed onto the rolling support, and the present invention is not particularly limited to this operation, and one skilled in the art will know how to do so. The rotating vessel may be a sugarcoating machine.
The spraying in the step (2) can be the same as the spraying way described above, and the invention is not described herein again.
According to the method of the present invention, the porous support may be a common porous substance suitable as a catalyst support. Specifically, the porous support may be at least one of a heat-resistant inorganic oxide, aluminum silicate, and activated carbon. The heat-resistant inorganic oxide is an inorganic oxygen-containing compound having a decomposition temperature of not less than 300 ℃ (for example, a decomposition temperature of 300 to 1000 ℃) in an oxygen or oxygen-containing atmosphere. Specific examples of the porous carrier may include, but are not limited to: at least one of alumina, magnesia, zirconia, calcia, silica, titania, aluminosilicate, molecular sieves, and rare earth oxides. Preferably, the porous support is selected from at least one of alumina, magnesia, zirconia, calcia, silica and titania. More preferably, the porous support is alumina.
The shape of the porous carrier is not particularly limited in the present invention, and may be a conventional shape, for example, a sphere, a tablet, a strip, etc., preferably a strip. According to the method of the present invention, the average particle diameter of the porous carrier may be selected according to the specific kind of the catalyst, and is preferably in the range of 0.5 to 6mm, more preferably in the range of 1 to 4 mm.
The invention has wide selection range of the drying conditions in the step (2), and the drying temperature is based on the capability of removing the solvent loaded on the porous carrier. Generally, preferably, the drying conditions include: the temperature is 40-90 ℃ and the time is 1-48 hours; further preferably, the drying is performed under vacuum conditions. The drying temperature is preferably 50 to 90 ℃ and the drying time is preferably 2 to 16 hours.
According to the process of the present invention, the type of the catalytically active component may be selected according to the intended application of the catalyst, based on the catalyst having the predetermined catalytic properties, such as the group VIII metal elements and/or the group VIB metal elements.
In a preferred embodiment of the invention, the catalytically active component is of a type such that the shell distributed catalyst prepared by the process of the invention is catalytic for the fischer-tropsch synthesis reaction. In this preferred embodiment, the catalytically active component may be a component having a catalytic effect on the fischer-tropsch synthesis reaction, and preferably, the catalytically active component is selected from group VIII metal elements, and specifically, may be one or more of iron, cobalt, and ruthenium.
According to the method of the present invention, the solution containing the catalytically active component may be provided by dissolving a compound containing the catalytically active component in a solvent. The kind of the compound containing the catalytically active component may be selected depending on the kind of the solvent, so as to be soluble in the solvent. For example, when the solvent is water, the compound containing a catalytically active component may be a water-soluble compound. In one embodiment of the present invention, when the catalytically active component is a group VIII metal element, the compound containing the catalytically active component may be a water-soluble non-metal salt of oxygen-containing inorganic acid having a group VIII metal as a cation, a water-soluble salt of organic acid having a group VIII metal as a cation, or two or more thereof. Preferably, the compound containing the catalytic active component is one or more of nitrate taking the VIII group metal as cation, acetate taking the VIII group metal as cation, and chloride taking the VIII group metal as cation of alkali carbonate taking the VIII group metal as cation. Specifically, the compound containing a catalytically active component may be selected from one or more of, but not limited to, iron nitrate, iron acetate, iron citrate, cobalt nitrate, cobalt acetate, cobalt hydroxycarbonate, ruthenium chloride, and ruthenium nitrosyl nitrate.
According to a preferred embodiment of the invention, the amount of the solution containing the catalytically active component in step (4) and the amount V of the solvent sprayed in step (2) are the same L2 Are equal. The preferred embodiment is more favorable for ensuring that the solution enters the carrier with the same depth when the solution containing the catalytic active component is immersed, and the thickness of the shell layer is uniform.
The concentration of the catalytically active component in the solution containing the catalytically active component may be selected according to the expected loading amount of the catalytically active component in the catalyst, and is not particularly limited.
According to the method of the present invention, the loading amount of the solution containing the catalytically active component on the product obtained in step (3) is determined so as to ensure that the finally prepared catalyst is loaded with a sufficient amount of the catalytically active component. Generally, the loading of the catalytically active component on the porous support is such that the content of the catalytically active component, calculated as oxide, is from 0.05 to 30% by weight, preferably from 0.1 to 25% by weight, such as from 1 to 20% by weight, based on the total amount of the finally prepared catalyst.
According to another preferred embodiment of the present invention, the shell-distributed catalyst has a catalytic effect on a hydrorefining reaction. The type of the catalytic active component enables the shell-distributed catalyst prepared by the method to have a catalytic effect on the hydrofining reaction. In this preferred embodiment, the catalytically active component may be a component having a catalytic effect on the hydrorefining reaction, and preferably, the catalytically active component is selected from at least one of group VIII metal elements and at least one of group VIB metal elements, and specifically, the catalytically active component contains cobalt and/or nickel and molybdenum and/or tungsten. The details of the solution containing a catalytically active component in this preferred embodiment may be as described above, and preferably, the compound containing a catalytically active component includes a compound containing a group VIII metal element and a compound containing a group VIB metal element. For example, the group VIII metal element-containing compound is selected from, but not limited to: one or more of nickel nitrate, nickel acetate, nickel sulfate, basic nickel carbonate, cobalt nitrate, cobalt acetate, cobalt sulfate, basic cobalt carbonate, cobalt chloride and nickel chloride; the compound containing the VIB group metal element is one or more than two of nitrate, acetate, sulfate, basic carbonate and chloride of the VIB group metal element, and the types of the compound are not described again. The concentration of the catalytically active component in the solution containing the catalytically active component may be selected according to the desired loading amount of the catalytically active component in the catalyst, and is not particularly limited. According to the method of the present invention, the loading amount of the solution containing the catalytically active component on the product obtained in step (3) is determined so as to ensure that the finally prepared catalyst is loaded with a sufficient amount of the catalytically active component. Generally, the loading of the catalytically active component on the porous support is such that the content of group VIII metal elements, calculated as oxides, is from 1 to 20 wt.%, for example from 3 to 10 wt.%, and the content of group VIB metal elements, calculated as oxides, is from 5 to 30 wt.%, for example from 8 to 20 wt.%, based on the total amount of the finally prepared catalyst.
According to the process of the invention, the solution containing the catalytically active component may also contain at least one promoter component. When the catalyst has a catalytic effect on the Fischer-Tropsch synthesis reaction, the catalyst promoter component can be one or more than two of Li, na, K, mg, ca, sr, cu, mo, ta, W, zr, ti, hf, ce, mn, V and noble metals (such as one or more than two of Pt, pd, re, rh and Ir). When the catalyst has a catalytic effect on a hydrofinishing reaction, the catalyst promoter component may be selected from elemental phosphorus and/or elemental fluorine.
The content of the catalyst promoter component in the solution containing the catalytically active component is based on the content of the catalyst promoter component expected in the finally prepared catalyst. The present invention is not particularly limited to this, and those skilled in the art can appropriately select the catalyst according to the field of application of the catalyst.
According to a specific embodiment of the present invention, the method further comprises drying the product obtained in step (4) before the roasting in step (5). The drying temperature is based on the solvent which can be removed from the solution loaded on the porous carrier. In general, the drying may be carried out at a temperature of from 40 to 250 ℃ for from 1 to 48h, preferably at a temperature of from 80 to 200 ℃ for from 2 to 24h. The drying may be performed under normal pressure or under reduced pressure.
In the present invention, the conditions for the calcination in the step (5) are not particularly limited, and may be selected conventionally. Generally, the calcination may be carried out at a temperature of 250 to 600 ℃, preferably at a temperature of 300 to 500 ℃. The duration of the calcination may be 1 to 48 hours, preferably 2 to 12 hours, more preferably 2 to 5 hours.
In a second aspect, the invention provides a shell distributed catalyst prepared by the method.
The third aspect of the invention provides an application of the shell layer distribution type catalyst in Fischer-Tropsch synthesis reaction or hydrofining reaction.
Specifically, the application of the shell-layer distribution type catalyst in the fischer-tropsch synthesis reaction can comprise contacting the synthesis gas with the catalyst under the fischer-tropsch synthesis reaction condition, wherein the catalyst is the shell-layer distribution type catalyst which is prepared by the method and has a catalytic effect on the fischer-tropsch synthesis reaction.
According to the application of the catalyst provided by the invention in Fischer-Tropsch synthesis reaction, before use, the active metal component in an oxidation state is subjected to reduction activation preferably in the presence of hydrogen. The conditions for reductive activation may include: the reduction temperature may be 200 ℃ to 1000 ℃, preferably 200 ℃ to 800 ℃, the reduction time may be 1 to 96 hours, preferably 2 to 24 hours, the reduction activation may be carried out in pure hydrogen, or in a mixed gas of hydrogen and an inert gas, such as a mixed gas of hydrogen and nitrogen, and the hydrogen pressure may be 0.1 to 4MPa, preferably 0.1 to 2MPa, the inert gas refers to a gas that does not participate in the chemical reaction under the conditions of the present invention, such as nitrogen and a group zero element gas.
According to the present invention, the reaction conditions for the Fischer-Tropsch reaction are not particularly limited, and may be carried out under conventional conditions. Specifically, the temperature may be 170 to 350 ℃, preferably 180 to 300 ℃; the total pressure can be 1-20MPa, preferably 1.5-15MPa; the gas hourly space velocity of the synthesis gas can be 1000-20000h -1 Preferably 2000-18000h -1 。
Specifically, the application of the shell-layer distributed catalyst in the hydrofining reaction can comprise that hydrocarbon oil is contacted with the catalyst under the hydrofining reaction condition, wherein the catalyst is the shell-layer distributed catalyst which is prepared by the method and has a catalytic effect on the hydrofining reaction.
According to the invention there is provided the use of a catalyst in a hydrofinishing reaction, said catalyst preferably being presulfided prior to use using methods conventional in the art. In general, the conditions of the prevulcanisation may include: presulfiding with one or more of sulfur, hydrogen sulfide, carbon disulfide, dimethyl disulfide, or polysulfide in the presence of hydrogen at a temperature of 360-400 ℃ for 2-4 hours. The pre-vulcanization can be carried out outside the hydrogenation reactor or can be carried out in situ in the hydrogenation reactor.
The catalyst of the invention is suitable for the refining processes of hydrodesulfurization, hydrodenitrogenation and the like of various hydrocarbon oil raw materials. The hydrocarbon oil feedstock may be, for example, one or more of gasoline, diesel oil, lubricating oil, kerosene, and naphtha; and may be one or more of atmospheric residue, vacuum residue, petroleum wax and Fischer-Tropsch synthetic oil.
According to the present invention, the specific reaction conditions for the hydrorefining reaction are not particularly limited, and may be carried out under conventional conditions. Generally, the hydrofinishing conditions include: the temperature can be 300-400 ℃; the pressure can be 1.0-8.0MPa in gauge pressure; the liquid hourly space velocity of the hydrocarbon oil can be 0.5-3.0 h -1 (ii) a The hydrogen to oil volume ratio may be 100-700.
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
In the following examples, the film-forming polymer EVOH (vinyl alcohol-ethylene copolymer) is commercially available from the Nippon Coli group under the designation E151; polyvinyl alcohol (PVA) is commercially available from shanghai alading reagent limited under the designation PVA1799.
Example 1
(1) A solution containing a film-forming polymer (the amount and type of which are shown in Table 1) was sprayed onto 200g of a rolling porous support (cylindrical gamma-alumina having a diameter of 2 mm), the rolling of the support during the spraying being carried out in a rotating vessel (model BY300 sugarcoating machine, jin Tai pharmaceutical machinery, inc., tanzhou) rotating at 46 revolutions per minute.
(2) The product obtained in step (1) was sprayed with a solvent, the kind and amount of which are shown in table 2.
(3) The product obtained in step (2) was dried at 80 ℃ for 4 hours.
(4) Dissolving ammonium metatungstate and nickel nitrate in water to prepare impregnation liquid (WO) 3 The concentration of (3) was 402 g/l and the concentration of NiO was 25 g/l). And according to V in Table 2 L2 /V C The product obtained in the step (3) is impregnated by the impregnation liquid according to the proportion;
(5) And drying at 120 ℃ for 4 hours after the impregnation is finished, and roasting the dried sample at 450 ℃ for 2 hours to obtain the shell-distributed catalyst S-1.
Comparative example 1
The procedure is as in example 1, except that step (2) is excluded. Thus obtaining the shell-distributed catalyst D-1. It was observed that a white streak appeared on the shell-distributed catalyst D-1, indicating that the impregnation was not uniform.
Examples 2 to 7
The process of example 1 was followed except that the amount and type of the solution containing the film-forming polymer in step (1) were as shown in Table 1 and the type and amount of the solvent in step (2) were as shown in Table 2. Preparing the catalysts S-2 to S-7 with distributed shells.
TABLE 1
TABLE 2
| Examples | Solvent(s) | V L2 /V C |
| 1 | Water (I) | 0.24 |
| 2 | Water (I) | 0.20 |
| 3 | Water (W) | 0.13 |
| 4 | Water (W) | 0.16 |
| 5 | Water (W) | 0.13 |
| 6 | Water (W) | 0.14 |
| 7 | Water (W) | 0.18 |
Example 8
According to the method of example 1, except that the composition of the impregnation solution is different, specifically, the preparation of the impregnation solution in step (4) comprises: dissolving ammonium molybdate, ammonium metatungstate, nickel nitrate and phosphoric acid in water to prepare impregnation liquid (MoO) 3 In a concentration of 225 g/l, WO 3 Has a concentration of 100 g/l, a NiO concentration of 50 g/l, P 2 O 5 At a concentration of 50 g/l). Obtaining the catalyst S-8 with a distributed shell layer.
Examples 9 to 15
The method of examples 1 to 7 was followed, respectively, except that the composition of the impregnation solution was different, and specifically, the preparation of the impregnation solution in step (4) included: 131 g of cobalt nitrate was weighed, and dissolved in water to prepare 100mL of a cobalt nitrate solution as a dipping solution. Obtaining the catalysts C-1 to C-7 with distributed shells.
Comparative example 2
The procedure is as in example 9, except that step (2) is excluded. Obtaining the catalyst D-2 with distributed shell layers. It was found by observation that a white streak appeared on the shell layer distribution type catalyst D-2, indicating that the impregnation was not uniform.
Example 16
The procedure of example 9 was repeated, except that the composition of the impregnation solution was changed, and specifically, the impregnation solution in step (4) was a ruthenium nitrosyl nitrate solution having a concentration of 0.52 mol/l. Obtaining the shell distributed catalyst C-8.
Example 17
The process of example 9 was followed except that the amount of the solvent sprayed in step (2) was varied in accordance with the pore volume V of the porous carrier C The ratio of (a) to (b) is 0.45:1. obtaining the shell-distributed catalyst C-9.
Test example 1
The catalysts prepared in examples 1-8 and comparative example 1 were evaluated on a 30 ml diesel hydrogenation unit, respectively.
The raw materials used were as follows: middle east straight run diesel; and (2) S content: 9700wppm, N content: 97wppm, density (20 ℃): 0.8321g/cm 3 Refractive index (20 ℃): 1.4658.
the catalyst is vulcanized before use, and the vulcanization conditions are as follows: the vulcanization pressure is 3.2MPa, and the vulcanized oil contains CS 2 2 percent of kerosene by weight and a volume space velocity of 2h -1 And the hydrogen-oil ratio is 300v/v, the constant temperature is kept for 6h at 230 ℃/h, then the temperature is raised to 360 ℃ for vulcanization for 8h, and the temperature raising rate of each stage is 10 ℃/h. And after vulcanization, reaction raw materials are switched to carry out hydrodesulfurization and denitrification activity test. The test conditions were: the pressure is 3.2MPa, and the liquid hourly volume space velocity is 2.0h -1 The hydrogen-oil ratio was 300v/v, and the reaction temperature was 330 ℃. The relative hydrodesulfurization activity and the relative hydrodenitrogenation activity of the catalysts are shown in table 3.
In Table 3, the hydrodesulfurization activity of the catalyst was evaluated by using the relative hydrodesulfurization activity calculated by treating the hydrodesulfurization reaction as a 1.65-stage reaction and calculating the reaction rate constant k (X) of the catalyst X according to the following formula HDS ：
Wherein LHSV is the liquid hourly volume space velocity of the hydrocarbon oil during the hydrorefining reaction,
with the hydrodesulfurization activity of catalyst D-1 (denoted as k (D-1) HDS ) For reference, the relative hydrodesulfurization activity of catalyst X was calculated as follows:
relative hydrodesulfurization activity (X) = [ k (X) HDS /k(D-1) HDS ]×100％。
In Table 3, the hydrodenitrogenation activity of the catalyst was evaluated by using the relative hydrodenitrogenation activity, which was calculated by treating the hydrodenitrogenation reaction as a 1-stage reaction and calculating the reaction rate constant k (X) of the catalyst X according to the following formula HDN ：
Wherein LHSV is the liquid hourly volume space velocity of the hydrocarbon oil during the hydrorefining reaction,
the hydrodenitrogenation activity of the catalyst D-1 (denoted as k (D-1)) HDN ) For reference, the relative hydrodenitrogenation activity of catalyst X was calculated as follows:
relative hydrodenitrogenation activity (X) = [ k (X) HDN /k(D-1) HDN ]×100％。
TABLE 3
As can be seen from the data in table 3, the catalyst prepared according to the method of the present invention shows higher catalytic activity in the hydrofinishing of hydrocarbon oil.
Test example 2
The catalysts prepared in examples 9 to 17 and comparative example 2 were tested for their performance in the fischer-tropsch synthesis reaction using the following method.
The test procedure was carried out in a fixed bed fischer-tropsch synthesis reactor using 5 g of catalyst.
The catalyst is reduced before use. The reduction is carried out at atmospheric pressure, with the other conditions being: the hydrogen flow was 1000 NL/(g-cat h), and the temperature was raised to 400 ℃ at a rate of 4 ℃/min and held for 5h.
The Fischer-Tropsch synthesis reaction conditions comprise: at a temperature of 223 ℃ H 2 The ratio of/CO is 2, the pressure is 2.5MPa, and the Gas Hourly Space Velocity (GHSV) is 2000h -1 . The results are listed in table 4.
TABLE 4
In Table 4, X CO The conversion rate of CO is shown in the specification,
is represented by C 5 Above (containing C) 5 ) Selectivity of hydrocarbons. The specific definition is given in the following expression:
as can be seen from the results in Table 4, catalyst pair C prepared by the process of the present invention 5+ Hydrocarbons have higher selectivity and can also achieve higher CO conversion.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (30)
1. A method of preparing a shell-distributed catalyst, the method comprising:
(1) Spraying a porous carrier with a solution containing a film-forming polymer, the amount of said solution sprayed being V L1 The pore volume of the porous carrier is V C ，V L1 /V C =0.01-0.6；
(2) Spraying the product obtained in the step (1) by using a solvent, wherein the spraying amount of the solvent is V L2 ，V L2 /V C =0.01-0.6；
(3) Drying the product obtained in the step (2);
(4) Impregnating the product obtained in the step (3) with a solution containing a catalytic active component;
(5) Roasting the product obtained in the step (4);
the film-forming polymer is at least one selected from polyvinyl alcohol, vinyl alcohol-olefin copolymer, partially hydrolyzed polyvinyl alcohol, partially hydrolyzed vinyl alcohol-olefin copolymer, polyvinyl acetate, polyethylene glycol, collagen, polyethylene terephthalate, polyethylene naphthalate, polyamide, polysaccharide, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyacrylate resin and copolymer containing acrylate unit;
the solvent of the solution containing the film-forming polymer and the solvent of step (2) are each independently selected from at least one of water, methanol, ethanol, propanol, acetone, ethyl acetate, furfural, benzene, toluene, and cyclohexane.
2. The method of claim 1, wherein,
the film-forming polymer is polyvinyl alcohol and/or a vinyl alcohol-olefin copolymer.
3. The method of claim 2, wherein,
the film-forming polymer is a vinyl alcohol-olefin copolymer.
4. The method of claim 3, wherein,
the film-forming polymer is a vinyl alcohol-ethylene copolymer.
5. The method of claim 1, wherein the concentration of the solution containing the film-forming polymer is 0.1 to 15 wt.%.
6. The method of claim 5, wherein the concentration of the solution containing the film-forming polymer is 0.3 to 10 wt.%.
7. The method of claim 6, wherein the concentration of the solution comprising the film-forming polymer is 0.5 to 8 wt.%.
8. The method of claim 7, wherein the concentration of the solution comprising the film-forming polymer is 1-5 wt.%.
9. The method of claim 1, wherein,
the solvent of the solution containing the film-forming polymer is the same as the solvent in the step (2).
10. The method according to any one of claims 1 to 9, wherein in step (1), V is L1 /V C =0.05-0.45。
11. The method of claim 10, wherein,
V L1 /V C =0.1-0.3。
12. the method of any one of claims 1-9,
in step (2), V L2 /V C =0.05-0.45。
13. The method of claim 12, wherein,
V L2 /V C =0.1-0.3。
14. the process of any one of claims 1-9, wherein the porous support is selected from at least one of alumina, magnesia, zirconia, calcia, silica, titania, aluminosilicate, molecular sieve, and rare earth oxide.
15. The method of any one of claims 1-9,
in the step (2), the drying conditions include: the temperature is 40-90 ℃ and the time is 1-48 hours.
16. The method of claim 15, wherein,
in the step (2), the drying conditions include: under the vacuum condition, the temperature is 50-90 ℃ and the time is 2-16 hours.
17. The method according to any one of claims 1 to 9, wherein the amount of the solution containing the catalytically active component in step (4) and the spraying amount V of the solvent in step (2) are the same L2 Are equal.
18. The method of any one of claims 1 to 9, wherein the shell distributed catalyst catalyzes a fischer-tropsch synthesis reaction.
19. The method of claim 18, wherein,
the catalytically active component is selected from the group VIII metal elements.
20. The method of claim 19, wherein,
the catalytic active component is one or more than two of iron, cobalt and ruthenium.
21. The method of claim 19, wherein,
the loading amount of the catalytically active component on the porous carrier is such that the content of the catalytically active component in terms of oxide is 0.05 to 30% by weight based on the total amount of the finally prepared catalyst.
22. The method of claim 21, wherein,
the loading amount of the catalytically active component on the porous carrier is such that the content of the catalytically active component in terms of oxide is 0.1 to 25% by weight based on the total amount of the finally prepared catalyst.
23. The process of any of claims 1-9, wherein the shell distributed catalyst catalyzes a hydrofinishing reaction.
24. The method of claim 23, wherein,
the catalytic active component is selected from at least one of VIII group metal elements and at least one of VIB group metal elements.
25. The method of claim 24, wherein,
the catalytically active component contains cobalt and/or nickel and molybdenum and/or tungsten.
26. The method of claim 24, wherein,
the loading capacity of the catalytic active component on the porous carrier is such that the content of the VIII group metal element calculated by oxide is 1-20 wt% and the content of the VIB group metal element calculated by oxide is 5-30 wt% based on the total amount of the finally prepared catalyst.
27. The method of any one of claims 1-9, wherein the firing conditions of step (5) comprise: the temperature is 250-600 ℃; the time is 1-48 hours.
28. The method of claim 27, wherein the firing conditions of step (5) comprise: the temperature is 300-500 ℃; the time is 2-12 hours.
29. A shell distributed catalyst prepared by the method of any one of claims 1-28.
30. Use of the shell distributed catalyst of claim 29 in a fischer-tropsch synthesis reaction or a hydrofinishing reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911037358.0A CN112742381B (en) | 2019-10-29 | 2019-10-29 | Shell-layer distributed catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911037358.0A CN112742381B (en) | 2019-10-29 | 2019-10-29 | Shell-layer distributed catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112742381A CN112742381A (en) | 2021-05-04 |
| CN112742381B true CN112742381B (en) | 2023-03-10 |
Family
ID=75640922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911037358.0A Active CN112742381B (en) | 2019-10-29 | 2019-10-29 | Shell-layer distributed catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112742381B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4599481A (en) * | 1984-09-13 | 1986-07-08 | Shell Oil Company | Process for the preparation of hydrocarbons |
| US5545674A (en) * | 1987-05-07 | 1996-08-13 | Exxon Research And Engineering Company | Surface supported cobalt catalysts, process utilizing these catalysts for the preparation of hydrocarbons from synthesis gas and process for the preparation of said catalysts |
| WO2006050778A1 (en) * | 2004-11-11 | 2006-05-18 | Degussa Gmbh | Sodium percarbonate particles having a shell layer comprising thiosulfate |
| CN101061063A (en) * | 2004-12-14 | 2007-10-24 | 德古萨有限责任公司 | Compressed molded bodies containing coated sodium percarbonate particles |
| CN101318133A (en) * | 2007-06-06 | 2008-12-10 | 中国科学院大连化学物理研究所 | Lamella catalyst for preparing petroleum naphtha and diesel oil, preparation method and application thereof |
| CN102127298A (en) * | 2010-12-29 | 2011-07-20 | 四川大学 | Polymer hollow nano microspheres and preparation method thereof |
| CN102463090A (en) * | 2010-10-29 | 2012-05-23 | 财团法人工业技术研究院 | Core-shell inorganic polymer composite material and method for producing same |
| JP2012101950A (en) * | 2010-11-05 | 2012-05-31 | Noritake Co Ltd | Method for producing porous carbon particle, and porous carbon material including the particle |
| CN103623818A (en) * | 2012-08-23 | 2014-03-12 | 中国石油天然气股份有限公司 | Thin-shell type precious metal catalyst and preparation method thereof |
| CN106311358A (en) * | 2015-07-08 | 2017-01-11 | 中国石油化工股份有限公司 | Shell-distributed catalyst and preparation method thereof, and Fischer-Tropsch synthesis method |
| CN107185509A (en) * | 2017-05-31 | 2017-09-22 | 北京三聚环保新材料股份有限公司 | One kind is with γ Al2O3For the preparation method of the hud typed carrier of shell |
| JP2018086629A (en) * | 2016-11-29 | 2018-06-07 | 東洋製罐グループホールディングス株式会社 | Forming method of particulate layer |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4977126A (en) * | 1987-05-07 | 1990-12-11 | Exxon Research And Engineering Company | Process for the preparation of surface impregnated dispersed cobalt metal catalysts |
| DE4239876C1 (en) * | 1992-11-27 | 1994-07-28 | Degussa | Process for the uniform and reproducible shell impregnation of fixed bed catalyst supports in bulk and device for carrying out the process |
| DE10015250A1 (en) * | 2000-03-28 | 2001-10-04 | Basf Ag | Shell catalyst for gas phase hydrogenation |
| EA018085B1 (en) * | 2006-06-12 | 2013-05-30 | Каптиджел Аб | Metal oxide hydrogels and hydrosols, their preparation and use |
| US7744675B2 (en) * | 2006-11-08 | 2010-06-29 | Shell Oil Company | Gas separation membrane comprising a substrate with a layer of coated inorganic oxide particles and an overlayer of a gas-selective material, and its manufacture and use |
| WO2008122636A2 (en) * | 2007-04-10 | 2008-10-16 | Shell Internationale Research Maatschappij B.V. | Steam or water treatment of a catalyst precursor in order to obtain an egg shell ft catalyst |
| CN101462079B (en) * | 2007-12-20 | 2011-07-20 | 中国石油化工股份有限公司 | Method for preparing catalyst with lamella distribution |
| DE102008004485A1 (en) * | 2008-01-14 | 2009-07-16 | Bayerisches Zentrum für Angewandte Energieforschung e.V. | Covering of organic and inorganic phase change material, comprises introducing the phase change material into a porous, open-cellular carrier structure and providing the filled porous granulates with water vapor-tight layer |
| KR101350690B1 (en) * | 2012-02-13 | 2014-01-14 | 금호석유화학 주식회사 | Highly conductive carbon nanotube having bundle moieties with ultra-low bulk density and its manufacturing method |
| CN105728020B (en) * | 2016-03-03 | 2019-02-26 | 华侨大学 | A kind of hud typed iron-carbonide catalyst preparation method |
| CN109722722B (en) * | 2018-11-21 | 2022-03-25 | 深圳大学 | Uniform-pore nanofiber and preparation method and application thereof |
-
2019
- 2019-10-29 CN CN201911037358.0A patent/CN112742381B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4599481A (en) * | 1984-09-13 | 1986-07-08 | Shell Oil Company | Process for the preparation of hydrocarbons |
| US5545674A (en) * | 1987-05-07 | 1996-08-13 | Exxon Research And Engineering Company | Surface supported cobalt catalysts, process utilizing these catalysts for the preparation of hydrocarbons from synthesis gas and process for the preparation of said catalysts |
| WO2006050778A1 (en) * | 2004-11-11 | 2006-05-18 | Degussa Gmbh | Sodium percarbonate particles having a shell layer comprising thiosulfate |
| CN101061063A (en) * | 2004-12-14 | 2007-10-24 | 德古萨有限责任公司 | Compressed molded bodies containing coated sodium percarbonate particles |
| CN101318133A (en) * | 2007-06-06 | 2008-12-10 | 中国科学院大连化学物理研究所 | Lamella catalyst for preparing petroleum naphtha and diesel oil, preparation method and application thereof |
| CN102463090A (en) * | 2010-10-29 | 2012-05-23 | 财团法人工业技术研究院 | Core-shell inorganic polymer composite material and method for producing same |
| JP2012101950A (en) * | 2010-11-05 | 2012-05-31 | Noritake Co Ltd | Method for producing porous carbon particle, and porous carbon material including the particle |
| CN102127298A (en) * | 2010-12-29 | 2011-07-20 | 四川大学 | Polymer hollow nano microspheres and preparation method thereof |
| CN103623818A (en) * | 2012-08-23 | 2014-03-12 | 中国石油天然气股份有限公司 | Thin-shell type precious metal catalyst and preparation method thereof |
| CN106311358A (en) * | 2015-07-08 | 2017-01-11 | 中国石油化工股份有限公司 | Shell-distributed catalyst and preparation method thereof, and Fischer-Tropsch synthesis method |
| JP2018086629A (en) * | 2016-11-29 | 2018-06-07 | 東洋製罐グループホールディングス株式会社 | Forming method of particulate layer |
| CN107185509A (en) * | 2017-05-31 | 2017-09-22 | 北京三聚环保新材料股份有限公司 | One kind is with γ Al2O3For the preparation method of the hud typed carrier of shell |
Non-Patent Citations (4)
| Title |
|---|
| NANOSTRUCTURED POWDERS: A NEW CLASS OF MATERIALS FOR FORMING;GANESH SKANDAN;《Materials Research Society》;19981231;第351-362页 * |
| 两种钴碳化钨涂层的组织性能研究;侯玉柏等;《热喷涂技术》;20180630;第22-25页 * |
| 热喷涂Cr/Al2O3 复合粉末的制备及性能研究;崔珊等;《表面技术》;20170731;第39-44页 * |
| 自愈性超疏水表面的方法及应用进展＊;耿敏等;《功能材料》;20180630;第06049-06056页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112742381A (en) | 2021-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4156859B2 (en) | Gas oil hydrotreating catalyst, method for producing the same, and gas oil hydrotreating method | |
| JP6506430B2 (en) | Improved resid hydroprocessing catalyst containing titania | |
| KR100209814B1 (en) | Hydrotreating catalyst composition, its preparation and use | |
| CN104117362B (en) | A kind of catalyst and preparation method of raising NiMo diesel oil hydrofining catalyst hydrogenation activities | |
| CA2360121C (en) | Hydroprocessing catalyst and use thereof | |
| JP5922372B2 (en) | Hydrotreating catalyst and method for producing the same | |
| KR930008440B1 (en) | Nickel/silica catalyst and the preparation and use thereof | |
| CN102125878B (en) | Modified Al2O3 carrier and preparation method thereof | |
| CN108187709B (en) | Preparation method of deep hydrodesulfurization catalyst and application of catalyst | |
| CN1169337A (en) | Catalyst treated by distillate added with hydrogen and preparation method thereof | |
| JP2019500200A (en) | Acid-resistant catalyst carrier and catalyst | |
| CN112742381B (en) | Shell-layer distributed catalyst and preparation method and application thereof | |
| CN109718819B (en) | Hydrofining catalyst, preparation method and application thereof, and hydrofining method of distillate oil | |
| RU2634705C2 (en) | Selenium-containing hydrotreating catalyst, its use and preparation method | |
| RU2761528C1 (en) | Catalyst of a protective layer for reactors of hydrogenation processing of petroleum feedstock and a method for its production | |
| CN1508224A (en) | Hydrocracking after-treatment catalyst and preparing method thereof | |
| RU2534999C1 (en) | Method of hydrofining hydrocarbon material | |
| RU2610869C2 (en) | Hydroprocessing catalyst and methods of making and using such catalyst | |
| CN111318294A (en) | Hydrotreating catalyst and preparation method and application thereof | |
| CN112300834B (en) | Heavy oil hydrotreating method | |
| CN111195525A (en) | Residual oil hydrodesulfurization catalyst and preparation method thereof | |
| CN110860285B (en) | Preparation method of catalyst for low-temperature thioetherification and diene selective hydrogenation | |
| CN114425446B (en) | Shell distributed catalyst and preparation method and application thereof | |
| CN114471550B (en) | Noble metal hydrogenation catalyst and preparation method and application thereof | |
| CN113231067B (en) | Dearsenifying agent for light distillate oil hydrogenation and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |