CN109395739A - A kind of hydrogenation of petroleum resin catalyst and preparation method thereof - Google Patents
A kind of hydrogenation of petroleum resin catalyst and preparation method thereof Download PDFInfo
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- CN109395739A CN109395739A CN201811411038.2A CN201811411038A CN109395739A CN 109395739 A CN109395739 A CN 109395739A CN 201811411038 A CN201811411038 A CN 201811411038A CN 109395739 A CN109395739 A CN 109395739A
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- Prior art keywords
- oxide
- aluminium
- catalyst
- hydrogenation
- silicon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 239000011347 resin Substances 0.000 title claims abstract description 55
- 229920005989 resin Polymers 0.000 title claims abstract description 55
- 239000003208 petroleum Substances 0.000 title claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical group [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 8
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 51
- 229910052782 aluminium Inorganic materials 0.000 claims description 49
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 49
- 239000006104 solid solution Substances 0.000 claims description 42
- 239000004411 aluminium Substances 0.000 claims description 37
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 35
- 229910052746 lanthanum Inorganic materials 0.000 claims description 35
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 35
- 229920000126 latex Polymers 0.000 claims description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002210 silicon-based material Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- 239000011863 silicon-based powder Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- HLRPCWSWHIWFHM-UHFFFAOYSA-N cerium(3+) lanthanum(3+) oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[O--].[O--].[O--].[Zr+4].[La+3].[Ce+3] HLRPCWSWHIWFHM-UHFFFAOYSA-N 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- -1 rectorite Chemical compound 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 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 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- DFQIABYLTKZUIA-UHFFFAOYSA-N [O].[Zr].[Ce].[La] Chemical compound [O].[Zr].[Ce].[La] DFQIABYLTKZUIA-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 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 claims 1
- NXGASACSZHOEHS-UHFFFAOYSA-N cerium lanthanum zirconium Chemical compound [Zr].[La].[Ce] NXGASACSZHOEHS-UHFFFAOYSA-N 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 abstract description 16
- 239000011593 sulfur Substances 0.000 abstract description 15
- 239000000047 product Substances 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 229920002857 polybutadiene Polymers 0.000 description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000006210 lotion Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000004816 latex Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical class [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 3
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 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
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-N aluminum oxygen(2-) hydrate Chemical compound O.[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 208000013403 hyperactivity Diseases 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000008601 oleoresin Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical group [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of hydrogenation of petroleum resin catalyst and preparation method thereof, catalyst includes carrier and active component, carrier is aluminium oxide-silicon oxide complex carrier, active component includes nickel oxide, tungsten oxide, in terms of mass percentage, aluminium oxide-silicon oxide complex carrier content is 70~90wt% in catalyst, and active component nickel oxide, tungsten oxide content are 10~30wt%.Catalyst hydrogenation of petroleum resin activity is high, and sulfur resistive ability is strong, and stability is good.
Description
Technical field
The present invention relates to a kind of hydrogenation of petroleum resin catalyst and preparation method thereof.
Background technique
The light dydrocarbon of by-product or C 9 fraction are either adopted through complexing polymerization catalyst when Petropols are cracking ethylene
With product obtained after thermal polymerization.Its molecular weight is generally less than 2000, and 5-150 DEG C of softening point, be in thermoplasticity thick liquid
Or solid.Petropols have tackifying, cementability and the compatibility with other naval stores, so often by itself and others
Polymer material mixes to improve the performance of various products jointly, and which are mainly applied to the fields such as coating, adhesive and ink.But
With the continuous development of technology, the quality of Petropols (form and aspect, softening point etc.) is required higher and higher.C 5 petroleum resin is former
Expect complicated component (often there are the impurity such as more colour developing group, gel, S, Cl), easily causes catalyst poisoning to inactivate, macromolecular
Polymer mass transfer difference is difficult to adsorption activation, while avoiding the fracture of C-C hydrogenolysis (causing the reduction of hydrogenated products softening point) again.Generally
Petropols primary product color is unstable to heat and oxidation compared with deep, stability is poor, especially because sulfur content is higher, by
Bad smell can be generated when hot, seriously hamper it in the application in high-end adhesive product field.Resin purification, which generally uses, to be added
Double bond remaining in resin and part phenyl ring are saturated by the method for hydrogen, to improve the color and stability of resin.Add hydrogen stone
Oleoresin solves the problems, such as smell, coloration and the oxidation stability of Petropols, has widened the application field of Petropols significantly.
C 5 petroleum resin after through hydrogenated processing is white or transparent, and stability is high and intersolubility is good.
Adding hydrogen into resin catalyst is broadly divided into the catalyst of noble metals and base metal two kinds of types, and early stage base metal is urged
It is mostly 40%-60% that agent, which is mostly carried on diatomite or aluminium oxide-diatomite Raney nickel, nickel content weight percent,.
United States Patent (USP) US2911395 discloses a kind of Raney nickel being carried on diatomite, reacts in 210-230 DEG C, 3-9.1MPa
Under the conditions of plus hydrogen 5-7 hour, resulting product yield is 95% or so, and saybolt colorimeter value is 25 or so, softening point 150-
180 DEG C, bromine valency 1-3gBr2/100g.The deficiency of the catalyst is that the activity of catalyst is not high, and product bromine valency is still higher, and
Catalyst life is shorter.The supported sulfided nickel-tungsten system for having stronger sulfur resistive ability or sulphurating nickel-molybdenum series catalysis are developed later
Agent.European patent EP 82716 discloses a kind of supported sulfided nickel-tungsten series catalysts, Ni weight content 2%-10%, W weight
Content 10%-25%.Reaction condition is 250-330 DEG C, 15.2-20.3MPa.The softening point of resin product is 85-150 DEG C, match
Baud colourimetric number is 20-30, and bromine valency is about 0, hence it is evident that improves the thermal stability of product.The catalyst sulfur resistive ability is strong, insufficient
Be that reaction temperature and pressure are higher.Chinese patent CN18033871A discloses a kind of Petropols autoclave catalytic hydrogenation decoloration
Method, this method using skeleton nickel as catalyst, catalyst amount be Petropols 1-20wt%, reaction condition are as follows: temperature
Spend 100-250 DEG C, pressure 1-10MPa, reaction time 2-10h.The catalyst activity is higher, resulting resin product it is of light color and
Better heat stability, unfortunately catalyst amount is larger and easy inactivation.Noble metal catalyst is mainly palladium system and palladium-platinum group
The advantages of catalyst, the series catalysts is active height, and start-up temperature is low, and product yield is high, high-quality.But the disadvantage is that poison such as sulphur
Object is sensitive, is very easy to poisoning and deactivation.Chinese patent CN102924659A discloses the side that two sections of fixed-bed resins of one kind add hydrogen
Method, first segment catalyst are Ni/Al2O3, mainly for the sulphur in removing material resin.Second segment is precious metals pt-Pd/
Al2O3 hydrogenation catalyst, the reaction condition of the catalyst are as follows: 250-350 DEG C of temperature, pressure 2-6MPa, liquid air speed 1-5h-1.
This method has given full play to the advantage of two-stage catalytic agent, improves the service life of noble metal catalyst.But unfortunately reaction temperature
It is higher, cause the softening point of resin product lower, influences the application range of resin.CN201510431240.1 one kind is used for petroleum
Adding hydrogen into resin method for preparing catalyst and application, and by high pressure fixed bed lab scale and pilot scale reaction unit, to its catalytic performance
It gives and tests and assesses, and be applied in industrialized production.It is characterized in that using active carbon or silica as carrier, carried metal nickel, nickel
Molybdenum, nickel tungsten active component, shared mass fraction are 30-50%, and using equi-volume impregnating, which is used for C5, C9 petroleum
Resin has good low temperature hydrogenation activity, and reduces molecule chain break using neutral carrier, and product after hydrogen is added to soften
Point amplitude of variation is smaller, and the anti-impurity ability of catalyst and excellent in stability, bromine number and coloration are in the ideal range.
CN201611257902.9 provides a kind of method of hydrotreating of C 5 petroleum resin, in a mixer by light dydrocarbon petroleum
Resin is dissolved in after organic solvent preheated after enter to fixed bed hydrogenation reactor, nickel molybdenum system hydrogenation catalyst is housed in reactor
Agent adds material after hydrogen to send to stripper, and the organic solvent of top extraction is recycled after destilling tower refines, and stripping tower bottom obtains
C 5 hydrogenated petroleum resin；The catalyst of nickeliferous carrier preparation obtained with specific crystalline form, can greatly improve active gold
The utilization rate of category and the preparation difficulty for reducing catalyst, while synergistic effect is played in the addition of selected active component, can be made
The C 5 hydrogenated petroleum resin that bromine valency is low, coloration and stability are good.
In conclusion poison resistance deficiency or C-C key hydrogenolysis existing for current C 5/C 9 petroleum resin hydrogenation catalyst
The problems such as hyperactivity causes hydrogenated products softening point to be greatly lowered is the technical bottleneck for restricting its development.Therefore, it is necessary to open
It is high to send out hydrogenation activity a kind of, the catalyst that sulfur resistive impurity ability is strong, activity stability is good.
Summary of the invention
The present invention provides a kind of hydrogenation of petroleum resin catalyst and preparation method thereof, catalyst hydrogenation of petroleum resin activity
Height, sulfur resistive ability is strong, and stability is good, and active component should not fall off, be crushed, and low temperature active is good, and production is long operation cycle, resulting
Resin product is of light color and thermal stability is good.
A kind of hydrogenation of petroleum resin catalyst, catalyst include carrier and active component, and carrier is multiple for aluminium oxide-silicon oxide
Carrier is closed, active component includes nickel oxide, tungsten oxide, in terms of mass percentage, the compound load of aluminium oxide-silicon oxide in catalyst
Body content is 70~90wt%, and active component nickel oxide, tungsten oxide content are 10~30wt%, the compound load of aluminium oxide-silicon oxide
It include lanthanum CeO2-ZrO2 solid solution in body, lanthanum CeO2-ZrO2 solid solution content is 3~25wt%, and aluminium oxide-silicon oxide is multiple
Closing alumina content in carrier is 55~85wt%.Catalyst is suitable for light dydrocarbon, C 9 petroleum resin adds hydrogen.
The aluminium oxide-silicon oxide complex carrier the preparation method is as follows: (a) by 50%~70% aluminum contained compound with
Silicon-containing compound is uniformly mixed, and inorganic acid solution is added and rubber latex obtains the mixture (1) containing aluminium and silicon；(b) residue 30
~50% aluminum contained compound is mixed with lanthanum CeO2-ZrO2 solid solution, adds inorganic acid solution and rubber latex, is contained
Aluminium and lanthanum CeO2-ZrO2 solid solution mixture (2)；In terms of oxide, rubber latex quality in the mixture (1) containing aluminium and silicon
Percentage composition is the 2 times or more containing rubber latex mass percentage in aluminium and lanthanum CeO2-ZrO2 solid solution mixture (2)；
(c) mixture (2) is slowly added in mixture (1), is stirred to react 1-3 hours, obtains aluminium oxide-oxygen through molding, drying, roasting
SiClx complex carrier.The silicon-containing compound is one or more of silica gel, sodium metasilicate or silicon powder.Aluminum contained compound is quasi-
One or more of boehmite, aluminium oxide, sodium metaaluminate, aluminum sulfate are also possible to kaolin, rectorite, in montmorillonite
One or more.It include lanthanum CeO2-ZrO2 solid solution in aluminium oxide-silicon oxide complex carrier of the present invention, it is mixed containing aluminium and silicon
Closing rubber latex mass percentage in object (1) is containing rubber latex matter in aluminium and lanthanum CeO2-ZrO2 solid solution mixture (2)
The 2 times or more of percentage composition is measured, the catalyst hydrogenation of petroleum resin activity of nickel-loaded tungsten active component, preparation is high, sulfur resistive ability
By force, resulting resin product is of light color and thermal stability is good.The inorganic acid is nitric acid, citric acid etc..
Be further improved, the aluminium oxide-silicon oxide complex carrier the preparation method is as follows:
(a) 50%~70% aluminum contained compound is uniformly mixed with silicon-containing compound, inorganic acid solution, rubber glue is added
Cream and polyvinyl alcohol obtain the mixture (1) containing aluminium and silicon；(b) aluminum contained compound and lanthanum cerium zirconium oxide of residue 30~50%
Solid solution mixing, adds inorganic acid solution, rubber latex and polyvinyl alcohol, obtains mixed containing aluminium and lanthanum CeO2-ZrO2 solid solution
It closes object (2)；Rubber latex and polyvinyl alcohol mass percentage, which are higher than, in terms of oxide, in the mixture (1) containing aluminium and silicon contains
Rubber latex and 1.6 times of polyvinyl alcohol mass percentage or more in aluminium and lanthanum CeO2-ZrO2 solid solution mixture (2)；(c)
Mixture (2) is slowly added in mixture (1), is stirred to react 1-3 hours, obtains alumina-silica through molding, drying, roasting
Silicon complex carrier.The silicon-containing compound is silica gel, sodium metasilicate or silicon powder.Aluminum contained compound be boehmite, aluminium oxide,
One or more of sodium metaaluminate, aluminum sulfate are also possible to one or more of kaolin, rectorite, montmorillonite.This hair
Bright mixture (1) containing aluminium and silicon and containing rubber latex and poly- is all added in aluminium and lanthanum CeO2-ZrO2 solid solution mixture (2)
Vinyl alcohol, and rubber latex and polyvinyl alcohol mass percentage are higher than containing aluminium and lanthanum cerium in the mixture (1) containing aluminium and silicon
Rubber latex and 1.6 times of polyvinyl alcohol mass percentage or more in Zirconium oxide solid solution mixtures (2)；Catalyst sulfur resistive energy
Power is strong, and low temperature active is good, and hydrogenation activity is high, and resulting resin product is of light color and thermal stability is good.
Lanthanum CeO2-ZrO2 solid solution La of the present inventionxCeyZr1-xO2(0 < x < 1,0 < y < 1) the preparation method is as follows: according to change
Metering is learned than weighing a certain amount of cerous nitrate, lanthanum nitrate, zirconium nitrate, mixed solution is configured to, adds rubber latex, continuous
In the case where stirring, to mixed solution and dripping ammonia spirit, so that it is carried out coprecipitation reaction, then filtered, dry, roasting
It burns, grind obtained lanthanum CeO2-ZrO2 solid solution.The preferred polybutadiene rubber lotion of rubber latex.Rubber latex additional amount accounts for lanthanum
1~40wt% of CeO2-ZrO2 solid solution quality.Under hot conditions, nickel and carrying alumina are known from experience generation strong interaction and are generated
Spinel structure is remarkably decreased so as to cause catalyst activity.Adding hydrogen into resin catalyst carrier of the present invention includes containing rubber latex
Lanthanum CeO2-ZrO2 solid solution, be conducive to inhibit hot conditions under nickel aluminate generation and catalyst surface intensity become
Difference, active component should not fall off, be crushed, and activity stability is good.
Preferably, the catalyst of the hydrogenation of petroleum resin, active component content is 12~26wt% in catalyst, wherein
Nickel oxide content is 4~15wt%, tungsten oxide content is 4~20wt%.
The preparation method of hydrogenation of petroleum resin catalyst of the present invention, include the following steps: will to contain active component can
Soluble wiring solution-forming, oxide impregnation aluminium-silica complex carrier, through drying, roasting obtains hydrogenation of petroleum resin catalyst.
Described through drying, roasting obtains hydrogenation of petroleum resin catalyst, refers to drying 4-8 hours at 120-150 DEG C,
It is roasted 6-10 hours at 450-650 DEG C and obtains catalyst.
Specific embodiment
It carries out by the following examples with catalyst and preparation method of the comparative example to hydrogenation of petroleum resin of the present invention into one
The detailed description of step.But these embodiments are not regarded as limiting of the invention.Prepare primary raw material source used in catalyst:
Reagent of the present invention is commercial product.
Embodiment 1
1) a certain amount of cerous nitrate, lanthanum nitrate, zirconium nitrate are weighed according to stoichiometric ratio, is configured to mixed solution, then plus
Enter polybutadiene rubber lotion, in the case where being stirred continuously, to mixed solution and dripping ammonia spirit, is co-precipitated it
Reaction, is then filtered, and is dried, and obtained lanthanum CeO2-ZrO2 solid solution La is ground in roasting0.38Ce0.53Zr0.62O2.Polybutadiene
Rubber latex additional amount accounts for the 28wt% of lanthanum CeO2-ZrO2 solid solution quality.
2) aluminium oxide-silicon oxide complex carrier the preparation method is as follows:
(a) 240 boehmites are uniformly mixed with 120g silicon powder, nitric acid solution and 86g polybutadiene rubber is added
Lotion obtains the mixture (1) containing aluminium and silicon；(b) 160g boehmite is mixed with 70g lanthanum CeO2-ZrO2 solid solution, then plus
Enter inorganic acid solution and 14g polybutadiene rubber lotion, obtains containing aluminium and lanthanum CeO2-ZrO2 solid solution mixture (2)；(c) it mixes
It closes object (2) to be slowly added in mixture (1), be stirred to react 3 hours, it is multiple to obtain aluminium oxide-silicon oxide through molding, drying, roasting
Close carrier.
3) by nickel nitrate, ammonium metatungstate wiring solution-forming, oxide impregnation aluminium-silica complex carrier, dry 5 is small at 130 DEG C
When, it roasts 7 hours at 580 DEG C and obtains catalyst, the composition of catalyst is shown in Table 1.
Embodiment 2
Lanthanum CeO2-ZrO2 solid solution La0.45Ce0.61Zr0.55O2The preparation method is the same as that of Example 1, polybutadiene rubber cream
Liquid additional amount accounts for the 32wt% of lanthanum CeO2-ZrO2 solid solution quality.The preparation method of aluminium oxide-silicon oxide complex carrier is the same as real
Apply example 1, in terms of oxide, mixture (1) containing aluminium and silicon and containing in aluminium and lanthanum CeO2-ZrO2 solid solution mixture (2) all plus
Enter rubber latex and polyvinyl alcohol, and rubber latex and polyvinyl alcohol mass percentage in the mixture (1) containing aluminium and silicon
Higher than 2 times containing rubber latex in aluminium and lanthanum CeO2-ZrO2 solid solution mixture (2) and polyvinyl alcohol mass percentage.It urges
The preparation method is the same as that of Example 1 for agent, and the composition of catalyst is shown in Table 1.
Embodiment 3
Lanthanum CeO2-ZrO2 solid solution La0.58Ce0.41Zr0.42O2The preparation method is the same as that of Example 1, polybutadiene rubber cream
Liquid additional amount accounts for the 24wt% of lanthanum CeO2-ZrO2 solid solution quality.The preparation method of aluminium oxide-silicon oxide complex carrier is the same as real
Apply example 1, in terms of oxide, mixture (1) containing aluminium and silicon and containing in aluminium and lanthanum CeO2-ZrO2 solid solution mixture (2) all plus
Enter rubber latex and polyvinyl alcohol, and rubber latex and polyvinyl alcohol mass percentage in the mixture (1) containing aluminium and silicon
Higher than 3.4 times containing rubber latex in aluminium and lanthanum CeO2-ZrO2 solid solution mixture (2) and polyvinyl alcohol mass percentage.
The preparation method is the same as that of Example 1 for catalyst, and the composition of catalyst is shown in Table 1.
Comparative example 1
1) aluminium oxide-silicon oxide complex carrier the preparation method is as follows:
(a) 240 boehmites are uniformly mixed with 120g silicon powder, nitric acid solution and 86g polybutadiene rubber is added
Lotion obtains the mixture (1) containing aluminium and silicon；(b) inorganic acid solution and 14g polybutadiene rubber are added in 160g boehmite
Latex solution obtains (2) containing aluminium mixture；(c) mixture (2) is slowly added in mixture (1), is stirred to react 3 hours, through at
Type, drying, roasting obtain aluminium oxide-silicon oxide complex carrier.
2) by nickel nitrate, ammonium metatungstate wiring solution-forming, oxide impregnation aluminium-silica complex carrier, dry 5 is small at 130 DEG C
When, it roasts 7 hours at 580 DEG C and obtains comparative catalyst 1, the composition of catalyst is shown in Table 1.
Comparative example 2
1) a certain amount of cerous nitrate, lanthanum nitrate, zirconium nitrate are weighed according to stoichiometric ratio, is configured to mixed solution, then plus
Enter polybutadiene rubber lotion, in the case where being stirred continuously, to mixed solution and dripping ammonia spirit, is co-precipitated it
Reaction, is then filtered, and is dried, and obtained lanthanum CeO2-ZrO2 solid solution La is ground in roasting0.38Ce0.53Zr0.62O2.Polybutadiene
Rubber latex additional amount accounts for the 28wt% of lanthanum CeO2-ZrO2 solid solution quality.
2) aluminium oxide-silicon oxide complex carrier the preparation method is as follows:
(a) 400 boehmites, 70g lanthanum CeO2-ZrO2 solid solution are uniformly mixed with 120g silicon powder, nitric acid is added
Solution and 100g polybutadiene rubber lotion are stirred to react 3 hours, and through molding, drying, that roasting obtains aluminium oxide-silicon oxide is compound
Carrier.
3) by nickel nitrate, ammonium metatungstate wiring solution-forming, oxide impregnation aluminium-silica complex carrier, dry 5 is small at 130 DEG C
When, it roasts 7 hours at 580 DEG C and obtains comparative catalyst 2, the composition of catalyst is shown in Table 1.
Adding hydrogen into resin reaction
Raw material is cracking of ethylene C9Petropols, Gardener coloration are 8, bromine valency 11.2gBr/100g oil, S content 56.3
μg·g-1, softening point 120.
The above-mentioned catalyst 1-3 being prepared and comparative catalyst are loaded in fixed bed reactors respectively, first use hydrogen
Reducing catalyst, 210 DEG C of reduction temperature, hydrogen partial pressure 2.5MPa, hydrogen flowing quantity 260mL/min, the recovery time is 10 hours.Reduction
After, using thiacyclohexane dissolution C5 Petropols as raw material, carry out hydrogenation reaction, reaction process condition: temperature of reactor 240
DEG C, reaction pressure 6.0MPa, volume space velocity 1.2h-1, hydrogen to oil volume ratio 300.Product is through vacuum distillation removing thiacyclohexane after adding hydrogen
After obtain hydrogenated petroleum resin, catalyst reaction product property is shown in Table 2.Catalyst 1-3 catalyst sulfur resistive ability is strong, low temperature active
Good, hydrogenation activity is high, and resulting resin product is of light color and thermal stability is good.Comparative example poor catalyst activity, sulfur resistive ability is poor,
Resin product color and thermal stability are poor compared with catalyst.
1 embodiment of table/comparative example catalyst composition/wt%
2 catalyst of table and comparative catalyst's reaction result
It the results are shown in Table 3 after catalyst 1-3 reaction 500 hours.Less, activity is not obvious for the variation of catalyst 1-3 bromine number
It reduces, illustrates that catalyst sulfur resistive ability is strong, stability is good, and catalyst introduces lanthanum CeO2-ZrO2 solid solution, is conducive to inhibit high
The generation of nickel aluminate and catalyst surface intensity are deteriorated under the conditions of temperature, and active component should not fall off, be crushed, activity stability
It is good.Comparative example catalyst 1 reacts 65 hours activity and is remarkably decreased, bromine valency 7.45gBr100g-1, 12.4 μ gg of sulfur content-1,
Illustrate that catalyst sulfur resistive ability is poor, stability is poor, and comparative catalyst 1 unloads catalyst from reactor and is obviously crushed.Comparative example is urged
Agent 2 reacts 65 hours bromine valency 5.62gBr100g-1, 9.5 μ gg of sulfur content-1, catalyst activity reduction, sulfur resistive ability is weak,
Resin product color and thermal stability are poor.
3 catalyst reaction result of table
Claims (10)
1. a kind of hydrogenation of petroleum resin catalyst, which is characterized in that catalyst includes carrier and active component, and carrier is oxidation
Aluminium-silica complex carrier, active component includes nickel oxide, tungsten oxide, in terms of mass percentage, aluminium oxide-in catalyst
Silica complex carrier content is 70~90wt%, and active component nickel oxide, tungsten oxide content are 10~30wt%, aluminium oxide-
It include lanthanum CeO2-ZrO2 solid solution in silica complex carrier, lanthanum CeO2-ZrO2 solid solution content is 3~25wt%, oxidation
Alumina content is 55~85wt% in aluminium-silica complex carrier.
2. hydrogenation of petroleum resin catalyst according to claim 1, which is characterized in that the compound load of aluminium oxide-silicon oxide
Body the preparation method is as follows: (a), 50%~70% aluminum contained compound is uniformly mixed with silicon-containing compound, inorganic acid is added
Solution and rubber latex obtain the mixture (1) containing aluminium and silicon；(b), the aluminum contained compound and lanthanum cerium zirconium oxygen of residue 30~50%
The mixing of compound solid solution, adds inorganic acid solution and rubber latex, obtains containing aluminium and lanthanum CeO2-ZrO2 solid solution mixture
(2)；In terms of oxide, rubber latex mass percentage is containing aluminium and lanthanum cerium zirconium oxide in the mixture (1) containing aluminium and silicon
The 2 times or more of rubber latex mass percentage in solid solution mixtures (2)；(c), mixture (2) is slowly added to mixture (1)
In, it is stirred to react 1-3 hours, obtains aluminium oxide-silicon oxide complex carrier through molding, drying, roasting.
3. hydrogenation of petroleum resin catalyst according to claim 1, which is characterized in that the compound load of aluminium oxide-silicon oxide
Body the preparation method is as follows: 50%~70% aluminum contained compound is uniformly mixed by (a) with silicon-containing compound, it is molten that inorganic acid is added
Liquid, rubber latex and polyvinyl alcohol obtain the mixture (1) containing aluminium and silicon；(b) aluminum contained compound and lanthanum of residue 30~50%
CeO2-ZrO2 solid solution mixing, adds inorganic acid solution, rubber latex and polyvinyl alcohol, obtains aoxidizing containing aluminium and lanthanum cerium zirconium
Object solid solution mixtures (2)；In terms of oxide, rubber latex and polyvinyl alcohol quality percentage in the mixture (1) containing aluminium and silicon
Content is higher than containing rubber latex and polyvinyl alcohol mass percentage 1.6 in aluminium and lanthanum CeO2-ZrO2 solid solution mixture (2)
Times or more；(c) mixture (2) is slowly added in mixture (1), is stirred to react 1-3 hours, obtains oxygen through molding, drying, roasting
Change aluminium-silica complex carrier.
4. the preparation method of hydrogenation of petroleum resin catalyst described in a kind of claim 1, which comprises the steps of:
By the soluble-salt wiring solution-forming containing active component, oxide impregnation aluminium-silica complex carrier, through drying, roasting obtains petroleum
Adding hydrogen into resin catalyst.
5. according to any one of Claims 2 or 3 hydrogenation of petroleum resin catalyst, which is characterized in that the silicon-containing compound
It is one or more of silica gel, sodium metasilicate or silicon powder.
6. according to any one of Claims 2 or 3 hydrogenation of petroleum resin catalyst, which is characterized in that the aluminum contained compound
It is one or more of boehmite, aluminium oxide, sodium metaaluminate, aluminum sulfate.
7. according to any one of Claims 2 or 3 hydrogenation of petroleum resin catalyst, which is characterized in that the aluminum contained compound
It is one or more of kaolin, rectorite, montmorillonite.
8. any one of -3 hydrogenation of petroleum resin catalyst according to claim 1, which is characterized in that the lanthanum cerium zirconium oxide
Solid solution LaxCeyZr1-xO2(0 < x < 1,0 < y < 1) the preparation method is as follows: weighing a certain amount of nitric acid according to stoichiometric ratio
Cerium, lanthanum nitrate, zirconium nitrate, are configured to mixed solution, add rubber latex, in the case where being stirred continuously, to mixed solution
Middle dropwise addition ammonia spirit makes it carry out coprecipitation reaction, is then filtered, and dries, and roasting, the obtained lanthanum cerium zirconium oxide of grinding are solid
Solution.
9. hydrogenation of petroleum resin catalyst according to claim 1, which is characterized in that active component content in the catalyst
For 12~26wt%, wherein nickel oxide content is 4~15wt%, tungsten oxide content is 4~20wt%.
10. the preparation method of hydrogenation of petroleum resin catalyst described in claim 4, which is characterized in that it is described through drying, it roasts
To hydrogenation of petroleum resin catalyst, refer at 120-150 DEG C it is 4-8 hours, 450-650 DEG C dry at roast 6-10 hours and obtain
Catalyst.
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