CN110013854A - The preparation and the application in C5/C9 Petropols catalytic hydrogenation of a kind of load-type nickel series catalysts - Google Patents
The preparation and the application in C5/C9 Petropols catalytic hydrogenation of a kind of load-type nickel series catalysts Download PDFInfo
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- CN110013854A CN110013854A CN201910386295.3A CN201910386295A CN110013854A CN 110013854 A CN110013854 A CN 110013854A CN 201910386295 A CN201910386295 A CN 201910386295A CN 110013854 A CN110013854 A CN 110013854A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 150000002815 nickel Chemical class 0.000 title claims abstract description 23
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000002077 nanosphere Substances 0.000 claims abstract description 21
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 13
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 13
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 40
- 239000001257 hydrogen Substances 0.000 claims description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 37
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 229910001220 stainless steel Inorganic materials 0.000 claims description 15
- 239000010935 stainless steel Substances 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 31
- 239000011347 resin Substances 0.000 abstract description 20
- 229920005989 resin Polymers 0.000 abstract description 20
- 239000003208 petroleum Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052794 bromium Inorganic materials 0.000 abstract description 7
- 239000002923 metal particle Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 14
- 239000003643 water by type Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000008601 oleoresin Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229910017929 Cu—SiO2 Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910002458 Co-SiO2 Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 244000147058 Derris elliptica Species 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
- 206010054949 Metaplasia Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000057114 Sapium sebiferum Species 0.000 description 1
- 235000005128 Sapium sebiferum Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- -1 hexamethylene, pentamethylene, acetone Chemical class 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000005303 weighing Methods 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of load-type nickel series catalysts and its preparations and its application in C5/C9 Petropols catalytic hydrogenation, and the catalyst is with SiO2It is the meso-porous hollow nano-sphere catalyst Ni-M-SiO of main active metal centre, addition promoter metal M (M=Cu/Co/Mg) preparation for carrier, Ni2, with biggish specific surface area, active metal particles size is small, is uniformly dispersed, is strong with the binding force of carrier, is not susceptible to be lost in reaction process and reunite.The catalyst is applied in the reaction of C5/C9 hydrogenation of petroleum resin, not only catalytic hydrogenation activity with higher and decoloration performance, and can effectively inhibit being greatly lowered for softening point, suitable for preparing the hydrogenated petroleum resin of high-quality, low (< 1.2 gBr of products obtained therefrom bromine valency2/100g)；Coloration is shallow (Gardner Color < 0.6)；Softening point height (> 84 DEG C).
Description
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to a kind of load-type nickel series catalysts and its preparation and its
Application in C5/C9 Petropols catalytic hydrogenation.
Background technique
Petropols are a kind of using the distillate of by-product in cracking ethylene preparation technical process as raw material, raw by polymerization reaction
The thermoplastic resin of production has a wide range of applications in industries such as coating, rubber chemicals, printings, but simultaneously, contains in Petropols
A large amount of impurity such as unsaturated hydrocarbons key and halogen, make Petropols there are form and aspect that deep, smell is pungent, poor adhesion, fast light
The disadvantages of thermal stability and poor oxidation stability, to limit it in the application in high-grade, precision and advanced field.
Hydrogenated petroleum resin be by C5/C9 Petropols structure unsaturated C=C double bond and phenyl ring be catalyzed
Add the special material haveing excellent performance made from hydrogen.The hydrogenated petroleum resin of catalytic hydrogenation C5/C9 Petropols preparation is in water white,
Weatherability, in terms of be substantially better than C5/C9 Petropols, in fields such as tackifier, high-grade ink, rubber, coating
With relatively broad application.Petropols price after catalytic hydrogenation treatment is approximately the 2-3 for not adding hydrogen rubble oleoresin
Times, added value with higher.
The catalyst applied to C5/C9 hydrogenation of petroleum resin reported at present mainly has nickel system and the system supported catalysis of palladium
Agent.
Although palladium series catalyst catalytic hydrogenation activity with higher for Petropols, while can effectively inhibit stone
Oleoresin adds hydrogen to degrade, but more sensitive to the sulfur-containing compound in Petropols, is easily poisoned, and causes irreversible inactivation,
And higher cost.Support type disclosed in patent US4953639, US4540480, CN101157029A, CN103386302A etc. is expensive
Metallic catalyst, active component are mainly Pd, Rh, Ru etc., and hydrogenation of petroleum resin with higher is active, but expensive,
There are problems that easy poisoning and deactivation.
And the hydrogen-absorbing ability of non-noble metal Ni is only second to Pd, and compared with precious metals pt, Pd etc., Ni is to catalytic poisons such as S
It is insensitive, it is therefore possible to replace active component of the precious metal element as hydrogenation catalyst, it is particularly suitable for sulfur-bearing oil tree
Rouge adds hydrogen, and it greatly reduces preparation cost and use cost for opposite noble metal, is conducive in scale, industry
Metaplasia is widely used in producing.
Patent EP 0308137A uses γ-Al2O3The Ni-W catalyst of load carries out the reaction of C5 hydrogenation of petroleum resin, still
The yield of hydrogenated resin is only 25.7%, and softening point only has 60-70 DEG C, this is because γ-Al2O3With stronger Louis
Acidity, it is acid to will lead to the raising of resin C-C key hydrogenolysis activity by force, and then lead to resin plus hydrogen degradation, both influence hydrogenation resin
Yield, and significantly reduce hydrogenation products softening point reduce.
In contrast, SiO2It is a kind of neutral carrier, applies in hydrogenation of petroleum resin, softening point can be effectively inhibited
It reduces.Patent CN 104941649A uses traditional infusion process to be prepared for nickel loading as the Ni-SiO of 30-50 wt.%2Load
Type catalyst, hydrogenated petroleum resin softening point fall is small, but higher (> 1 gBr of bromine valency2/ 100 g), is because using passing
The infusion process preparation high load amount catalyst of system be easy to cause nickel Active components distribution uneven, nickel active component occurs due to poly-
Collect the phenomenon for causing particle larger, causes amount of activated center that cannot play its catalytic action.Liu Weixing et al. (" Ni/SiO2It urges
Influence of the agent preparation condition to C5 resin catalysis hydrogenation reaction performance ", " China Petroleum and chemical standard and quality ", 2014,
2,31-31.) Ni/SiO prepared with coprecipitation2Catalyst activity component is uniformly dispersed, but whole solid close, outer to compare table
Area is smaller, and number exposure in aperture is less, so that contact of the reactant molecule with activated centre is limited, causes to Petropols insatiable hunger
It is low with hydrocarbon key degree of hydrogenation.
In conclusion key, which is to improve, lives to develop a kind of hydrogenation of petroleum resin catalyst with high hydrogenation activity
Property component dispersion degree while can be improved more active sites, improve the accessibility of Petropols molecule and activated centre,
To enhance catalyst to the catalytic activity of Petropols.The exploitation of efficient nickel system supported catalyst is for producing high added value
Hydrogenated petroleum resin have highly important scientific meaning and practical value.
Summary of the invention
To solve the above problems, the present invention develops a kind of load-type nickel series catalysts, it is to be prepared with Stober method
The silica nanosphere of uniform particle sizes is as carrier, under alkaline condition, use surface etching methods supported active metals nickel with
And promoter metal component, to improve the dispersion degree of catalyst active center and the accessibility in activated centre significantly, control
The size of active particle.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of load-type nickel series catalysts are using the silica nanosphere of uniform particle sizes as carrier, and Ni is main active metal
Center, and add the meso-porous hollow nano-sphere catalyst of promoter metal preparation, wherein the load capacity of Ni is 20-40 wt.%, excellent
It is selected as 20-30 wt.%, the load capacity of promoter metal is 2-5 wt.%, preferably 3 wt.%；
The promoter metal is copper, cobalt, any one in magnesium.
The silica nanosphere is synthesized using Stober method, synthesis step are as follows:
A) preparation of solution C: according to volume ratio 1:6-1:11(being preferably 1:7-1:9 by tetraethyl orthosilicate and ethyl alcohol) mixing is equal
It is even；
B) preparation of solution D: with deionized water being preferably 1:2 according to volume ratio 1:1-1:3(by ethyl alcohol) it mixes, then press ethyl alcohol
The volume ratio of aqueous solution and ammonia spirit is that 4:1-8:1(is preferably 1:6-1:7) ammonia spirit of 25-28 vol% is added；
C) preparation of silica nanosphere: solution C is added rapidly in solution D, is preferably 600- in 400-1100 rpm(
1000 rpm) it is centrifuged after 3 h of stirring at normal temperature under revolving speed, gained white solid is washed with deionized 2 times, after ethanol washing 3 times,
Being placed in baking oven 100 DEG C, drying to constant weight to get silica nanosphere.
The preparation methods of the load-type nickel series catalysts the following steps are included:
(1) silica nanosphere is add to deionized water ultrasonic treatment 30-50 min, forms solution A；
(2) presoma of the presoma of nickel and promoter metal is dissolved in deionized water, is added dropwise a certain amount of 25-28 vol%'s
Ammonia spirit forms metal ammonia solution, and a certain amount of ammonium salt is then added, and stirring 5-10 min is uniformly mixed, and forms solution B；
(3) solution B is added dropwise in solution A, continues to stir 5-10 min, then gained mixed solution is transferred to poly- four
In the stainless steel cauldron of vinyl fluoride liner, being placed in 95-180 DEG C of reaction 10-24 h(in baking oven is preferably 15-20 h)；
(4) reaction product is placed in reducing atmosphere, after 600-950 DEG C (preferably 650-800 DEG C) reduction 4-6 h,
Obtain SiO2The nickel catalyst Ni-M-SiO of load2。
The presoma of nickel described in step (2) is nickel sulfate, nickel chloride, nickel nitrate or nickel acetate；
The presoma of the promoter metal is the villaumite or nitrate of copper, cobalt, magnesium；
It is preferably 3-5:1 that the dripping quantity of the ammonia spirit, which is 1.5-8:1(by the molar ratio of ammonia and silica nanosphere) into
Row conversion；
The ammonium salt is ammonium hydrogen carbonate, ammonium sulfate, ammonium chloride or ammonium nitrate, preferably ammonium chloride and ammonium nitrate, additive amount with
The molar ratio of silica nanosphere used is that 1-3:1(is preferably 2-3:1).
Reducing atmosphere described in step (4) is the gaseous mixture of hydrogen and inert gas, and wherein the concentration of hydrogen is 10 %
(V/V), the inert gas is argon gas or nitrogen.
The load-type nickel series catalysts can be applied in the catalytic hydrogenation of C5/C9 Petropols.Its concrete application method
Are as follows: the load-type nickel series catalysts are fitted into the stainless steel reaction pipe of fixed-bed micro-reactor, with hydrogen purge 30
Air in min metathesis reactor and pipeline, 1 h of activated catalyst under 220 DEG C, 50 ml/min hydrogen flow rates, so
C5/C9 Petropols solution is injected into fixed-bed micro-reactor by high-pressure pump afterwards and carries out hydrogenation reaction, reaction condition are as follows: temperature
180-260 DEG C (preferably 200-220 DEG C) is spent, Hydrogen Vapor Pressure 40-70 bar(is preferably 50-60 bar), volume space velocity
0.5-2.5 h-1(preferably 1-1.5 h-1), hydrogen-oil ratio 400-800:1(is preferably 600:1-800:1)；Product after hydrogenation reaction
It is evaporated under reduced pressure, obtains solid hydride C5/C9 Petropols.
The C5/C9 Petropols solution is that C5 or C9 Petropols are dissolved in organic solvent to be formulated, dense
Degree is 10-20 wt.%；The organic solvent is one in hexamethylene, pentamethylene, acetone, hexahydrotoluene, toluene or dimethylbenzene
Kind is several, preferably hexamethylene.
The beneficial effects of the present invention are:
(1) the nickel system supported catalyst prepared by the present invention is a kind of meso-porous hollow nanosphere with high-specific surface area,
Active metal component particle is small (< 5 nm), and dispersion degree is high and stability is strong, not easy to reunite, long service life when reaction.
(2) the nickel system supported catalyst prepared by the present invention is used for the catalytic hydrogenation of C5/C9 Petropols, hydrogenates C5 stone
Low (< 0.85 gBr of the bromine valency of oleoresin2/100 g)；Coloration is shallow (Gardner Color < 0.5)；Softening point height (> 84 DEG C)；Hydrogenation
The bromine valency of C9 Petropols < 1.2 gBr2/100 g；Gardner Color < 0.6；Softening point > 94 DEG C, and alkene with higher
And aromatic hydrocarbons key hydrogenation conversion.
Detailed description of the invention
Fig. 1 is that the SEM of 1 prepared catalyst of embodiment schemes.
Fig. 2 is TEM figure of 1 prepared catalyst of embodiment under different multiples.
Fig. 3 is the N of 1 prepared catalyst of embodiment2Adsorption-desorption isothermal and graph of pore diameter distribution.
Fig. 4 is the XRD comparison diagram of catalyst prepared by embodiment 1 and comparative example 2.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
The raw material is SILVER REAGENT.In embodiment, XRD is using the Japanese Ultima type X-ray powder diffraction produced
Instrument, the Tecnai G2 F20 type Flied emission transmission electron microscope observing catalyst structure produced using FEI Co., the U.S., using Czech FEI
The production of CZECH REPUBLIC S.R.O. company /230 field emission scanning electron microscope of Nova NanoSEM observation catalyst
Pattern, BET use Merck & Co., Inc, the U.S. produce 2460 surface area of ASAP and porosity analyser.After reaction, to gained
Solid hydride product carries out Physical Property Analysis, measures product bromine valency using domestic BR-1 type bromine valency bromine index analyzer, use is domestic
The full-automatic softening point apparatus of SYD-2806G measures product softening point, measures product coloration using Gardner's colorimeter.
Silica nanosphere used the preparation method comprises the following steps: 5 ml tetraethyl orthosilicates are added to group in 45 ml ethyl alcohol
At solution C, 16 ml ethyl alcohol and 24 ml deionized waters are mixed into ethanol water, 10 ml, 25-28 vol% are then added
Ammonia spirit forms solution D, and solution C is added rapidly in solution D, is centrifuged after 3 h of stirring at normal temperature under 800 rpm revolving speeds,
Gained white solid is washed with deionized 2 times, and after ethanol washing 3 times, in 100 DEG C of baking ovens, drying to constant weight, obtains 2.5 g
SiO2Nanosphere.
Embodiment 1
Take 0.2g SiO2It is added in 50 ml deionized waters, 40 min of ultrasonic disperse, forms solution A, weigh 0.25 g
NiCl2•6H2O、0.02 g CuCl2•2H2O is dissolved in 40 ml deionized waters, and 2 ml, 25-28 vol% ammonia spirit are added dropwise
(molar ratio of ammonia and silica is 6:1), and 0.5g NH is added45 min are stirred after Cl, obtain metal ammonia solution B, it will be molten
Liquid B be added in solution A continue stir 5 min after, be transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, be placed in
It is cooled to room temperature after 150 DEG C of 12 h of reaction in baking oven, decompression suction filtration is simultaneously multiple with deionized water and ethanol washing, then in baking
70 DEG C of dryings obtain green powder, gained powder are placed in tube furnace, under 850 DEG C of reducing atmospheres also to constant weight in case
6 h are to get load-type nickel series catalysts Ni-Cu-SiO for original2。
Taking 3.5g(2.5 ml) the 20-40 mesh catalyst granules of above-mentioned preparation is packed into the stainless steel of fixed-bed micro-reactor
In reaction tube, with the air in 30 min replacement piping of hydrogen purge, activated under 220 DEG C, 50 ml/min hydrogen flow rates
Prepared 10 wt.% C5/C9 Petropols/cyclohexane solution is placed in head tank, is infused by high-pressure pump by 1 h of catalyst
Enter and carry out hydrogenation reaction, reaction condition in fixed bed reactors are as follows: 200 DEG C of temperature, hydrogen press 50 bar, liquid volume air speed 1.5
h-1, hydrogen-oil ratio 800:1 (V/V) adds the product after hydrogen that solid product is precipitated through gas-liquid separation, vacuum distillation and carries out physical property point
Analysis.
Fig. 1 is that the SEM of 1 prepared catalyst of embodiment schemes.It can be seen from the figure that the catalyst is receiving for uniform particle diameter
Rice ball (300-400 nm).
Fig. 2 is that the TEM of 1 prepared catalyst of embodiment schemes.It can be seen from the figure that the catalyst is that surface has dispersion
The tiny balloon of nanometer sheet, and active metal particles are dispersed on carrier, and its partial size is small (< 5 nm), can make petroleum
Molecular resin can be contacted more effectively with catalyst activity position, so that hydrogenation of petroleum resin activity can be improved.
Fig. 3 is the N of 1 prepared catalyst of embodiment2Adsorption-desorption isothermal and graph of pore diameter distribution.Catalyst has IV
Type adsorption-desorption isothermal, in P0There is H2 type hysteresis loop, average pore size is 3.8 nm, illustrates that catalyst has at=0.5-0.95
There is meso-hole structure；With biggish specific surface area (322.2 m2/ g) and pore volume (0.47 cm3/ g), active component be easy to instead
Substrate is answered to contact, to improve hydrogenation activity.
Embodiment 2
Take 0.2g SiO2It is added in 50 ml deionized waters, 40 min of ultrasonic disperse, forms solution A, weigh 0.3 g Ni
(NO3)2•6H2O、0.02 g Co(NO3)2•2H2O is dissolved in 40 ml deionized waters, and 1.5 ml, 25-28 vol% ammonium hydroxide are added dropwise
Solution (molar ratio of ammonia and silica is 5:1), and 0.5g NH is added45 min are stirred after Cl, obtain metal ammonia solution B,
Solution B is added in solution A after continuing to stir 5 min, is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining,
It is placed in baking oven and is cooled to room temperature after 120 DEG C of 10 h of reaction, decompression suction filtration is simultaneously multiple with deionized water and ethanol washing, then
70 DEG C of dryings obtain green powder, gained powder are placed in tube furnace to constant weight in baking oven, 800 DEG C of reducing atmospheres
6 h are to get load-type nickel series catalysts Ni-Co-SiO for lower reduction2。
Taking 3.5g(2.5 ml) the 20-40 mesh catalyst granules of above-mentioned preparation is packed into the stainless steel of fixed-bed micro-reactor
In reaction tube, with the air in 30 min replacement piping of hydrogen purge, activated under 220 DEG C, 50 ml/min hydrogen flow rates
Prepared 15 wt.% C5/C9 Petropols/cyclohexane solution is placed in head tank, is infused by high-pressure pump by 1 h of catalyst
Enter and carry out hydrogenation reaction, reaction condition in fixed bed reactors are as follows: 200 DEG C of temperature, hydrogen press 50 bar, liquid volume air speed 1.5
h-1, hydrogen-oil ratio 800:1 (V/V) adds the product after hydrogen that solid product is precipitated through gas-liquid separation, vacuum distillation and carries out physical property point
Analysis.
Embodiment 3
Take 0.2g SiO2It is added in 50 ml deionized waters, 40 min of ultrasonic disperse, forms solution A, weigh 0.25 g Ni
(OAC)2•6H2O、0.02 g Mg(NO3)2•2H2O is dissolved in 40 ml deionized waters, and 1.0 ml, 25-28 vol% ammonium hydroxide are added dropwise
Solution (molar ratio of ammonia and silica is 3:1), and 0.5g NH is added45 min are stirred after Cl, obtain metal ammonia solution B,
Solution B is added in solution A after continuing to stir 5 min, is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining,
It is placed in baking oven and is cooled to room temperature after 120 DEG C of 10 h of reaction, decompression suction filtration is simultaneously multiple with deionized water and ethanol washing, then
70 DEG C of dryings obtain green powder, gained powder are placed in tube furnace to constant weight in baking oven, 800 DEG C of reducing atmospheres
6 h are to get load-type nickel series catalysts Ni-Mg-SiO for lower reduction2。
Taking 3.5g(2.5 ml) the 20-40 mesh catalyst granules of above-mentioned preparation is packed into the stainless steel of fixed-bed micro-reactor
In reaction tube, with the air in 30 min replacement piping of hydrogen purge, activated under 220 DEG C, 50 ml/min hydrogen flow rates
Prepared 20 wt.% C5/C9 Petropols/cyclohexane solution is placed in head tank, is infused by high-pressure pump by 1 h of catalyst
Enter and carry out hydrogenation reaction, reaction condition in fixed bed reactors are as follows: 200 DEG C of temperature, hydrogen press 50 bar, liquid volume air speed 1.5
h-1, hydrogen-oil ratio 800:1 (V/V) adds the product after hydrogen that solid product is precipitated through gas-liquid separation, vacuum distillation and carries out physical property point
Analysis.
Embodiment 4
Take 0.2g SiO2It is added in 50 ml deionized waters, 40 min of ultrasonic disperse, forms solution A, weigh 0.2 g Ni
(NO3)2•6H2O、0.015 g Cu(NO3)2•2H2O is dissolved in 40 ml deionized waters, and 2.0 ml, 25-28 vol% ammonia are added dropwise
Aqueous solution (molar ratio of ammonia and silica is 6:1), and 0.5g NH is added45 min are stirred after Cl, obtain metal ammonia solution
Solution B is added in solution A after continuing to stir 5 min, is transferred to the stainless steel cauldron with polytetrafluoroethyllining lining by B
In, it is placed in baking oven and is cooled to room temperature after 95 DEG C of 12 h of reaction, decompression suction filtration is simultaneously multiple with deionized water and ethanol washing, so
70 DEG C of dryings obtain green powder, gained powder are placed in tube furnace to constant weight in baking oven afterwards, 700 DEG C of reproducibility gas
6 h are restored under atmosphere to get load-type nickel series catalysts Ni-Cu-SiO2。
Taking 3.5g(2.5 ml) the 20-40 mesh catalyst granules of above-mentioned preparation is packed into the stainless steel of fixed-bed micro-reactor
In reaction tube, with the air in 30 min replacement piping of hydrogen purge, activated under 220 DEG C, 50 ml/min hydrogen flow rates
Prepared 10 wt.% C5/C9 Petropols/cyclohexane solution is placed in head tank, is infused by high-pressure pump by 1 h of catalyst
Enter and carry out hydrogenation reaction, reaction condition in fixed bed reactors are as follows: 200 DEG C of temperature, hydrogen press 50 bar, liquid volume air speed 1.5
h-1, hydrogen-oil ratio 800:1 (V/V) adds the product after hydrogen that solid product is precipitated through gas-liquid separation, vacuum distillation and carries out physical property point
Analysis.
Embodiment 5
Take 0.2g SiO2It is added in 50 ml deionized waters, 40 min of ultrasonic disperse, forms solution A, weigh 0.18 g Ni
(NO3)2•H2O、0.015 g Co(NO3)2•2H2O is dissolved in 40 ml deionized waters, and 1.5 ml, 25-28 vol% ammonium hydroxide are added dropwise
Solution (molar ratio of ammonia and silica is 5:1), and 0.5g NH is added45 min are stirred after Cl, obtain metal ammonia solution B,
Solution B is added in solution A after continuing to stir 5 min, is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining,
Be placed in baking oven and be cooled to room temperature after 95 DEG C of 12 h of reaction, decompression filter simultaneously it is multiple with deionized water and ethanol washing, then in
70 DEG C of dryings obtain green powder, gained powder are placed in tube furnace, under 700 DEG C of reducing atmospheres to constant weight in baking oven
6 h are restored to get load-type nickel series catalysts Ni-Co-SiO2。
Taking 3.5g(2.5 ml) the 20-40 mesh catalyst granules of above-mentioned preparation is packed into the stainless steel of fixed-bed micro-reactor
In reaction tube, with the air in 30 min replacement piping of hydrogen purge, activated under 220 DEG C, 50 ml/min hydrogen flow rates
Prepared 15 wt.% C5/C9 Petropols/cyclohexane solution is placed in head tank, is infused by high-pressure pump by 1 h of catalyst
Enter and carry out hydrogenation reaction, reaction condition in fixed bed reactors are as follows: 200 DEG C of temperature, hydrogen press 50 bar, liquid volume air speed 1.5
h-1, hydrogen-oil ratio 800:1 (V/V) adds the product after hydrogen that solid product is precipitated through gas-liquid separation, vacuum distillation and carries out physical property point
Analysis.
Embodiment 6
Take 0.2g SiO2It is added in 50 ml deionized waters, 40 min of ultrasonic disperse, forms solution A, weigh 0.18 g Ni
(NO3)2•6H2O、0.015 g Mg(NO3)2•2H2O is dissolved in 40 ml deionized waters, and 1.0 ml, 25-28 vol% ammonia are added dropwise
Aqueous solution (molar ratio of ammonia and silica is 3:1), and 0.5g NH is added45 min are stirred after Cl, obtain metal ammonia solution
Solution B is added in solution A after continuing to stir 5 min, is transferred to the stainless steel cauldron with polytetrafluoroethyllining lining by B
In, it is placed in baking oven and is cooled to room temperature after 120 DEG C of 10 h of reaction, decompression suction filtration is simultaneously multiple with deionized water and ethanol washing, so
70 DEG C of dryings obtain green powder, gained powder are placed in tube furnace to constant weight in baking oven afterwards, 750 DEG C of reproducibility gas
6 h are restored under atmosphere to get load-type nickel series catalysts Ni-Mg-SiO2。
Taking 3.5g(2.5 ml) the 20-40 mesh catalyst granules of above-mentioned preparation is packed into the stainless steel of fixed-bed micro-reactor
In reaction tube, with the air in 30 min replacement piping of hydrogen purge, activated under 220 DEG C, 50 ml/min hydrogen flow rates
Prepared 20 wt.% C5/C9 Petropols/cyclohexane solution is placed in head tank, is infused by high-pressure pump by 1 h of catalyst
Enter and carry out hydrogenation reaction, reaction condition in fixed bed reactors are as follows: 200 DEG C of temperature, hydrogen press 50 bar, liquid volume air speed 1.5
h-1, hydrogen-oil ratio 800:1 (V/V) adds the product after hydrogen that solid product is precipitated through gas-liquid separation, vacuum distillation and carries out physical property point
Analysis.
Comparative example 1
To investigate influence of the promoter metal to catalyst activity component and to final hydrogenation of petroleum resin effect, this comparative example is adopted
The catalyst n i-SiO of Ni is only loaded with preparation condition preparation same as Example 12, and petroleum tree is used for identical operation
Rouge adds hydrogen, to compare with embodiment 1.
Comparative example 2
To investigate influence of the carrying method to catalyst activity component and to final hydrogenation of petroleum resin effect, this comparative example is adopted
Bimetallic catalyst Ni-Cu-SiO is prepared with traditional infusion process2, preparation method is specific as follows: weighing 0.25 g NiCl 2•
6H2O、0.02 g CuCl 2•2H2O is dissolved in 50 ml deionized waters, and 0.2 g SiO is added2, it is transferred in round-bottomed flask, passes through
Rotary evaporation removes moisture removal, and 70 DEG C of oven dryings obtain cyan powders, and gained powder is placed in 850 DEG C of reduction in tube furnace
6 h are restored under property atmosphere to get nickel system supported catalyst Ni-Cu-SiO2.It is commented using hydrogenation reaction same as Example 1
Valence condition.
Fig. 4 is catalyst XRD comparison diagram prepared by embodiment 1 and comparative example 2.It can be seen from the figure that by hydrogen
After reduction, there is Ni at 44.4 °, 51.6 ° and 76.1 ° in two catalyst0Diffraction maximum, calculated by Scherrer formula
Obtaining catalyst activity metallic particles partial size prepared by embodiment 1 is 5.2 nm, is consistent with TEM result, and prepared by comparative example 2 urges
Agent active metal particles partial size is 30 nm, hence it is evident that greater than the active component particles size of 1 catalyst of embodiment, it was demonstrated that dipping
The catalyst particle size of method preparation is big, causes amount of activated center that cannot play its catalytic action.Therefore, using surface etch
The catalyst of method preparation is applied to hydrogenation of petroleum resin, has preferable result.
Above-described embodiment 1-6 and comparative example 1, the evaluation result of comparative example 2 are as shown in table 1, table 2.
The Contrast on effect of 1 embodiment of table and comparative example hydrogenation C5 Petropols
The Contrast on effect of 2 embodiment of table and comparative example hydrogenation C9 Petropols
By table 1, table 2 as it can be seen that compared with comparative example 1, the catalyst that the present invention adds the preparation of Cu auxiliary agent has preferably plus hydrogen is living
Property, compared with comparative example 2, the bimetallic catalyst for the surface etch method preparation that the present invention uses is than passing through traditional infusion process institute
Prepare hydrogenation degree of the catalyst with higher active component dispersion degree and higher unsaturated hydrocarbons key.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (8)
1. a kind of load-type nickel series catalysts, it is characterised in that: the catalyst is with the silica nanosphere of uniform particle sizes
Carrier, Ni is main active metal centre, and adds the meso-porous hollow nano-sphere catalyst of promoter metal preparation, wherein Ni's is negative
Carrying capacity is 20-40 wt.%, and the load capacity of promoter metal is 2-5 wt.%；
The promoter metal is copper, cobalt, any one in magnesium.
2. load-type nickel series catalysts according to claim 1, it is characterised in that: the silica nanosphere uses
The synthesis of Stober method, synthesis step are as follows:
A) preparation of solution C: tetraethyl orthosilicate and ethyl alcohol are uniformly mixed according to volume ratio 1:6-1:11；
B) preparation of solution D: ethyl alcohol is mixed with deionized water according to volume ratio 1:1-1:3, then presses ethanol water and ammonia
The volume ratio of aqueous solution is the ammonia spirit that 25-28 vol% is added in 4:1-8:1；
C) preparation of silica nanosphere: solution C is added rapidly in solution D, the room temperature under 400-1100 rpm revolving speed
It is centrifuged after stirring 3 h, gained white solid is washed with deionized 2 times, after ethanol washing 3 times, is placed in 100 DEG C of bakings in baking oven
It does to constant weight to get silica nanosphere.
3. a kind of preparation method of load-type nickel series catalysts as described in claim 1, it is characterised in that: the following steps are included:
(1) silica nanosphere is add to deionized water and is ultrasonically treated, form solution A；
(2) presoma of the presoma of nickel and promoter metal is dissolved in deionized water, is added dropwise a certain amount of 25-28 vol%'s
Ammonia spirit forms metal ammonia solution, and a certain amount of ammonium salt is then added, and stirring 5-10 min is uniformly mixed, and forms solution B；
(3) solution B is added dropwise in solution A, continues to stir 5-10 min, then gained mixed solution is transferred to poly- four
In the stainless steel cauldron of vinyl fluoride liner, it is placed in baking oven and is reacted；
(4) reaction product is placed in reducing atmosphere after restoring, obtains SiO2The nickel catalyst of load.
4. the preparation method of load-type nickel series catalysts according to claim 3, it is characterised in that: ultrasonic in step (1)
The time of processing is 30-50 min.
5. the preparation method of load-type nickel series catalysts according to claim 3, it is characterised in that: described in step (2)
The presoma of nickel is nickel sulfate, nickel chloride, nickel nitrate or nickel acetate；
The presoma of the promoter metal is the villaumite or nitrate of copper, cobalt, magnesium；
The dripping quantity of the ammonia spirit is that 1.5-8:1 converts by the molar ratio of ammonia and silica nanosphere；
The ammonium salt is ammonium hydrogen carbonate, ammonium sulfate, ammonium chloride or ammonium nitrate, and additive amount rubs with silica nanosphere used
You are than being 1-3:1.
6. the preparation method of load-type nickel series catalysts according to claim 3, it is characterised in that: reaction in step (3)
Time be 10-24 h, temperature be 95-180 DEG C.
7. the preparation method of load-type nickel series catalysts according to claim 3, it is characterised in that: described in step (4)
Reducing atmosphere is the gaseous mixture of hydrogen and inert gas, and wherein the concentration of hydrogen is 10 % (V/V), and the inert gas is argon
Gas or nitrogen；The temperature of the reduction is 600-950 DEG C, and the time is 4-6 h.
8. a kind of application of load-type nickel series catalysts as described in claim 1 in C5/C9 Petropols catalytic hydrogenation.
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