CN107252688A - A kind of DCPD hydrogenation of petroleum resin catalyst and its preparation method and application - Google Patents
A kind of DCPD hydrogenation of petroleum resin catalyst and its preparation method and application Download PDFInfo
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- CN107252688A CN107252688A CN201710340210.9A CN201710340210A CN107252688A CN 107252688 A CN107252688 A CN 107252688A CN 201710340210 A CN201710340210 A CN 201710340210A CN 107252688 A CN107252688 A CN 107252688A
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- catalyst
- carrier
- hydrogenation
- dcpd
- pore volume
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 56
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000011347 resin Substances 0.000 title claims abstract description 41
- 229920005989 resin Polymers 0.000 title claims abstract description 41
- 239000003208 petroleum Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 31
- 229910001593 boehmite Inorganic materials 0.000 claims description 24
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000003292 glue Substances 0.000 claims description 22
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- -1 polyoxyethylene Polymers 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 238000007037 hydroformylation reaction Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 230000006872 improvement Effects 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- 239000002994 raw material Substances 0.000 description 17
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 13
- 229910052794 bromium Inorganic materials 0.000 description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005470 impregnation Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000000395 magnesium oxide Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 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 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical group CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 244000147058 Derris elliptica Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 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
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J35/635—0.5-1.0 ml/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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
It is used for DCPD hydrogenation of petroleum resin catalyst and its preparation method and application the invention discloses one kind.Catalyst composition includes：The Al that alkaline earth oxide is modified2O3Carrier and active metal component Ni, with modified Al2O3On the basis of the quality of carrier, the content of alkaline earth oxide is 1.0% ~ 4.8%, on the basis of the quality of catalyst, and active metal component Ni content is 12.0% ~ 30.0%, the Al that alkaline earth oxide is modified2O3The content of carrier is 70.0% ~ 88.0%.The catalyst first prepares γ Al2O3Carrier, then supported alkaline earth metal is after high-temperature roasting, then supported active metals component Ni, is obtained through low-temperature bake.The catalyst activity is higher and selectivity is good, and during for DCPD hydrogenation of petroleum resin, the hydrogenated resin unsaturated bond content of gained is substantially reduced, and colourity also has larger improvement, and softening point reduction is less.
Description
Technical field
The invention belongs to catalyst technical field, more particularly to a kind of hydrogenation of petroleum resin catalyst and preparation method thereof,
Especially a kind of DCPD hydrogenation of petroleum resin Ni loaded catalysts and its preparation method and application.
Background technology
Dicyclopentadiene（DCPD）Alicyclic C5 Petropols, abbreviation DCPD Petropols are one in C5 Petropols
Kind of important component, its relative molecular weight is between 1000 ~ 3000, and the resin has that stability is strong, Efficient Adhesive Promotion is good, soft
Change point it is high the characteristics of, also possess preferable compatibility, dissolubility and excellent acidproof, alkaline resistance properties, enjoy people to like, by with
Completely or partially to substitute rosin, drying oil, terpene resin etc..The maximum purposes of DCPD Petropols is compounding rubber and oil
Black auxiliary agent field, this product can improve coating property with improved compound rubber, in printing-ink, paint, pressure-sensitive adhesive, hot melt
The industries such as type bonding agent are widely used.
But hue difference, heat endurance and poor chemical stability occurs in common DCPD Petropols in use
The problems such as, can produce niff, long-term illumination hypostome color tolerance when heated easily deepens, and significantly limit it and applies model
Enclose.This is due to that the double bond formed in resin synthesis process has chemical instability.At present, in order to improve DCPD oil trees
The quality of fat, generally uses catalytic hydrogenation process with the double bond in saturation DCPD Petropols both at home and abroad.It becomes after being hydrogenated with
White or water white transparency, high stability and intersolubility DCPD hydrogenated petroleum resins.
With developing rapidly and the improvement of people's living standards for petroleum chemical industry, petroleum resin products increasingly tend to
Become more meticulous with it is superior, especially under the high speed development demand in the fields such as PUR, special adhesive, road surface paint, exterior wall paint,
Demand sharp increase to light high-quality resin both at home and abroad.Therefore, grinding for hydrogenation of petroleum resin catalyst and reaction process is accelerated
Hair is current important topic.
At present, the catalyst system that hydrogenation of petroleum resin reaction is used is mainly noble metal and the major class of base metal two.It is expensive
Metallic catalyst has palladium, platinum, rhodium, osmium, ruthenium etc., mostly loaded catalyst, and carrier generally uses aluminum oxide and diatomite；Non-noble
Metal system mainly includes nickel, load-type nickel, molybdenum sulfide, supported sulfided nickel-tungsten system and supported sulfided nickel-molybdenum system etc..
CN103386308A discloses a kind of C5Hydrogenation of petroleum resin Raney nickel and its preparation method and application.This is urged
Agent is that, using activated carbon as carrier, the non-crystaline amorphous metal nano particle of load Ni nano particles and Ni and metal promoter, Ni is born
Carrying capacity is only 3% ~ 8%.The catalyst uses activated carbon as carrier, and Ni load capacity is relatively low, for hydrogenation of petroleum resin
During reaction, the hydrogenation ratio of Petropols is relatively low.
CN102451691A discloses a kind of nickel-base catalyst preparation method for hydrogenation of petroleum resin.This method be by
Alumina catalyst support and/or silica are made slurries with active metal component and auxiliary agent and then added in manner of cocurrent flow with precipitating reagent
Be made catalyst precursors in reactor, then with peptizing agent and water kneading, shaping, dry and be calcined, obtain nickel-base hydrogenation and be catalyzed
Agent.What the active metal component in this method was loaded by way of precipitation, it can so make active metal scattered on carrier
It is uneven, or even aggregation occurs, so as to influence the performance of catalyst activity.
The content of the invention
In view of the shortcomings of the prior art, it is used for DCPD hydrogenation of petroleum resin catalyst and its preparation the invention provides one kind
Method.The catalyst activity is higher and selectivity is good, during for DCPD hydrogenation of petroleum resin, the hydrogenated resin unsaturated bond of gained
Content is substantially reduced, and colourity also has larger improvement, and softening point reduction is less.
It is used for DCPD hydrogenation of petroleum resin catalyst the invention provides one kind, its composition includes：Alkaline earth oxide
Modified Al2O3Carrier and active metal component Ni, with modified Al2O3On the basis of the quality of carrier, alkaline earth oxide
Content is 1.0% ~ 4.8%, preferably 1.5 ~ 3.0%, and on the basis of the quality of catalyst, active metal component Ni content is
12.0% ~ 30.0%, preferably 17.5 ~ 23.0%, the Al that alkaline earth oxide is modified2O3The content of carrier is 70.0% ~ 88.0%,
Preferably 77.0% ~ 82.5%.
The alkaline earth oxide is at least one of MgO, CaO, SrO, BaO, preferably MgO.
The Al that the alkaline earth oxide is modified2O3The pore-size distribution of carrier is：Bore dia is shared by 5 ~ 25nm hole
Pore volume is the 35% ~ 45% of total pore volume, and bore dia is that the pore volume shared by 130 ~ 230nm hole is the 40% ~ 50% of total pore volume.
The Al that the alkaline earth oxide is modified2O3The specific surface area of carrier is 125 ~ 185m2/ g, pore volume be 0.67 ~
0.80cm3/g。
The present invention is used for the preparation method of DCPD hydrogenation of petroleum resin catalyst, including：
（1）γ-Al2O3The preparation of carrier；
（2）By γ-Al2O3Carrier, which is placed in the dipping solution containing alkaline-earth metal, to be impregnated, drying, and 4 ~ 8 are calcined at 800 ~ 950 DEG C
H, obtains Al2O3Carrier；
（3）By step（2）The Al of the modification of gained2O3Carrier, which is placed in the dipping solution containing Ni, to be impregnated, drying, 400 ~
4 ~ 8h is calcined at 600 DEG C, described hydrogenation catalyst is obtained.
Step（1）In, γ-Al2O3Carrier prepare can using in aluminium hydroxide preparation process by reaming by the way of
（Such as add expanding agent）It is prepared from.It is preferred to use following process in the present invention to prepare：By boehmite dry glue powder A, intend
Boehmite dry glue powder B and expanding agent, surfactant, peptizing agent kneading, dry and are calcined, obtain γ-Al2O3Carrier.Wherein
Boehmite dry glue powder A and boehmite dry glue powder B mass ratio is with Al2O3It is calculated as 1：0.5 ~ 2.0, the addition of expanding agent
Amount accounts for boehmite dry glue powder A and boehmite dry glue powder B with Al2O3Count the 1% ~ 4% of gross mass.Surfactant plus
Enter amount and account for boehmite dry glue powder A and boehmite dry glue powder B with Al2O3Count the 2% ~ 5% of gross mass.Expanding agent and surface
The weight ratio of activating agent is 5:1~1:5.Expanding agent is preferably carbon black powder, and surfactant is preferably alkyl phenol polyoxyethylene
Ether, more preferably NPE, OPEO, dodecyl phenol polyethenoxy ether and dinonyl
At least one of phenol polyethenoxy ether.Peptizing agent is preferably the quality of the mixed acid of acetic acid and citric acid, acetic acid and citric acid
Than for 1：10~10：1, preferably 1：2~1：8.Described γ-Al2O3Carrier can without shaping or formed body, it is necessary to
Can be shape conventional in the art when being molded, such as spherical, cylindrical, bar shaped, five teeth are spherical etc..Described drying
It is as follows with roasting condition：4 ~ 8h is dried under the conditions of 100 ~ 150 DEG C；In 450 ~ 650 DEG C of 4 ~ 8h of roasting temperature；Further,
Temperature programming is carried out to sintering temperature with 100 ~ 200 DEG C/h heating rate, is calcined in air atmosphere.
The property of the boehmite dry glue powder A is as follows：Pore volume be 0.5 ~ 1.0mL/g, specific surface area be 180 ~
400m2/ g, most probable bore dia is 3 ~ 10nm；The property of the boehmite dry glue powder B is as follows：Pore volume is 0.7 ~ 1.5mL/
G, specific surface area is 100 ~ 350m2/ g, most probable bore dia is 15 ~ 40nm.
In the present invention, pore volume, specific surface area and the most probable bore dia of boehmite dry glue powder are to be calcined 6 in 550 DEG C
Measured after hour.
Step（2）In, described dipping solution is that the soluble-salt of alkaline-earth metal is dissolved in deionized water to mix equal
Even formation, the soluble-salt of described alkaline-earth metal is nitrate, according to step（1）It is calcined obtained γ-Al2O3Carrier
Water absorption rate, the dipping is incipient impregnation.Described immersion condition is：4 ~ 6h is impregnated under normal temperature.
Step（2）With（3）In, described drying condition is as follows：4 ~ 8h is dried under the conditions of 110 ~ 150 DEG C.
Step（2）In, after drying, with 100 ~ 200 DEG C/h heating rate temperature programming to sintering temperature, in air atmosphere
It is lower to be calcined.It is further preferably as follows：Multi-segment program heats up, and 1 ~ 2h is calcined under the conditions of 250 ~ 320 DEG C, at 480 ~ 560 DEG C
Under the conditions of be calcined 1 ~ 2h, under the conditions of 800 ~ 950 DEG C be calcined 2 ~ 4h.
Step（3）In, after drying, with 100 ~ 200 DEG C/h heating rate temperature programming to sintering temperature, in air atmosphere
It is lower to be calcined.
Step（3）In, described dipping solution is that the soluble-salt of Ni elements is dissolved in deionized water to be well mixed
Formed, the soluble-salt of the Ni elements is nickel nitrate or nickel acetate, according to step（2）It is calcined the suction of obtained modified support
Water rate, the dipping is incipient impregnation.Described immersion condition is：4 ~ 6h is impregnated under normal temperature.
Step（2）With（3）In, preferably rotated before baking, described revolving condition is as follows：On a rotary evaporator
Rotated under 50 ~ 60 DEG C of vacuum conditions and 0.5 ~ 1.0h is rotated under 0.5 ~ 1.0h, 65 ~ 75 DEG C of vacuum conditions.
Present invention also offers a kind of method of hydrotreating of DCPD Petropols, using catalyst of the present invention, use
Slurry bed system batch tank hydrogenation technique, its process includes：
（1）The hydrogenation catalyst is pre-processed；
（2）DCPD Petropols are dissolved in saturated hydrocarbons organic solvent and obtain reaction solution, polymerization inhibitor is selectively added, are added to
In high pressure batch reactor, then above-mentioned pretreated catalyst is added and reacted into reactor, after reaction terminates
It is isolated to DCPD hydrogenated petroleum resins.
The preprocess method of hydrogenation catalyst of the present invention, including：
A, by above-mentioned hydrogenation catalyst H2Reduced；
B, the catalyst after reduction is passivated；
Reducing condition described in step A is as follows：Also Primordial Qi is hydrogen, and 6 ~ 8h is reduced under conditions of normal pressure, 350 ~ 550 DEG C.
Passivating conditions described in step B are as follows：With O2Volume fraction is in the range of 0 ~ 5%, O2Content gradually increased bar
Under part, it is passed through passivating gas and catalyst is passivated.Passivating gas is O2And N2, passivation is entered under conditions of normal pressure, 45 ~ 55 DEG C
OK.
Application of the above-mentioned hydrogenation catalyst that the present invention is provided in the reaction of DCPD hydrogenation of petroleum resin, including：Using slurry
State bed batch tank hydrogenation technique, DCPD Petropols are dissolved in saturated hydrocarbons organic solvent and obtain reaction solution, selectivity adds
Enter polymerization inhibitor（Polymerization inhibitor can be added according to actual conditions, polymerization inhibitor can also be added without）, it is added to high pressure intermittent reaction
In kettle, then above-mentioned pretreated catalyst is added and reacted into reactor, reacted after terminating through isolated
DCPD hydrogenated petroleum resins.The reaction condition is specific as follows：240 ~ 300 DEG C of reaction temperature, 4 ~ 10MPa of reaction pressure, agitating paddle
Hydrogenation reaction under conditions of 60 ~ 180r/min of rotating speed, the mass ratio of the hydrogenation catalyst and reaction solution is 1: 14 ~ 18.
Application of the above-mentioned hydrogenation catalyst of the present invention in the reaction of DCPD hydrogenation of petroleum resin, the DCPD Petropols with
The mass ratio of saturated hydrocarbons organic solvent is 1: 6 ~ 12；The saturated hydrocarbons organic solvent is hexamethylene, and the polymerization inhibitor is to tertiary fourth
Base catechol；The quality for adding polymerization inhibitor is less than 3/10000ths of reaction solution gross mass.
Compared with prior art, the invention has the advantages that：
1st, the Al that the present invention is modified using alkaline earth oxide2O3Carrier, especially with specific structure of double peak holes
Alumina support, suitable active metal nickel is loaded, when react for DCPD hydrogenation of petroleum resin, with higher hydrogenation work
Property and selectivity, making the hydrogenated resin unsaturated bond content of gained substantially reduces, and colourity also has a larger improvement, softening point reduction compared with
It is few.
2nd, catalyst of the present invention first prepares γ-Al2O3Carrier, then supported alkaline earth metal, through high-temperature roasting at 800 ~ 950 DEG C,
Then supported active metals nickel again, through low-temperature bake at 400 ~ 600 DEG C, is so conducive to adjusting the property of carrier surface, simultaneously
Promote the interaction of alkaline-earth metal and carrier, so that the active metal nickel subsequently loaded is preferably scattered in carrier surface,
And the component for being more beneficial for reduction is generated, be conducive to improving catalyst activity.
3rd, catalyst of the present invention is preferred to use the boehmite dry glue powder A and boehmite dry glue powder of Different Pore Structures
B prepares γ-Al with expanding agent, surfactant, peptizing agent kneading2O3Carrier, the structure of double peak holes being consequently formed more is suitable for
DCPD hydrogenation of petroleum resin reacts, and reactant can be made fully to be reacted, moreover it is possible to product is spread in time, so that favorably
In improving the activity and selectivity of catalyst.
4th, during the present invention prepares hydrogenation catalyst, the step of substep is calcined especially is used in supported alkaline earth metal,
While contributing to the alkali salt presoma fully to decompose, alkaline-earth metal and Al are additionally aided2O3Good collaboration is formed to make
With being conducive to improving the activity of follow-up supported active metals.
Embodiment
With reference to embodiment, the present invention will be further described.It is emphasized that the description below is only
Exemplary, the scope being not intended to be limiting of the invention and its application.In the present invention, wt% is mass fraction.
The evaluation index of DCPD Petropols and hydrogenated petroleum resin is：Bromine number, colourity, softening point.Specific evaluation method
Referring to following professional standard and national standard：
SH/T 0236-1992 oil product bromine number determination methods；
GB/T 22295-2008 color of transparent liquids assay methods（Gardner Color）；
GB/T 4507-2014 asphalt softening point determination methods --- ring and ball method.
Hydrogenation ratio：Evaluation index of the hydrogenation ratio that DCPD Petropols bromine number is changed as catalyst.Hydrogenation ratio is calculated
Formula is as follows：
Wherein：Y --- the hydrogenation ratio of DCPD hydrogenated petroleum resins, wt%；
X1--- the bromine number of DCPD Petropols raw materials, gBr/100g；
X2--- the bromine number of DCPD hydrogenated petroleum resins, gBr/100g.
The property of aluminium hydroxide raw material used in the embodiment of the present invention and comparative example is shown in Table 1.
The property of aluminium hydroxide raw material used in the embodiment of the present invention of table 1 and comparative example
| Boehmite A1 | Boehmite B1 | |
| Specific surface area, m2/g | 260 | 220 |
| Pore volume, mL/g | 0.9 | 1.3 |
| Most probable bore dia, nm | 8 | 20 |
The raw material A property of DCPD Petropols used is as follows in the embodiment of the present invention and comparative example：Colourity：11#, softening point：
110.2 DEG C, bromine number is 18.420gBr/ (100g)；Raw material B properties are as follows：Colourity：11#, softening point：111.3 DEG C, bromine number is
16.694gBr/(100g)。
Embodiment 1
（1）γ-Al2O3The preparation of carrier：Weigh the powder of raw material A 1 and B1 powder that mass ratio is 1: 1 and the carbon that mass fraction is 3%
Black powder, it is dry-mixed uniform；Then it is 1 to add mass ratio:3 acetic acid and citric acid are soluble in water to obtain peptization acid, adds and carbon
The OPEO of the quality such as black powder, through kneading, extruded moulding and pelletizing dry 4h, with 150 under the conditions of 120 DEG C
DEG C/h heating rate carries out temperature programming to 600 DEG C, 4h is calcined in air atmosphere, obtains γ-Al2O3Carrier A.
（2）The preparation of magnesium oxide modified alumina support：By 12.72g magnesium nitrate hexahydrate be dissolved in 89.32mL go from
In sub- water, the completely rear 100g carriers A that adds to be dissolved carries out normal temperature incipient impregnation 5h, on a rotary evaporator 60 DEG C of vacuum bars
Rotated under part and rotate 0.6h under 0.6h, 75 DEG C of vacuum conditions, dry 4h under the conditions of 120 DEG C afterwards；It is calcined under the conditions of 300 DEG C
2h, 2h is calcined under the conditions of 500 DEG C, and 2h is calcined under the conditions of 850 DEG C, obtains magnesium oxide modified alumina support A, magnesia
Quality of the content based on the modified support is 2.04%.Magnesium oxide modified alumina support A property is as follows：Specific surface area is
151.50m2/ g, pore volume is 0.68 cm3/ g, pore-size distribution is：Bore dia is that the pore volume shared by 5 ~ 25nm hole is total pore volume
40%, bore dia is that the pore volume shared by 130 ~ 230nm hole is the 48% of total pore volume.
（3）The preparation of catalyst：120.95g six water nickel nitrates are dissolved in 42.19mL deionized water, it is to be dissolved
Above-mentioned modified aluminium oxide supports A is added after completely and carries out normal temperature incipient impregnation 5h, on a rotary evaporator 60 DEG C of vacuum conditions
0.6h is rotated under lower revolving 0.6h, 75 DEG C of vacuum conditions, 4h is dried under the conditions of 120 DEG C afterwards；In 450 DEG C of roasting temperatures
4h, obtains catalyst A of the present invention, quality of the content based on the catalyst of nickel is 19.7%.
（4）The reduction and passivation of catalyst：Catalyst A is reduced in 450 DEG C, hydrogen atmosphere, 50 DEG C of normal pressure passivation are
Can.
（5）DCPD hydrogenation of petroleum resin reactions are carried out in high pressure batch reactor：Catalyst grinding, 20 ~ 40 mesh of screening
Grain filling, loadings are 15mL, 240 DEG C of reaction temperature, the cyclohexane solution of reaction pressure 4MPa, DCPD Petropols and catalysis
Agent A mass ratio is 14, and the mass ratio of resin/hexamethylene is 1: 10, and polymerization inhibitor is p-tert-Butylcatechol, and addition is
The cyclohexane solution gross mass 1/10000th of DCPD Petropols, rotating speed of agitator 120r/min, reaction time 7h, the results are shown in Table
2。
Embodiment 2
（1）γ-Al2O3The preparation of carrier：Be the same as Example 1；
（2）The preparation of calcium oxide modified aluminium oxide supports：8.42g four water-calcium nitrate is dissolved in 92.11mL deionized water
In, completely rear 100g carriers A to be dissolved carries out normal temperature incipient impregnation 5h, is rotated on a rotary evaporator under 60 DEG C of vacuum conditions
0.6h is rotated under 0.6h, 75 DEG C of vacuum conditions, 4h is dried under the conditions of 120 DEG C afterwards；2h is calcined under the conditions of 300 DEG C, 520
2h is calcined under the conditions of DEG C, 2h is calcined under the conditions of 900 DEG C, modified support B is obtained, the content of calcium oxide is based on the modified support
Quality be 2.05%.Calcium oxide modified aluminium oxide supports B property is as follows：Specific surface area is 143.74m2/ g, pore volume is 0.68
cm3/ g, pore-size distribution is：Bore dia is that the pore volume shared by 5 ~ 25nm hole is the 42% of total pore volume, and bore dia is 130 ~ 230nm
Hole shared by pore volume be total pore volume 46%.
（3）The preparation of catalyst：120.76g six water nickel nitrates are dissolved in 40.76mL deionized water, it is to be dissolved
Modified support B is added after completely and carries out normal temperature incipient impregnation 4h, 0.6h is rotated under 60 DEG C of vacuum conditions on a rotary evaporator,
0.6h is rotated under 75 DEG C of vacuum conditions, 4h is dried under the conditions of 120 DEG C afterwards；In 450 DEG C of roasting temperature 4h, catalyst is obtained
B, quality of the content based on the catalyst of nickel is 19.7%；
（4）The reduction and passivation of catalyst：Be the same as Example 1；
（5）DCPD hydrogenation of petroleum resin reactions are carried out in high pressure batch reactor：Change the catalyst A in embodiment 1 into catalysis
Agent B, other be the same as Examples 1, the results are shown in Table 2.
Embodiment 3
（1）γ-Al2O3The preparation of carrier：Be the same as Example 1
（2）The preparation of strontium oxide strontia modified aluminium oxide supports：By 3.94g strontium nitrate solid dissolving 94.68mL deionized water
In, it is to be dissolved completely after add carrier A normal temperature incipient impregnation 4h wherein, 60 DEG C of vacuum condition backspins on a rotary evaporator
Steam and rotate 0.6h under 0.6h, 75 DEG C of vacuum conditions, dry 4h under the conditions of 120 DEG C afterwards；2h is calcined under the conditions of 300 DEG C,
2h is calcined under the conditions of 520 DEG C, 2h is calcined under the conditions of 850 DEG C, modified support C can be obtained, the content of strontium oxide strontia is based on the modification
The quality of carrier is 1.96%, and its property is as follows：Specific surface area is 179.64m2/ g, pore volume is 0.78 cm3/ g, pore-size distribution is：
Bore dia is that the pore volume shared by 5 ~ 25nm hole is the 41% of total pore volume, and bore dia is total for the pore volume shared by 130 ~ 230nm hole
The 47% of pore volume.
（3）The preparation of catalyst：126.87g six water nickel nitrates are dissolved in 40.90mL deionized water, it is to be dissolved
Modified support C is added after completely and carries out normal temperature incipient impregnation 5h, 0.6h is rotated under 60 DEG C of vacuum conditions on a rotary evaporator,
0.6h is rotated under 75 DEG C of vacuum conditions, 4h is dried under the conditions of 120 DEG C afterwards；In 450 DEG C of roasting temperature 4h, catalyst is obtained
C, quality of the content based on the catalyst of nickel is 20.6%.
（4）The reduction and passivation of catalyst：Be the same as Example 1.
（5）DCPD hydrogenation of petroleum resin reactions are carried out in high pressure batch reactor：Catalyst A in embodiment 1 is changed into
Catalyst C, other be the same as Examples 1, the results are shown in Table 2.
Embodiment 4
（1）γ-Al2O3The preparation of carrier：Be the same as Example 1；
（2）The preparation of modified aluminium oxide supports：By 3.41g barium nitrate solid dissolving in 94.68mL deionized water, treat molten
The completely rear carrier A that adds of solution carries out normal temperature incipient impregnation 4h, rotates 0.6h, 75 under 60 DEG C of vacuum conditions on a rotary evaporator
0.6h is rotated under DEG C vacuum condition, 4h is dried under the conditions of 120 DEG C afterwards；2h is calcined under the conditions of 300 DEG C, in 520 DEG C of conditions
Lower roasting 2h, 2h is calcined under the conditions of 900 DEG C, obtains modified support D, quality of the content based on the modified support of barium monoxide
For 2.04%, its property is as follows：Specific surface area is 159.56m2/ g, pore volume is 0.69 cm3/ g, pore-size distribution is：Bore dia be 5 ~
Pore volume shared by 25nm hole is the 40% of total pore volume, and bore dia is that the pore volume shared by 130 ~ 230nm hole is the 46% of total pore volume；
（3）The preparation of catalyst：121.24g six water nickel nitrates are dissolved in 41.30mL deionized water, it is to be dissolved complete
Modified support D is added afterwards and carries out normal temperature incipient impregnation 5h, rotates 0.6h, 75 DEG C under 60 DEG C of vacuum conditions on a rotary evaporator
0.6h is rotated under vacuum condition, 4h is dried under the conditions of 120 DEG C afterwards；In 450 DEG C of roasting temperature 4h, catalyst D, nickel are obtained
Quality of the content based on the catalyst be 19.7%；
（4）The reduction and passivation of catalyst：Be the same as Example 1；
（5）DCPD hydrogenation of petroleum resin reactions are carried out in high pressure batch reactor：Change the catalyst A in embodiment 1 into catalysis
Agent D, other be the same as Examples 1, the results are shown in Table 2.
Embodiment 5
（1）-（4）Preparation, the pretreatment of modified support and catalyst：Be the same as Example 1；
（5）DCPD hydrogenation of petroleum resin reactions are carried out in high pressure batch reactor：Change hydrogenation conditions, evaluating catalyst knot
Really, 3 are shown in Table.
Comparative example 1
Compared with Example 1, do not use magnesium oxide modified, that is, omit step（2）, catalyst DA is obtained, 2 are the results are shown in Table.
Comparative example 2
Compared with Example 1, γ-Al2O3The preparation of carrier is different, specific as follows：The powder of raw material A 1 and B1 powder, add peptization acid
Nitric acid, through kneading, extruded moulding and pelletizing dry 4h under the conditions of 120 DEG C, line program liter are entered with 150 DEG C/h heating rate
Temperature is calcined 4h, obtains γ-Al in air atmosphere to 600 DEG C2O3Carrier DB；
The preparation of magnesium oxide modified alumina support：Be the same as Example 1, magnesium oxide modified alumina support DB property is as follows：Than
Surface area is 160m2/ g, pore volume is 0.58 cm3/ g, pore-size distribution is：Bore dia is that the pore volume shared by 5 ~ 25nm hole is total hole
65% held, bore dia is that the pore volume shared by 130 ~ 230nm hole is the 5% of total pore volume；
Other step be the same as Examples 1, obtain catalyst DB, the results are shown in Table 2.
Comparative example 3
Compared with comparative example 1, change hydrogenation conditions, evaluating catalyst result is shown in Table 4.
Comparative example 4
Compared with comparative example 2, change hydrogenation conditions, evaluating catalyst result is shown in Table 4.
Table 2
| Embodiment | Catalyst | Raw material | Raw material bromine number, gBr/ (100g) | Product bromine number, gBr/ (100g) | Hydrogenation ratio, % | Colourity, # | Softening point, DEG C |
| Embodiment 1 | A | Raw material A | 18.420 | 1.746 | 90.5 | 2 | 87.2 |
| Embodiment 2 | B | Raw material B | 16.694 | 1.925 | 88.5 | 2 | 88.3 |
| Embodiment 3 | C | Raw material B | 16.694 | 1.894 | 88.7 | 2 | 87.8 |
| Embodiment 4 | D | Raw material A | 18.420 | 2.083 | 88.7 | 2 | 88.0 |
| Comparative example 1 | DA | Raw material A | 18.420 | 3.846 | 79.1 | 3 | 91.6 |
| Comparative example 2 | DB | Raw material A | 18.420 | 3.264 | 82.3 | 3- | 90.7 |
Evaluating catalyst result under the different technology conditions of table 3（Catalyst A）
| Reaction time, h | Reaction temperature, DEG C | Reaction pressure ,/MPa | Product bromine number, gBr/ (100g) | Raw material bromine number, gBr/ (100g) | Hydrogenation ratio, % | Colourity | Softening point, DEG C |
| 7 | 240 | 4 | 1.746 | 18.420 | 90.5 | 2 | 87.2 |
| 7 | 260 | 4 | 1.081 | 18.420 | 94.1 | 1+ | 86.0 |
| 7 | 280 | 4 | 1.044 | 18.420 | 94.3 | 1+ | 84.5 |
| 7 | 290 | 4 | 1.498 | 18.420 | 91.9 | 2 | 82.7 |
| 7 | 300 | 4 | 1.829 | 18.420 | 90.1 | 2 | 80.5 |
| 7 | 240 | 6 | 1.135 | 16.694 | 93.0 | 2- | 86.3 |
| 7 | 240 | 8 | 0.848 | 16.694 | 94.9 | 1+ | 85.5 |
| 7 | 240 | 9 | 0.765 | 16.694 | 95.4 | 1+ | 85.1 |
| 7 | 240 | 10 | 0.720 | 16.694 | 95.7 | 1 | 84.6 |
| 14 | 260 | 8 | 0.728 | 16.694 | 95.6 | 1 | 84.8 |
Evaluating catalyst result under the different technology conditions of table 4
| Catalyst | Reaction time, h | Reaction temperature, DEG C | Reaction pressure ,/MPa | Product bromine number, gBr/ (100g) | Raw material bromine number, gBr/ (100g) | Hydrogenation ratio, % | Colourity | Softening point, DEG C |
| DA | 7 | 260 | 8 | 2.921 | 18.420 | 84.1 | 2+ | 78.4 |
| DB | 7 | 260 | 8 | 2.527 | 18.420 | 86.4 | 2+ | 77.9 |
Claims (10)
1. one kind is used for DCPD hydrogenation of petroleum resin catalyst, its composition includes：The Al that alkaline earth oxide is modified2O3Carrier
With active metal component Ni, with modified Al2O3On the basis of the quality of carrier, the content of alkaline earth oxide for 1.0% ~
4.8%, preferably 1.5 ~ 3.0%, on the basis of the quality of catalyst, active metal component Ni content is 12.0% ~ 30.0%, excellent
Elect 17.5 ~ 23.0%, the Al that alkaline earth oxide is modified as2O3The content of carrier be 70.0% ~ 88.0%, preferably 77.0% ~
82.5%；The alkaline earth oxide is at least one of MgO, CaO, SrO, BaO, preferably MgO.
2. according to the catalyst described in claim 1, it is characterised in that：The Al that the alkaline earth oxide is modified2O3Carrier
Pore-size distribution is：Bore dia is that the pore volume shared by 5 ~ 25nm hole is the 35% ~ 45% of total pore volume, and bore dia is 130 ~ 230nm's
Pore volume shared by hole is the 40% ~ 50% of total pore volume.
3. according to the catalyst described in claim 1, it is characterised in that：The Al that the alkaline earth oxide is modified2O3Carrier
Specific surface area is 125 ~ 185m2/ g, pore volume is 0.67 ~ 0.80cm3/g。
4. the preparation method of any catalyst of claim 1 ~ 3, including：
（1）γ-Al2O3The preparation of carrier；
（2）By γ-Al2O3Carrier, which is placed in the dipping solution containing alkaline-earth metal, to be impregnated, drying, and 4 ~ 8 are calcined at 800 ~ 950 DEG C
H, obtains the Al of alkaline earth oxide modification2O3Carrier；
（3）By step（2）The Al of the modification of gained2O3Carrier, which is placed in the dipping solution containing Ni, to be impregnated, drying, 400 ~ 600
4 ~ 8h is calcined at DEG C, described hydrogenation catalyst is obtained.
5. in accordance with the method for claim 4, it is characterised in that：Step（1）In, γ-Al2O3The preparation of carrier：Thin water will be intended
Aluminium stone dry glue powder A, boehmite dry glue powder B and expanding agent, surfactant, peptizing agent kneading, dry and are calcined, obtain
γ-Al2O3Carrier；The property of the boehmite dry glue powder A is as follows：Pore volume be 0.5 ~ 1.0mL/g, specific surface area be 180 ~
400m2/ g, most probable bore dia is 3 ~ 10nm；The property of the boehmite dry glue powder B is as follows：Pore volume is 0.7 ~ 1.5mL/
G, specific surface area is 100 ~ 350m2/ g, most probable bore dia is 15 ~ 40nm；Described drying and roasting condition is as follows：100 ~
4 ~ 8h is dried under the conditions of 150 DEG C；In 450 ~ 650 DEG C of 4 ~ 8h of roasting temperature.
6. in accordance with the method for claim 5, it is characterised in that：Boehmite dry glue powder A and boehmite dry glue powder B
Mass ratio with Al2O3It is calculated as 1：0.5 ~ 2.0, the addition of expanding agent accounts for boehmite dry glue powder A and boehmite dry glue
Powder B is with Al2O3Count the 1% ~ 4% of gross mass；The addition of surfactant accounts for boehmite dry glue powder A and done with boehmite
Rubber powder B is with Al2O3Count the 2% ~ 5% of gross mass；The weight ratio of expanding agent and surfactant is 5:1~1:5；Expanding agent is carbon black
Powder, surfactant is polyoxyethylene alkylphenol ether, preferably NPE, OPEO, ten
At least one of dialkyl phenol APEO and Dinonylphenol Polyoxyethylene Ether；Peptizing agent is the mixing of acetic acid and citric acid
The mass ratio of acid, acetic acid and citric acid is 1：10~10：1, preferably 1：2~1：8.
7. in accordance with the method for claim 4, it is characterised in that：Step（2）Described in roasting use multi-segment program liter
Temperature, is calcined 1 ~ 2h under the conditions of 250 ~ 320 DEG C, and 1 ~ 2h is calcined under the conditions of 480 ~ 560 DEG C, 2 are calcined under the conditions of 800 ~ 950 DEG C
~4h。
8. in accordance with the method for claim 4, it is characterised in that：Step（2）With（3）In, rotated before baking, it is described
Revolving condition it is as follows：Rotated on a rotary evaporator under 50 ~ 60 DEG C of vacuum conditions under 0.5 ~ 1.0h, 65 ~ 75 DEG C of vacuum conditions
Rotate 0.5 ~ 1.0h.
9. a kind of method of hydrotreating of DCPD Petropols, it is characterised in that：Using any described catalyst of claim 1 ~ 3,
Using slurry bed system batch tank hydrogenation technique, its process includes：
（1）The hydrogenation catalyst is pre-processed；
（2）DCPD Petropols are dissolved in saturated hydrocarbons organic solvent and obtain reaction solution, polymerization inhibitor is selectively added, are added to
In high pressure batch reactor, then above-mentioned pretreated catalyst is added and reacted into reactor, after reaction terminates
It is isolated to DCPD hydrogenated petroleum resins.
10. in accordance with the method for claim 9, it is characterised in that：Step（1）In, the hydrogenation catalyst is located in advance
Reason process is as follows：First hydrogenation catalyst is reduced, processing is then passivated again；Step（2）In, DCPD Petropols add
Hydroformylation reaction condition is as follows：240 ~ 300 DEG C of reaction temperature, 4 ~ 10MPa of reaction pressure, 60 ~ 180r/min of rotating speed of agitator condition
Lower hydrogenation reaction, the mass ratio of the hydrogenation catalyst and reaction solution is 1: 14 ~ 18；The DCPD Petropols have with saturated hydrocarbons
The mass ratio of machine solvent is 1: 6 ~ 12；The quality for adding polymerization inhibitor is less than 3/10000ths of reaction solution gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN108329429A (en) * | 2018-03-07 | 2018-07-27 | 宁波金海晨光化学股份有限公司 | A kind of continuous method for preparing light dicyclopentadiene petroleum resin |
| CN108865449A (en) * | 2018-06-04 | 2018-11-23 | 北京石油化工学院 | The method and catalyst of biodiesel hydro-upgrading |
| CN110142044A (en) * | 2019-06-03 | 2019-08-20 | 北京柯通科技有限公司 | A kind of hydrogenation of petroleum resin catalyst and its preparation method and application |
| CN110961127A (en) * | 2019-12-09 | 2020-04-07 | 大连理工大学 | Method for preparing loaded DCPD resin hydrogenation catalyst by using hydrotalcite-like compound as precursor |
| CN111760574A (en) * | 2020-07-30 | 2020-10-13 | 淄博鲁华泓锦新材料股份有限公司 | C9 petroleum resin hydrogenation catalyst, preparation method and application thereof |
| CN111905776A (en) * | 2019-05-09 | 2020-11-10 | 中国石油化工股份有限公司 | Continuous reforming catalyst and preparation and application thereof |
| CN115069294A (en) * | 2022-07-08 | 2022-09-20 | 北京石油化工学院 | Supported catalyst and application thereof in preparation of tert-butylhydroquinone |
| CN115212887A (en) * | 2022-07-05 | 2022-10-21 | 南京大学 | Preparation method of reforming catalyst with high dispersion degree of active metal components |
| CN116273015A (en) * | 2023-03-06 | 2023-06-23 | 上海迅凯新材料科技有限公司 | Petroleum resin hydrogenation catalyst and its preparation method and application |
| CN116328770A (en) * | 2023-03-23 | 2023-06-27 | 福州大学 | Supported nickel-based catalyst and application thereof in hydrogenation of DCPD petroleum resin |
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| CN108329429A (en) * | 2018-03-07 | 2018-07-27 | 宁波金海晨光化学股份有限公司 | A kind of continuous method for preparing light dicyclopentadiene petroleum resin |
| CN108329429B (en) * | 2018-03-07 | 2020-08-21 | 宁波金海晨光化学股份有限公司 | Method for continuously preparing light-colored dicyclopentadiene petroleum resin |
| CN108865449A (en) * | 2018-06-04 | 2018-11-23 | 北京石油化工学院 | The method and catalyst of biodiesel hydro-upgrading |
| CN111905776A (en) * | 2019-05-09 | 2020-11-10 | 中国石油化工股份有限公司 | Continuous reforming catalyst and preparation and application thereof |
| CN110142044A (en) * | 2019-06-03 | 2019-08-20 | 北京柯通科技有限公司 | A kind of hydrogenation of petroleum resin catalyst and its preparation method and application |
| CN110142044B (en) * | 2019-06-03 | 2022-07-26 | 北京柯通科技有限公司 | Petroleum resin hydrogenation catalyst, and preparation method and application thereof |
| CN110961127A (en) * | 2019-12-09 | 2020-04-07 | 大连理工大学 | Method for preparing loaded DCPD resin hydrogenation catalyst by using hydrotalcite-like compound as precursor |
| CN111760574A (en) * | 2020-07-30 | 2020-10-13 | 淄博鲁华泓锦新材料股份有限公司 | C9 petroleum resin hydrogenation catalyst, preparation method and application thereof |
| CN111760574B (en) * | 2020-07-30 | 2023-04-18 | 淄博鲁华泓锦新材料集团股份有限公司 | C9 petroleum resin hydrogenation catalyst, preparation method and application thereof |
| CN115212887A (en) * | 2022-07-05 | 2022-10-21 | 南京大学 | Preparation method of reforming catalyst with high dispersion degree of active metal components |
| CN115212887B (en) * | 2022-07-05 | 2023-06-06 | 南京大学 | Preparation method of reforming catalyst with high dispersity of active metal component |
| CN115069294A (en) * | 2022-07-08 | 2022-09-20 | 北京石油化工学院 | Supported catalyst and application thereof in preparation of tert-butylhydroquinone |
| CN116273015A (en) * | 2023-03-06 | 2023-06-23 | 上海迅凯新材料科技有限公司 | Petroleum resin hydrogenation catalyst and its preparation method and application |
| CN116328770A (en) * | 2023-03-23 | 2023-06-27 | 福州大学 | Supported nickel-based catalyst and application thereof in hydrogenation of DCPD petroleum resin |
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