CN107774257A - A kind of hydrogenation catalyst and its application and a kind of preparation method of the cyclohexanedimethanodibasic dibasic ester of hexamethylene 1,2 - Google Patents
A kind of hydrogenation catalyst and its application and a kind of preparation method of the cyclohexanedimethanodibasic dibasic ester of hexamethylene 1,2 Download PDFInfo
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- CN107774257A CN107774257A CN201610785108.5A CN201610785108A CN107774257A CN 107774257 A CN107774257 A CN 107774257A CN 201610785108 A CN201610785108 A CN 201610785108A CN 107774257 A CN107774257 A CN 107774257A
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- Prior art keywords
- hydrogenation
- liquid
- gas
- hydrogenation catalyst
- catalyst
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 323
- 239000003054 catalyst Substances 0.000 title claims abstract description 179
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 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 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims description 15
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 139
- 238000000034 method Methods 0.000 claims abstract description 105
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000002148 esters Chemical class 0.000 claims abstract description 26
- 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
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 22
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 22
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 19
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 19
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 19
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 13
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 11
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 212
- 239000000203 mixture Substances 0.000 claims description 101
- 239000001257 hydrogen Substances 0.000 claims description 98
- 229910052739 hydrogen Inorganic materials 0.000 claims description 98
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 94
- 239000007789 gas Substances 0.000 claims description 74
- 239000012530 fluid Substances 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 40
- 239000011148 porous material Substances 0.000 claims description 30
- 238000002347 injection Methods 0.000 claims description 22
- 239000007924 injection Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 239000007791 liquid phase Substances 0.000 claims description 21
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical group N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 14
- 239000011800 void material Substances 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 description 34
- 239000000047 product Substances 0.000 description 30
- 239000000284 extract Substances 0.000 description 16
- 238000002803 maceration Methods 0.000 description 16
- 229910052707 ruthenium Inorganic materials 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- -1 phthalic acid ester Chemical class 0.000 description 14
- 239000010948 rhodium Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 10
- 229910052703 rhodium Inorganic materials 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000004014 plasticizer Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 4
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000004439 Isononyl alcohol Substances 0.000 description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 229940057402 undecyl alcohol Drugs 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of hydrogenation catalyst and its application, the catalyst contains carrier and the main active element and auxiliary element that are supported on carrier, and main active element is Rh and/or Ru, and auxiliary element is selected from Sm, Eu and Yb, and carrier is selected from activated carbon, Al2O3And SiO2.The invention also discloses the method for preparing the cyclohexanedimethanodibasic dibasic ester of hexamethylene 1,2 using the hydrogenation catalyst.Higher high active of hydrogenation catalysis is had according to the hydrogenation catalyst of the present invention, as phthalic acid dibasic ester Hydrogenation for hexamethylene 1, during the catalyst of 2 cyclohexanedimethanodibasic dibasic esters, higher catalytic activity is also showed that under relatively low reaction temperature, higher feed stock conversion and selectivity of product can be obtained.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and its application, and the invention further relates to the hexamethylene using the hydrogenation catalyst
The preparation method of alkane -1,2- cyclohexanedimethanodibasic dibasic esters.
Background technology
Plasticizer is the auxiliary agent kind that application amount is maximum in plastics industry, to promoting plastics industry particularly polyvinyl chloride
(PVC) industrial expansion plays conclusive effect.Traditional phthalic acid dibasic ester dosage is maximum in plasticizer, industrially
The plasticizer and softening agent of the rubber-plastics materials such as polyvinyl chloride are mainly used as, also makes an addition to daily high molecular plastics and rubber product extensively in addition
In, such as toy for children, packaging material for food, medical material, family expenses and automobile-used ornament materials.But phthalic acid dibasic ester
Carcinogenic suspicion and toxicity cause the close attentions of global all circles, accelerated in world wide environment-friendlyplasticizer plasticizer product with
And meet the application study of the plastic products of hygienic requirements.
Phthalic acid dibasic ester can transform into hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester by being hydrogenated with, hexamethylene -1,
2- cyclohexanedimethanodibasic dibasic esters are a kind of non-phthalic acid ester class environment-friendly plasticizers, but it has and knot as phthalate
Structure, phthalic ester plasticizer can be substituted completely, and function is more outstanding, such as：Migration is small, water white transparency, completely
Environmental protection, can with common organic solvent and common plasticizers mutual tolerance, and elasticity, the transparency and cryogenic property be much better than adjacent benzene two
Formate ester plasticizer, it is often more important that there are excellent toxicological characteristics.Therefore, hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester is plasticized
Agent can be that medicine equipment, packaging for foodstuff, medical supplies, toy for children and the other and PVC product of human body close contact manufacture
Business provides up the ideal solution of safety requirements, thus prohibits the use of the country of phthalic acid dibasic ester to obtain in many
It is mutatis mutandis in packaging for foodstuff, medicine equipment and toy for children.
Therefore, researcher starts to be directed to the preparation research of hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester.
CN102898309A discloses a kind of method of Hydrogenation for hexamethylene -1,2- dioctyl phthalate di-isooctyl, wherein, instead
System is answered to be made up of diisooctyl phthalate, hydrogen and catalyst, reaction condition is：Reaction temperature is 100-250 DEG C, instead
It is 5-18MPa, H to answer pressure2Volume ratio with diisooctyl phthalate is 2000-200：1, diisooctyl phthalate
Liquid air speed be 0.1-2.5h-1.The catalyst is with Al2O3For carrier, active component in for Ru, Pd, Ni one
Kind is several, and the loading of active component is the 1-3% of catalyst weight.
CN101417950A discloses the method that one kind prepares hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester, and reaction system is by neighbour
Phthalic acid dibasic ester, hydrogen and catalyst composition；Reaction condition is：Reaction temperature is 100-250 DEG C, reaction pressure 3.0-
12.0MPa H2Mol ratio with phthalic acid dibasic ester is 50-450, the liquid air speed 0.1- of phthalic acid dibasic ester
2.5h-1；Hydrogenation catalyst is with Al2O3、ZrO2、TiO2Or SiO2-Al2O3For carrier, active component Ru, Pd, Pt, Rh, Fe,
One or more in Co, Ni, Cu, the loading of active component are the 1-3% of catalyst weight.
Although researcher has developed a variety of methods for preparing hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester, existing
Method still has some shortcomings：
(1) need to carry out under higher reaction temperature (usually not less than 100 DEG C), carrying out reaction at high temperature causes
The operating cost increase of device, this is that manufacturing enterprise is reluctant to see；
(2) selectivity of product is not high enough, is on the one hand embodied in the overall selectivity of hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester not
Height, the suitable inverse ratio that is on the other hand embodied in product be not high (i.e., to the selectivity of cis hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester not
It is high)；
(3) hydrogen usage is still higher, causes operating cost to increase；
(4) feed stock conversion is not sufficiently stable.
In summary, it is still desirable to develop the new method for preparing hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester.
The content of the invention
It is an object of the invention to overcome to react temperature existing for existing hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester preparation methods
Spend high and technical problem of the selectivity of product still up for further improving, there is provided a kind of hydrogenation catalyst and use should
Hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester preparation method of hydrogenation catalyst, the catalyst show higher activity at low temperature,
Higher feed stock conversion can not only be obtained, and higher selectivity of product can be obtained.
According to the first aspect of the invention, the invention provides a kind of hydrogenation catalyst, the catalyst contain carrier with
And load main active element and auxiliary element on the carrier, the main active element are Rh and/or Ru, the auxiliary agent
Element is selected from Sm, Eu and Yb, and the carrier is selected from activated carbon, Al2O3And SiO2。
According to the second aspect of the invention, the invention provides the hydrogenation catalyst work according to one side of the invention
Catalyst application for phthalic acid dibasic ester Hydrogenation for hexamethylene -1,2- cyclohexanedimethanodibasic dibasic esters.
According to the third aspect of the present invention, the invention provides a kind of preparation of hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester
Method, this method are included under hydrogenation conditions, by the raw mixture containing phthalic acid dibasic ester and hydrogen with adding
Hydrogen catalyst contacts in the reactor, wherein, the hydrogenation catalyst is the hydrogenation catalyst described in one side of the invention.
According to the fourth aspect of the present invention, the invention provides a kind of preparation of hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester
Method, this method comprise the following steps：
(1) first hydrogenation step, in the first hydrogenation step, hydrogen is sent into the raw material containing phthalic acid dibasic ester
In liquid, the first gas-liquid mixture is formed, first gas-liquid mixture is sent into and is filled with the first anti-of the first hydrogenation catalyst
Answer in device, and under the first hydrogenation conditions, first gas-liquid mixture is contacted with first hydrogenation catalyst, obtain
Reaction solution after to the first hydrogenation；
(2) second hydrogenation steps, in the second hydrogenation step, reacted after the first hydrogen make-up is sent into first hydrogenation
In liquid, the second gas-liquid mixture is formed, second gas-liquid mixture is sent into and is filled with the second anti-of the second hydrogenation catalyst
Answer in device, and under the second hydrogenation conditions, second gas-liquid mixture is contacted with second hydrogenation catalyst, obtain
Reaction solution after to the second hydrogenation；
(3) the 3rd hydrogenation steps, in the 3rd hydrogenation step, reacted after the second hydrogen make-up is sent into second hydrogenation
In liquid, the 3rd gas-liquid mixture is formed, the 3rd gas-liquid mixture is sent into and is filled with the 3rd anti-of the 3rd hydrogenation catalyst
Answer in device, and under the 3rd hydrogenation conditions, the 3rd gas-liquid mixture is contacted with the 3rd hydrogenation catalyst, obtain
To the mixed liquor containing hexamethylene -1,2- cyclohexanedimethanodibasic dibasic esters；
Wherein, first hydrogenation catalyst, the second hydrogenation catalyst and the 3rd hydrogenation catalyst are respectively the present invention the
Catalyst described in one side.
Higher high active of hydrogenation catalysis is had according to the hydrogenation catalyst of the present invention, added as phthalic acid dibasic ester
When hydrogen prepares the catalyst of hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester, also showed that under relatively low reaction temperature higher
Catalytic activity, higher feed stock conversion and selectivity of product can be obtained.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is used for a kind of preferred embodiment of the schematically air and liquid mixer that the explanation present invention uses.
Fig. 2 is used to illustrate a kind of preferred embodiment according to the 4th aspect methods described of the present invention.
Description of reference numerals
1：For abutting gas passage and the component of fluid passage
2：Housing 3：Gas access
4：Liquid inlet 5：Liquid outlet
11：Pump 21：First air and liquid mixer
22：Second air and liquid mixer 23：3rd air and liquid mixer
31：First reactor 32：Second reactor
33：3rd reactor 41：Pipeline
42：Pipeline 43：Pipeline
44：Pipeline 51：High pressure knockout drum
52：Liquid phase stream 53：Gas
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
According to the first aspect of the invention, the invention provides a kind of hydrogenation catalyst, the catalyst contain carrier with
And the main active element and auxiliary element of load on the carrier.
The main active element is Rh and/or Ru.
The auxiliary element is selected from Sm, Eu and Yb.
Load capacity of the main active element on carrier can be Conventional selective.Usually, with the hydrogenation catalyst
On the basis of the total amount of agent, the content of the main active element in terms of element can be 0.05-8 weight %, preferably 0.1-5 weights
Measure %.
The content of the auxiliary element can be selected according to the content of main active element.With the hydrogenation catalyst
On the basis of total amount, the content of the auxiliary element in terms of element can be 0.05-8 weight %, preferably 0.1-5 weight %.
It is described in terms of element from the angle for further improving the catalytic activity of the hydrogenation catalyst at low temperature
The mol ratio of auxiliary element and the main active element is preferably 0.01-8：1, more preferably 0.03-6：1.
According to the hydrogenation catalyst of the present invention, the carrier is selected from activated carbon, Al2O3And SiO2.The activated carbon, Al2O3
And SiO2Source be not particularly limited, can be various sources the carrier for being adapted as loaded catalyst activated carbon,
Al2O3And SiO2。
Conventional method can be used to prepare according to the hydrogenation catalyst of the present invention.Specifically, the catalyst can use
Combination more than one or both of the precipitation method, infusion process, hydrothermal synthesis method is made.
In a preferred embodiment, the hydrogenation catalyst is prepared using dipping method.This method includes following
Step：
(1) water soluble compound containing main active element and the water soluble compound containing auxiliary element are dispersed in
In water, maceration extract is formed；
(2) with the maceration extract impregnated carrier；
(3) carrier through dipping is contacted with reducing agent, by the water soluble compound containing main active element with
And the compound reduction containing auxiliary element.
The species of the water soluble compound containing main active element is not particularly limited, and its instantiation can include
But it is not limited to：It is more than one or both of radium chloride, ruthenic chloride, rhodium nitrate, nitric acid ruthenium, rhodium acetate and ruthenium acetate.
The water soluble compound containing auxiliary element can be conventional selection, such as can be chloride and/or nitre
Hydrochlorate.
The dipping can be carried out under normal conditions.Usually, dipping can be in environment temperature, such as 10-60 DEG C of temperature
Degree is lower to be carried out.
The reducing agent can be it is common it is various be enough the water soluble compound containing main active element and
The water soluble compound reduction containing auxiliary element turns into the reducing substances of corresponding metallic element.Preferably, it is described
Reducing agent is the combination more than one or both of hydrazine hydrate, sodium borohydride and formaldehyde.
The reduction can be carried out under normal conditions, reduction reaction can be made to be defined.Usually, the reduction can
To be carried out at a temperature of 20-80 DEG C, carried out preferably at a temperature of 30-60 DEG C.The duration of the reduction reaction is with energy
By the water soluble compound containing main active element and the water soluble compound reduction containing auxiliary element or base
This reduction is defined.Usually, the duration of the reduction reaction can be 1-10 hours, preferably 4-6 hours.
Reducing obtained hydrogenation catalyst can be dried under normal conditions, to remove solvent therein.Usually,
The drying can be carried out at a temperature of 40-150 DEG C, be carried out preferably at a temperature of 50-120 DEG C.The drying continues
Time can be selected according to the temperature being dried, so that solvent removal therein or basic removing can be defined.Usually,
The duration of the drying can be 8-24 hours, preferably 12-20 hours.The drying can enter in air atmosphere
OK, can also be carried out in non-oxidizing atmosphere, the non-oxidizing atmosphere such as nitrogen atmosphere and/or group 0 element atmosphere
(such as argon gas).When being dried in air atmosphere, the drying is preferably carried out at a temperature of no more than 100 DEG C, such as in 40-
Carried out at a temperature of 80 DEG C.The drying can be carried out under normal pressure (that is, 1 standard atmospheric pressure), can also be in the condition of decompression
Lower progress, is not particularly limited.
According to the hydrogenation catalyst of the present invention before use, reduction work can be carried out in reactor using conventional method
Change.For example, it can be reduced at reducing atmosphere (such as under hydrogen atmosphere) at a temperature of 20-80 DEG C, preferably 30-60 DEG C.
Higher high active of hydrogenation catalysis is had according to the hydrogenation catalyst of the present invention, added as phthalic acid dibasic ester
During the catalyst of hydrogen reaction, under relatively low reaction temperature, higher catalytic activity can be also obtained.
Thus, according to the second aspect of the invention, the invention provides the hydrogenation described in one side of the invention to urge
Agent prepares the application of the catalyst of hexamethylene -1,2- cyclohexanedimethanodibasic dibasic esters as phthalic acid dibasic ester.
According to the third aspect of the present invention, the invention provides a kind of preparation of hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester
Method, this method are included under hydrogenation conditions, by the raw mixture containing phthalic acid dibasic ester and hydrogen with adding
Hydrogen catalyst contacts in the reactor.
Method according to third aspect of the present invention, the hydrogenation catalyst are described in one side of the invention
Hydrogenation catalyst.The hydrogenation catalyst has been carried out being described in detail above, is this time no longer described in detail.
Method according to third aspect of the present invention, conventional method can be used by hydrogen and contain phthalic acid
The material liquid mixing of dibasic ester, so as to obtain the raw mixture.For example, by hydrogen and adjacent benzene can be contained in a mixer
The material liquid mixing of cyclohexanedimethanodibasic dibasic ester, the blender can be one or both of dynamic mixer, static mixer
Combination above.Gas is well mixed by the static mixer by changing the flow regime of fluid to realize with liquid, tool
Body can be but be not limited to SV types static mixer, SK types static mixer, SX types static mixer, SH types static mixer and
One or more in SL type static mixers.The dynamic mixer can be realized for the various motions by moving component will
The mixing apparatus that gas is well mixed with liquid, the moving component for example can be the common various portions with agitating function
Part.
Selectivity of product and the angle of feed stock conversion are improved from further, in a preferred embodiment,
Hydrogen is injected in the material liquid by a kind of air and liquid mixer, so as to obtain the raw mixture, the gas-liquid mixed
Device includes at least one fluid passage for being used to accommodate the material liquid and at least one gas for being used to accommodate the hydrogen leads to
Road, is abutted between the fluid passage and the gas passage by a component, and the component at least partially has porose area, institute
State hydrogen has porose area to be injected into the material liquid by described.
In the present invention, term " fluid passage " is the space for referring to accommodate liquid phase stream；Term " gas passage " refers to
The space of hydrogen can be accommodated.
The component at least partially has porose area, the length direction extension for having porose area along the component.Preferably,
It is described to there is porose area to cover whole component (that is, by with the average pore size between described fluid passage and the gas passage
For the component adjoining in the hole of nano-scale, the hydrogen is injected into by the hole in the liquid phase stream).It is described to have hole
Area has the hole that the average pore size is nano-scale, so that hydrogen passes through the hole quilt with average pore size for nano-scale
Inject in the liquid phase stream.
In the preferred embodiment, the hole having in porose area can be micron openings and/or nano-pore.The present invention
In, term " micron openings " refers to that average pore size is more than 1000nm hole, and the average pore size of the micron openings is preferably not greater than 20 μ
M, more preferably not more than 15 μm, more preferably no more than 10 μm.In the present invention, term " nano-pore " refers to average pore size
Hole no more than 1000nm, such as the hole that average pore size is 1nm to 1000nm.It is highly preferred that the hole having in porose area is nanometer
Hole.It is further preferred that the average pore size for having the hole in porose area is 30nm to 1000nm.It is it is further preferred that described
The average pore size for having the hole in porose area is 30nm to 800nm, is such as 50nm to 800nm.The average pore size uses ESEM
Method determines.
In the preferred embodiment, the component can be perforated membrane, porous plate and void channels in one kind or
Two or more combinations.The void channels refer to that the wall of passage is porous.The inner surface of the void channels and/or outer
Surface can adhere to perforated membrane, and so the aperture in the hole on pipeline can be adjusted, such as：Hole on the wall of the pipeline
Can be micron openings, be attached to hole on the perforated membrane on the inner surface and/or outer surface of the pipeline can be with nano-pore, this hair
In bright, the pipeline that the perforated membrane that hole therein is nano-pore is attached with inner surface and/or outer surface has been also considered as in porose area
Hole be nano-pore.As an example of the pipeline with perforated membrane, the void channels can be membrane tube.The antipriming pipe
The quantity of passage in road is not particularly limited, and usually, the quantity of the passage in the void channels can be 4-20 bars.
In actual mechanical process, the component and a housing can be used cooperatively, so as to form the gas-liquid mixed
Device.The housing is internally provided with least one component, and the inner space of the housing is separated into liquid by the component
Body passage and gas passage.The housing has gas access, liquid inlet and liquid outlet, the both ends point of the fluid passage
Do not connected with the liquid inlet and the liquid outlet, the gas passage connects with the gas access.Fig. 1 shows institute
State a kind of preferred embodiment of air and liquid mixer.As shown in figure 1, component 1 (component in Fig. 1 is void channels) can be with shell
Body 2 is used cooperatively.That is, at least one component 1 is placed in housing 2, and makes to deposit between the outer wall of component 1 and the inwall of housing 2
In space.By the passage that component 1 surrounds as accommodating the fluid passage of liquid phase stream, the outer wall of component 1 is interior with housing 2
The space that wall is formed is as the gas passage for accommodating hydrogen；Or the passage that component 1 surrounds is as accommodating hydrogen
Gas passage, the outer wall of component 1 is with the space that the inwall of housing 2 is formed as the fluid passage for accommodating liquid phase stream.It is excellent
Selection of land, the passage surrounded of component 1 is as the fluid passage for accommodating liquid phase stream, the outer wall of component 1 and the inwall of housing 2
The space of formation is as the gas passage for accommodating hydrogen.
In the passage that the component surrounds as the fluid passage for accommodating liquid phase stream, the outer wall of the component and institute
When stating the space of the inwall formation of housing as being used to accommodate the gas passage of hydrogen, as shown in figure 1, can be set on housing 2
Put gas access 3, liquid inlet 4 and liquid outlet 5, the both ends of the fluid passage respectively with liquid inlet 3 and liquid outlet 5
Connection, the gas passage connect with gas access 3.Hydrogen is sent into housing 2 by gas access 3, liquid phase stream is sent
In the passage for entering component 1, in the presence of pressure differential, hydrogen is set to enter by the hole on tube wall in the liquid phase stream, so as to
Obtain hydrogeneous liquid phase stream.
The material for forming the component can be inorganic material (such as inorganic ceramic), or organic material, as long as shape
With hydrogen and liquid phase stream chemical interaction does not occur for the material into the component.
In the preferred embodiment, the air and liquid mixer can be arranged on to the arrival end of the reactor, so as to
The raw mixture that air and liquid mixer exports is sent directly into reactor.
Method according to third aspect of the present invention, the injection rate of hydrogen can be according to the O-phthalic in material liquid
The content of sour dibasic ester is selected, to be enough diethyl phthalate hydrogenation being defined.As an example, before use
When literary preferred embodiment methods described injects hydrogen in the material liquid by a kind of air and liquid mixer, the injection rate of hydrogen
Mol ratio with the phthalic acid dibasic ester in the material liquid can be 3-15：1.Preferably, the injection rate of hydrogen and institute
The mol ratio for stating the phthalic acid dibasic ester in material liquid is 3.2-7：1, such as 3.2：1、3.3：1、3.4：1、3.5：1、3.6：
1、3.7：1、3.8：1、3.9：1、4：1、4.1：1、4.2：1、4.3：1、4.4：1、4.5：1、4.6：1、4.7：1、4.8：1、4.9：
1、5：1、5.1：1、5.2：1、5.3：1、5.4：1、5.5：1、5.6：1、5.7：1、5.8：1、5.9：1、6：1、6.1：1、6.2：1、
6.3：1、6.4：1、6.5：1、6.6：1、6.7：1、6.8：1、6.9：1、7：1.It is highly preferred that in preferred embodiment described previously
In, when to have the hole in porose area be nano-pore, the injection rate of hydrogen can be further reduced, now the injection rate of hydrogen and the original
The mol ratio of phthalic acid dibasic ester in feed liquid is preferably 3.5-5.5：1.
Method according to third aspect of the present invention, by using the hydrogenation catalyst of the present invention, even in relatively low
At a temperature of by hydrogen and phthalic acid dibasic ester and hydrogenation catalyst haptoreaction, also can by phthalic acid dibasic ester with
Higher conversion, and the selectivity to hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester can be significantly improved.Specifically, can be with
Hydrogen and phthalic acid dibasic ester are contacted at a temperature of 35-100 DEG C with hydrogenation catalyst.Preferably, by hydrogen
Contacted with phthalic acid dibasic ester with hydrogenation catalyst at a temperature of 40-85 DEG C, such as 40 DEG C, 41 DEG C, 42 DEG C, 43
℃、44℃、45℃、46℃、47℃、48℃、49℃、50℃、51℃、52℃、53℃、54℃、55℃、56℃、57℃、58
℃、59℃、60℃、61℃、62℃、63℃、64℃、65℃、66℃、67℃、68℃、69℃、70℃、71℃、72℃、73
℃、74℃、75℃、76℃、77℃、78℃、79℃、80℃、81℃、82℃、83℃、84℃、85℃.In an example,
Hydrogen and phthalic acid dibasic ester are contacted at a temperature of 60-70 DEG C with hydrogenation catalyst.In another example,
Hydrogen and phthalic acid dibasic ester are contacted at a temperature of 50-60 DEG C with hydrogenation catalyst.In another example,
Hydrogen and phthalic acid dibasic ester are contacted at a temperature of 40-50 DEG C with hydrogenation catalyst.In another example,
Hydrogen and phthalic acid dibasic ester are contacted at a temperature of 70-85 DEG C with hydrogenation catalyst.
Method according to third aspect of the present invention, can be at lower pressures by hydrogen and phthalic acid two
First ester contacts with hydrogenation catalyst.Specifically, in terms of gauge pressure, the pressure in reactor can be 0.4-9MPa.Preferably, with table
Pressure meter, the pressure in reactor is 0.5-7MPa, as 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa,
1.1MPa、1.2MPa、1.3MPa、1.4MPa、1.5MPa、1.6MPa、1.7MPa、1.8MPa、1.9MPa、2MPa、2.1MPa、
2.2MPa、2.3MPa、2.4MPa、2.5MPa、2.6MPa、2.7MPa、2.8MPa、2.9MPa、3MPa、3.1MPa、3.2MPa、
3.3MPa、3.4MPa、3.5MPa、3.6MPa、3.7MPa、3.8MPa、3.9MPa、4MPa、4.1MPa、4.2MPa、4.3MPa、
4.4MPa、4.5MPa、4.6MPa、4.7MPa、4.8MPa、4.9MPa、5MPa、5.1MPa、5.2MPa、5.3MPa、5.4MPa、
5.5MPa、5.6MPa、5.7MPa、5.8MPa、5.9MPa、6MPa、6.1MPa、6.2MPa、6.3MPa、6.4MPa、6.5MPa、
6.6MPa、6.7MPa、6.8MPa、6.9MPa、7MPa.In an example, in terms of gauge pressure, the pressure in reactor is 1-
7MPa.In another example, in terms of gauge pressure, the pressure in reactor is 3-5MPa.
Method according to third aspect of the present invention, the hydrogenation catalyst of use show that higher hydrogenation catalyst is lived
Property, also can be with higher feed space velocity, effectively by phthalic acid binary at relatively low temperature and relatively low pressure
Ester hydrogenation, and obtain higher selectivity of product.Specifically, the heavy space-time of the raw mixture in terms of phthalic acid dibasic ester
Speed can be 0.5-16h-1, such as 0.5h-1、1h-1、1.5h-1、2h-1、2.5h-1、3h-1、3.5h-1、4h-1、4.5h-1、5h-1、5.5h-1、6h-1、6.5h-1、7h-1、7.5h-1、8h-1、8.5h-1、9.5h-1、10h-1、10.5h-1、11h-1、11.5h-1、12h-1、12.5h-1、13h-1、13.5h-1、14h-1、14.5h-1、15h-1、15.5h-1、16h-1.Preferably, the original in terms of phthalic acid dibasic ester
The weight (hourly) space velocity (WHSV) for expecting mixture is 1-12h-1。
Method according to third aspect of the present invention, can be by hydrogen and phthalic acid dibasic ester and hydrogenation catalyst
Agent is contacted in common various reactors.In a preferred embodiment, by hydrogen and phthalic acid binary
Ester is contacted with hydrogenation catalyst in fixed bed reactors, and it is anti-now the hydrogenation catalyst can be seated in into fixed bed
Answer in device, will be sent into containing the raw mixture of hydrogen and phthalic acid dibasic ester in fixed bed reactors, with hydrogenation catalyst
Agent contacts.In the preferred embodiment, when using previously described air and liquid mixer to form the raw mixture,
The air and liquid mixer can be arranged on to the arrival end of the fixed bed reactors.In the preferred embodiment, from entering
The angle that one step improves hydrogenation reaction effect is set out, and is preferably sent into the raw mixture in a manner of from bottom to top described anti-
Answer in device.
Method according to third aspect of the present invention, the phthalic acid dibasic ester can be conventional selection.Tool
Body, the phthalic acid dibasic ester can be combination more than one or both of compound shown in Formulas I,
In Formulas I, R1And R2Respectively C1-C12Alkyl, as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl,
Isobutyl group, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, isohesyl, n-heptyl, different heptyl, n-octyl, iso-octyl, positive decyl,
Isodecyl, n-undecane base, 1- methyldecyls, dodecyl or 1- methylundecyls.
In Formulas I, R1And R2It is preferred that it is respectively C4-C10Alkyl, more preferably respectively C6-C10Alkyl, it is further preferably each
From for C7-C10Alkyl.
The instantiation of the phthalic acid dibasic ester can include but is not limited to：N-butyl phthalate, neighbour
Group more than one or both of the isodecyl ester of phthalic acid two, diisooctyl phthalate and diisononyl phthalate
Close.
Method according to third aspect of the present invention, the raw mixture can contain solvent, can also be free of
There is solvent.In one embodiment, the raw mixture does not contain solvent, can now effectively improve the effective of device
Treating capacity.In another embodiment, the raw mixture also contains at least one solvent, now can be to reaction rate
It is adjusted.The solvent can be conventional selection.Usually, the solvent can be that can dissolve the adjacent benzene two as raw material
The liquid substance of formic acid dibasic ester and hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester as product, such as alcohol system can be used molten
Agent, can also use corresponding hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester as solvent (now preferably as solvent hexamethylene -
1,2- cyclohexanedimethanodibasic dibasic ester and hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester as product are preferably identical), it can also use above-mentioned
The mixture of two kinds of solvents.The instantiation of the alcohol series solvent can include but is not limited to isooctanol, isoamyl alcohol, isononyl alcohol,
Combination more than one or both of isodecanol, carbon undecyl alcohol and carbon lauryl alcohol.The dosage of the solvent can be conventional choosing
Select.Usually, the dosage of the solvent can make it that the content of phthalic acid dibasic ester in the raw mixture is 5-99
Weight %, preferably 6-80 weight %, more preferably 8-70 weight %, more preferably 10-60 weight %, such as 10-50 weights
Measure %.
Method according to third aspect of the present invention, what is be prepared contains hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester
Mixed liquor can directly export, such as：Be free of solvent in material liquid, or the solvent be the hexamethylene consistent with product-
During 1,2- cyclohexanedimethanodibasic dibasic ester, the mixed liquor that directly can be obtained the 3rd reactor exports；The normal of this area can also be used
The mixed liquor that rule method exports to the 3rd reactor is handled, such as removes solvent therein (such as alcohol series solvent)；Can be with
By the mixed liquor containing hexamethylene -1,2- cyclohexanedimethanodibasic dibasic esters being prepared further using described in third aspect of the present invention
Method carry out once, above hydrotreating twice or thrice, further to improve the conversion ratio of phthalic acid dibasic ester.
According to the fourth aspect of the present invention, invention further provides a kind of hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester
Preparation method, this method comprises the following steps：
(1) first hydrogenation step, in the first hydrogenation step, hydrogen is sent into the raw material containing phthalic acid dibasic ester
In liquid, the first gas-liquid mixture is formed, first gas-liquid mixture is sent into and is filled with the first anti-of the first hydrogenation catalyst
Answer in device, and under the first hydrogenation conditions, first gas-liquid mixture is contacted with first hydrogenation catalyst, obtain
Reaction solution after to the first hydrogenation；
(2) second hydrogenation steps, in the second hydrogenation step, reacted after the first hydrogen make-up is sent into first hydrogenation
In liquid, the second gas-liquid mixture is formed, second gas-liquid mixture is sent into and is filled with the second anti-of the second hydrogenation catalyst
Answer in device, and under the second hydrogenation conditions, second gas-liquid mixture is contacted with second hydrogenation catalyst, obtain
Reaction solution after to the second hydrogenation；
(3) the 3rd hydrogenation steps, in the 3rd hydrogenation step, reacted after the second hydrogen make-up is sent into second hydrogenation
In liquid, the 3rd gas-liquid mixture is formed, the 3rd gas-liquid mixture is sent into and is filled with the 3rd anti-of the 3rd hydrogenation catalyst
Answer in device, and under the 3rd hydrogenation conditions, the 3rd gas-liquid mixture is contacted with the 3rd hydrogenation catalyst, obtain
To the mixed liquor containing hexamethylene -1,2- cyclohexanedimethanodibasic dibasic esters；
Wherein, first hydrogenation catalyst, second hydrogenation catalyst and the 3rd hydrogenation catalyst are respectively
Catalyst described in one side of the invention.
In third aspect of the present invention methods described, in " the first ×× ", " the second ×× " and " the 3rd ×× " " the
One ", " second " and " the 3rd " is only used for the method for more clearly illustrating the present invention, has no other restriction effects.
The hydrogenation catalyst and its composition have been carried out being described in detail above, are no longer described in detail herein.According to this
The method described in the 4th aspect is invented, from the further suitable inverse ratio for improving selectivity of product, particularly further improving product
Angle set out, the carrier of first hydrogenation catalyst is preferably SiO2And/or Al2O3, more preferably Al2O3；Described second
The carrier of hydrogenation catalyst and the 3rd hydrogenation catalyst is respectively activated carbon and/or SiO2, the load of second hydrogenation catalyst
Body is more preferably SiO2, the carrier of the 3rd hydrogenation catalyst is more preferably activated carbon.
In first hydrogenation step, the second hydrogenation step and the 3rd hydrogenation step, by the method in hydrogen injection liquid phase stream
Have been carried out being described in detail in third aspect of the present invention methods described, be no longer described in detail herein.According to the present invention the 4th
Method described in individual aspect, can be first when using previously described air and liquid mixer by hydrogen injection liquid phase stream
The arrival end of reactor, second reactor and the 3rd reactor each sets at least one air and liquid mixer.
According to the method described in the 4th aspect of the present invention, the dosage of hydrogen is with can be by the phthalic acid two in material liquid
First ester hydrogenation is defined.It can be selected according to the content of phthalic acid dibasic ester in the feeding mode and material liquid of hydrogen
Select.
In a preferable example, it is sent into the hydrogen in the material liquid, the first hydrogen make-up and the material liquid
The mol ratio of phthalic acid dibasic ester is 0.8-3：0.5-2.5：1.From the further angle for improving feed stock conversion, send
Entering the hydrogen in the material liquid, the first hydrogen make-up and the mol ratio of phthalic acid dibasic ester in the material liquid is preferably
1-2.8：0.8-2.2：1, more preferably 1.1-2.5：1-2：1, more preferably 1.2-2.2：1.1-2：1.In the 3rd hydrogenation
In step, the second hydrogen make-up and the volume ratio of the material liquid are preferably 3-80, are so advantageous in high-pressure separation apparatus
The mixed liquor containing hexamethylene -1,2- cyclohexanedimethanodibasic dibasic esters that 3rd hydrogenation step exports is separated.In the 3rd hydrogenation step
In rapid, the second hydrogen make-up and the volume ratio of the material liquid are more preferably 5-60.
According to the method described in the 4th aspect of the present invention, the first hydrogenation step, the second hydrogenation step and the 3rd hydrogenation step
In rapid, the temperature that gas-liquid mixture contacts with hydrogenation catalyst can be 35-100 DEG C, preferably 40-85 DEG C.First hydrogenation step
Suddenly, in the second hydrogenation step and the 3rd hydrogenation step, in terms of gauge pressure, the pressure in reactor can be 0.4-9MPa, be preferably
0.5-7MPa.In an example, in terms of gauge pressure, the pressure in reactor is 3MPa.In another example, in terms of gauge pressure,
Pressure in reactor is 5MPa.In another example, in terms of gauge pressure, the pressure in reactor is 7MPa.In another reality
In example, in terms of gauge pressure, the pressure in reactor is 0.5MPa.
From the further angle for improving selectivity of product, the first hydrogenation step, the second hydrogenation step and the 3rd hydrogenation
The temperature of step is in the trend gradually risen.That is, the temperature contacted in the first hydrogenation step is less than in the second hydrogenation step
The temperature contacted, the temperature contacted in the second hydrogenation step are less than the temperature contacted in the 3rd hydrogenation step.
Specifically, in the first hydrogenation step, the contact can be carried out at a temperature of 35-80 DEG C, such as 35 DEG C, 36 DEG C,
37℃、38℃、39℃、40℃、41℃、42℃、43℃、44℃、45℃、46℃、47℃、48℃、49℃、50℃、51℃、52
℃、53℃、54℃、55℃、56℃、57℃、58℃、59℃、60℃、61℃、62℃、63℃、64℃、65℃、66℃、67
℃、68℃、69℃、70℃、71℃、72℃、73℃、74℃、75℃、76℃、77℃、78℃、79℃、80℃.First hydrogenation
In step, the contact is carried out preferably at a temperature of 40-70 DEG C.In second hydrogenation step, the contact can be at 40-90 DEG C
At a temperature of carry out, such as 40 DEG C, 41 DEG C, 42 DEG C, 43 DEG C, 44 DEG C, 45 DEG C, 46 DEG C, 47 DEG C, 48 DEG C, 49 DEG C, 50 DEG C, 51 DEG C, 52
℃、53℃、54℃、55℃、56℃、57℃、58℃、59℃、60℃、61℃、62℃、63℃、64℃、65℃、66℃、67
℃、68℃、69℃、70℃、71℃、72℃、73℃、74℃、75℃、76℃、77℃、78℃、79℃、80℃、81℃、82
℃、83℃、84℃、85℃、86℃、87℃、88℃、89℃、90℃.In second hydrogenation step, the contact is preferably in 50-85
Carry out at a temperature of DEG C, connect it is highly preferred that the temperature contacted described in the second hydrogenation step is higher than described in the first hydrogenation step
Tactile temperature.In 3rd hydrogenation step, the contact can be carried out at a temperature of 50-100 DEG C, such as 50 DEG C, 51 DEG C, 52 DEG C,
53℃、54℃、55℃、56℃、57℃、58℃、59℃、60℃、61℃、62℃、63℃、64℃、65℃、66℃、67℃、68
℃、69℃、70℃、71℃、72℃、73℃、74℃、75℃、76℃、77℃、78℃、79℃、80℃、81℃、82℃、83
℃、84℃、85℃、86℃、87℃、88℃、89℃、90℃、91℃、92℃、93℃、94℃、95℃、96℃、97℃、98
℃、99℃、100℃.In 3rd hydrogenation step, the contact is carried out preferably at a temperature of 60-85 DEG C, more preferably in 70-85
Carried out at a temperature of DEG C, it is highly preferred that the temperature contacted described in the 3rd hydrogenation step is higher than institute in the second hydrogenation step
State the temperature of contact.
According to the present invention the 4th aspect described in method, using the total amount of phthalic acid dibasic ester in the material liquid as
Benchmark, the weight (hourly) space velocity (WHSV) of first gas-liquid mixture and the second gas-liquid mixture can be each 0.5-16h-1, such as 0.5h-1、
1h-1、1.5h-1、2h-1、2.5h-1、3h-1、3.5h-1、4h-1、4.5h-1、5h-1、5.5h-1、6h-1、6.5h-1、7h-1、7.5h-1、8h-1、8.5h-1、9.5h-1、10h-1、10.5h-1、11h-1、11.5h-1、12h-1、12.5h-1、13h-1、13.5h-1、14h-1、14.5h-1、15h-1、15.5h-1、16h-1.On the basis of the total amount of phthalic acid dibasic ester in the material liquid, first gas-liquid is mixed
The weight (hourly) space velocity (WHSV) of compound and the second gas-liquid mixture is respectively preferably 0.8-12h-1, more preferably 1-10h-1.3rd gas-liquid
The weight (hourly) space velocity (WHSV) of mixture can be 2-16h-1, preferably 4-15h-1, more preferably 5-9h-1。
According to the method described in the 4th aspect of the present invention, from the further angle for improving hydrogenation reaction effect, institute
The feeding manner for stating first reactor, second reactor and the 3rd reactor is preferably from bottom to top.
According to the method described in the 4th aspect of the present invention, the phthalic acid dibasic ester can be conventional selection.Tool
Body, the phthalic acid dibasic ester can be combination more than one or both of compound shown in Formulas I,
In Formulas I, R1And R2Respectively C1-C12Alkyl, such as：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding
Base, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, isohesyl, n-heptyl, different heptyl, n-octyl, iso-octyl, the positive last of the ten Heavenly stems
Base, isodecyl, n-undecane base, 1- methyldecyls, dodecyl or 1- methylundecyls.
In Formulas I, R1And R2It is preferred that it is respectively C4-C10Alkyl, more preferably respectively C6-C10Alkyl, it is further preferably each
From for C7-C10Alkyl.
The instantiation of the phthalic acid dibasic ester can include but is not limited to：N-butyl phthalate, neighbour
Group more than one or both of the isodecyl ester of phthalic acid two, diisooctyl phthalate and diisononyl phthalate
Close.
According to the method described in the 4th aspect of the present invention, the material liquid can contain solvent, can also not contain molten
Agent.In one embodiment, the material liquid does not contain solvent, can now improve the effective treating capacity of device.Another
In kind embodiment, the material liquid also contains at least one solvent, and now reaction rate can be adjusted.The solvent
It can be conventional selection.Usually, the solvent can be that can dissolve the phthalic acid dibasic ester and work as raw material
For the liquid substance of hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester of product, such as alcohol series solvent can be used, can also used corresponding
Hexamethylene -1,2- cyclohexanedimethanodibasic dibasic esters as solvent (now preferably as solvent hexamethylene -1,2- cyclohexanedimethanodibasic dibasic esters with
Hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester as product is preferably identical), can also be using the mixture of above two solvent.
The instantiation of the alcohol series solvent can include but is not limited to isooctanol, isoamyl alcohol, isononyl alcohol, isodecanol, carbon undecyl alcohol and
Combination more than one or both of carbon lauryl alcohol.The dosage of the solvent can be conventional selection.Usually, the solvent
Dosage can cause the content of phthalic acid dibasic ester in the material liquid for 5-99 weight %, preferably 6-80 weights
%, more preferably more preferably 8-70 weight %, 10-60 weight % are measured, such as 10-50 weight %.
According to the method described in the 4th aspect of the present invention, what is be prepared contains hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester
Mixed liquor can directly export, such as：Be free of solvent in material liquid, or the solvent be the hexamethylene consistent with product-
During 1,2- cyclohexanedimethanodibasic dibasic ester, the mixed liquor that directly can be obtained the 3rd reactor exports；The normal of this area can also be used
The mixed liquor that rule method exports to the 3rd reactor is handled, such as removes solvent therein (such as alcohol series solvent).
According to the method described in the 4th aspect of the present invention, reaction temperature can not only be effectively reduced, and can substantially carry
High product selectivity, particularly can obtain higher cis hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester selectively (can for 95% with
On, preferably more than 98%, it might even be possible to be more than 99%), while higher feed stock conversion can also be obtained, from the 3rd reaction
Mass content in the reaction solution exported in device as the phthalic acid dibasic ester of raw material can be below 10ppm, generally
Below 6ppm.
Fig. 2 shows a kind of preferred embodiment of the method according to the 4th aspect of the present invention, below in conjunction with
The embodiment is described in detail Fig. 2.
In Fig. 2, the first air and liquid mixer 21, the second air and liquid mixer 22 and the 3rd air and liquid mixer 23 are described previously
Air and liquid mixer (air and liquid mixer as shown in Figure 1), there is gas passage and fluid passage.As shown in Fig. 2 material liquid leads to
Cross pump 11 to be pumped in the fluid passage of the first air and liquid mixer 21, while hydrogen is sent into the first gas-liquid mixed by pipeline 41
In the gas passage of device 21, so that by the porous region on the component of adjacent fluid passage and gas passage, hydrogen injection is former
In feed liquid, the first gas-liquid mixture is formed.First gas-liquid mixture of the first air and liquid mixer output is in a manner of flowing up
Into in first reactor 31, contacted with the first hydrogenation catalyst being seated in first reactor 31 (wherein, first hydrogenation urge
The carrier of agent is preferably SiO2And/or Al2O3), obtain reaction solution after the first hydrogenation.Reaction solution after first hydrogenation is sent into the
In the fluid passage of two air and liquid mixers 22, while the first hydrogen make-up is sent into by the second air and liquid mixer 22 by pipeline 42
In gas passage, and it will be reacted by the component of adjacent fluid passage and gas passage after the first hydrogen make-up the first hydrogenation of injection
In liquid, the second gas-liquid mixture is formed.Second gas-liquid mixture is sent into a manner of flowing up in second reactor 32, with
Be seated in second reactor 32 the second hydrogenation catalyst (carrier of the second hydrogenation catalyst be preferably activated carbon and/or
SiO2, more preferably SiO2) contact, obtain reaction solution after the second hydrogenation.Reaction solution after second hydrogenation is sent into the 3rd gas-liquid mixed
In the fluid passage of device 23, at the same by pipeline 43 by the second hydrogen make-up be sent into the 3rd air and liquid mixer 23 gas passage
In, and by the component of adjacent fluid passage and gas passage by reaction solution after the second hydrogen make-up the second hydrogenation of injection, shape
Into the 3rd gas-liquid mixture.3rd gas-liquid mixture is sent into a manner of flowing up in the 3rd reactor 33, with filling
In the 3rd reactor 33 the 3rd hydrogenation catalyst (carrier of the 3rd hydrogenation catalyst be preferably activated carbon and/or
SiO2, more preferably activated carbon) and contact, obtain the mixed liquor containing hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester.By the 3rd reactor
The mixed liquor of output is sent into high pressure knockout drum 51 and carries out gas-liquid separation, wherein, sent by pipeline 44 into high pressure knockout drum 51
Enter hydrogen, to supplement the pressure in high pressure knockout drum 51.The liquid phase stream 53 that high pressure knockout drum 51 is isolated is used as hydrogenation products
It can directly export, can also be sent into follow-up refining step and be refined, a small amount of gas 52 isolated can be sent into tail gas
Handled in system.
According to the present invention the 4th aspect described in method, compared with existing phthalic acid dibasic ester method of hydrotreating,
Have the following advantages that：
(1) hydrogenation conditions relax, and can be effectively reduced reaction temperature, and can grasp at lower pressures
Make；
(2) hydrogen usage is small, and a large amount of recycle hydrogens need not be maintained in reactor, is effectively reduced the cost of investment and fortune of device
Row cost；
(3) more excellent hydrogenation reaction effect can be obtained, high phthalic acid binary ester conversion rate can not only be obtained
(up to 100%), and higher selectivity of product can be obtained, it can particularly obtain ＞ 95/5 suitable inverse ratio (that is, cis hexamethylene
Alkane -1,2- cyclohexanedimethanodibasic dibasic esters/trans cyclohexane -1,2- cyclohexanedimethanodibasic dibasic esters).
Describe the present invention in detail with reference to embodiments, but and be not so limited the scope of the present invention.
In following examples and comparative example, average pore size is determined using ESEM method.
In following examples and comparative example, pressure is in terms of gauge pressure.
In following examples and comparative example, using gas chromatography and proton nmr spectra (H1- NMR) method measure reactor
The composition of the reaction solution of output, and feed stock conversion and selectivity of product are calculated according to the composition data of measure.
Embodiment 1-11 is used to illustrate the present invention.
Embodiment 1
In the present embodiment, the first hydrogenation catalyst (Rh-Sm/C, containing 0.6 weight %Rh and 5.0 weight %Sm) is using following
It is prepared by method：
(1) by 1.53 grams of RhCl3·3H2O and 12.15 gram of SmCl3·6H2O is made into 100mL maceration extracts；
(2) 94.4 grams of activated carbons are placed in maceration extract, impregnated 10 hours under environment temperature (25 DEG C)；
(3) activated carbon through dipping is placed in hydrazine hydrate aqueous solution at a temperature of 50 DEG C, reacted 6 hours；
(4) solid matter is isolated in the reactant mixture obtained from step (3), and be washed with deionized 3 times, 80
Dried 12 hours in air atmosphere at a temperature of DEG C, so as to obtain the first hydrogenation catalyst.
Using with the first hydrogenation catalyst identical method prepare the second hydrogenation catalyst Ru-Eu/C (containing 2 weight %Ru and
0.1 weight %Eu), unlike, the corresponding composition for changing maceration extract.
The 3rd hydrogenation catalyst Ru-Eu/SiO is prepared using with the first hydrogenation catalyst identical method2(contain 2.8 weights
Measure %Ru and 0.8 weight %Eu), unlike, the corresponding composition and carrier for changing maceration extract.
The present embodiment prepares hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester using the method shown in Fig. 2, wherein, the gas-liquid of use
(purchased from Jiangsu, my high-tech share is limited long for perforated membrane for the component for being used for abutting gas passage and fluid passage in blender
Company), the average pore size in the hole in the perforated membrane is 100nm.Specific method is as follows.
(1) first hydrogenation step
By H2It is sent into the gas passage of the first air and liquid mixer, by the isooctanol solution of diisooctyl phthalate
(content of diisooctyl phthalate is 50 weight %) is sent into the fluid passage of the first air and liquid mixer, so as to by hydrogen
Inject in isooctanol solution, form the first gas-liquid mixture.First gas-liquid mixture is sent into first in a manner of flowing up
In reactor, contacted with the first hydrogenation catalyst being seated in first reactor, and is exported from the first hydrogenation reactor
Logistics after one hydrogenation.
(2) second hydrogenation steps
H is supplemented by first2It is sent into the gas passage of the second air and liquid mixer, the second gas is sent into logistics after the first hydrogenation
In the fluid passage of liquid mixer, so as to by logistics after the hydrogenation of the first hydrogen make-up injection first, form the second gas-liquid mixed
Thing.Second gas-liquid mixture is sent into second reactor in a manner of flowing up, be seated in second reactor
Two hydrogenation catalysts contact, and the logistics after the hydrogenation of output second from the second hydrogenation reactor.
(3) the 3rd hydrogenation steps
H is supplemented by second2It is sent into the gas passage of the 3rd air and liquid mixer, the 3rd gas is sent into logistics after the second hydrogenation
In the fluid passage of liquid mixer, so as to by logistics after the hydrogenation of the second hydrogen make-up injection second, form the 3rd gas-liquid mixed
Thing.3rd gas-liquid mixture is sent into a manner of flowing up in the 3rd reactor, be seated in the 3rd reactor
Three hydrogenation catalysts contact, and the logistics after the hydrogenation of output the 3rd from the 3rd hydrogenation reactor.
The reaction condition of each step is listed in table 1.The conversion of the composition, raw material of logistics after the hydrogenation of each reactor output
The selectivity of rate, the overall selectivity of product and cis-product is listed in table 3.
Embodiment 2
Hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester is prepared using method same as Example 1, unlike, the first hydrogenation
The carrier of catalyst is Al2O3, i.e. Rh-Sm/Al2O3(containing 0.6 weight %Rh and 5.0 weight %Sm).
Embodiment 3
Hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester is prepared using method same as Example 1, unlike, the 3rd catalysis
The carrier of agent is Al2O3, i.e. Ru-Eu/Al2O3(containing 2.8 weight %Ru and 0.8 weight %Eu).
Embodiment 4
Hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester is prepared using method same as Example 1, unlike, the second hydrogenation
The carrier of catalyst is Al2O3, i.e. Ru-Eu/Al2O3(containing 2 weight %Ru and 0.1 weight %Eu).
Comparative example 1
The first hydrogenation catalyst, the second hydrogenation catalyst and the 3rd hydrogenation are prepared using method same as Example 1 to urge
Agent, unlike, the first hydrogenation catalyst of preparation is without Sm (for Rh/C, containing 0.6 weight %Rh), the second hydrogenation of preparation
Catalyst is without Eu (for Ru/C, containing 2 weight %Ru), and the 3rd hydrogenation catalyst of preparation is without Eu (for Ru/SiO2, containing 2.8 weights
Measure %Ru).
Hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester is prepared using method same as Example 1, unlike, the first hydrogenation
Catalyst, the second hydrogenation catalyst and the 3rd hydrogenation catalyst be respectively comparative example 1 prepare the first hydrogenation catalyst, second plus
Hydrogen catalyst and the 3rd hydrogenation catalyst.
Comparative example 2
Hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester is prepared using with the identical method of comparative example 1, unlike, reaction condition
As shown in table 2.
Comparative example 3
The first hydrogenation catalyst, the second hydrogenation catalyst and the 3rd hydrogenation are prepared using method same as Example 1 to urge
Agent, unlike, in the Sm in the first hydrogenation catalyst, the Eu in the second hydrogenation catalyst and the 3rd hydrogenation catalyst
Eu with etc. the La of weight replace.
Table 1
1：The volume ratio of liquid phase stream after hydrogen and the second hydrogenation
Table 2
Table 3
Embodiment 5
In the present embodiment, the first hydrogenation catalyst (Rh-Yb/C, containing 3.0 weight %Rh and 0.5 weight %Yb) is using following
It is prepared by method：
(1) by 7.66 grams of RhCl3·3H2O and 1.12 gram of YbCl3·6H2O is made into 100mL maceration extracts；
(2) 96.5 grams of activated carbons are placed in maceration extract, impregnated 10 hours under environment temperature (30 DEG C)；
(3) activated carbon through dipping is placed in hydrazine hydrate aqueous solution, at a temperature of 55 DEG C, reacted 4 hours；
(4) solid matter is isolated in the reactant mixture obtained from step (3), and be washed with deionized 3 times,
In N at a temperature of 120 DEG C2Dried 20 hours in atmosphere, so as to obtain the first hydrogenation catalyst.
Using with the first hydrogenation catalyst identical method prepare the second hydrogenation catalyst Ru-Sm/C (containing 2 weight %Ru and
4.0 weight %Sm), unlike, the corresponding composition for changing maceration extract.
The 3rd hydrogenation catalyst Ru-Eu/Al is prepared using with the first hydrogenation catalyst identical method2O3(contain 0.9 weight
Measure %Ru and 0.3 weight %Eu), unlike, the species of the corresponding composition and carrier for changing maceration extract.
The present embodiment prepares hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester using the method shown in Fig. 2, wherein, the first gas-liquid is mixed
It is perforated membrane (purchased from Jiangsu my limited public affairs of high-tech share long to be used for the component of abutting gas passage and fluid passage in clutch
Department), the average pore size in the hole in the perforated membrane is 50nm；It is used for abutting gas passage and fluid passage in second air and liquid mixer
Component be porous sieve plate, the average pore size in the hole in the porous sieve plate is 500nm；It is used to abut gas in 3rd air and liquid mixer
The component of body passage and fluid passage is porous sieve plate, and the average pore size in the hole in the porous sieve plate is 1000nm.
(1) first hydrogenation step
By H2It is sent into the gas passage of the first air and liquid mixer, diisononyl phthalate is sent into the first gas-liquid and mixed
In the fluid passage of clutch, so as to by hydrogen injection diisononyl phthalate, form the first gas-liquid mixture.By first
Gas-liquid mixture is sent into first reactor in a manner of flowing up, with the first hydrogenation catalyst being seated in first reactor
Agent contacts, and the logistics after the hydrogenation of output first from the first hydrogenation reactor.
(2) second hydrogenation steps
H is supplemented by first2It is sent into the gas passage of the second air and liquid mixer, the second gas is sent into logistics after the first hydrogenation
In the fluid passage of liquid mixer, so as to by logistics after the hydrogenation of the first hydrogen make-up injection first, form the second gas-liquid mixed
Thing.Second gas-liquid mixture is sent into second reactor in a manner of flowing up, be seated in second reactor
Two hydrogenation catalysts contact, and the logistics after the hydrogenation of output second from the second hydrogenation reactor.
(3) the 3rd hydrogenation steps
H is supplemented by second2It is sent into the gas passage of the 3rd air and liquid mixer, the 3rd gas is sent into logistics after the second hydrogenation
In the fluid passage of liquid mixer, so as to by logistics after the hydrogenation of the second hydrogen make-up injection second, form the 3rd gas-liquid mixed
Thing.3rd gas-liquid mixture is sent into a manner of flowing up in the 3rd reactor, be seated in the 3rd reactor
Three hydrogenation catalysts contact, and the logistics after the hydrogenation of output the 3rd from the 3rd hydrogenation reactor.
The reaction condition of each step is listed in table 4.The conversion of the composition, raw material of logistics after the hydrogenation of each reactor output
The selectivity of rate, the overall selectivity of product and cis-product is listed in table 5.
Embodiment 6
Hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester is prepared using method same as Example 5, unlike, the first hydrogenation
The carrier of catalyst is Al2O3, i.e. the first hydrogenation catalyst is Rh-Yb/Al2O3(containing 3.0 weight %Rh and 0.5 weight %Yb).
Embodiment 7
Hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester is prepared using method same as Example 5, unlike, the 3rd hydrogenation
The carrier of catalyst is activated carbon, i.e. the 3rd hydrogenation catalyst is that Ru-Eu/ activated carbons (contain 0.9 weight %Ru and 0.3 weight %
Eu)。
Embodiment 8
Hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester is prepared using method same as Example 5, unlike, the second hydrogenation
The carrier of catalyst is SiO2, i.e. the second hydrogenation catalyst is Ru-Sm/SiO2(containing 2 weight %Ru and 4.0 weight %Sm).
Comparative example 4
The first hydrogenation catalyst, the second hydrogenation catalyst and the 3rd hydrogenation are prepared using method same as Example 7 to urge
Agent, unlike, in the Yb in the first hydrogenation catalyst, the Sm in the second hydrogenation catalyst and the 3rd hydrogenation catalyst
Eu with etc. the Ce of weight replace.
Table 4
1：The volume ratio of liquid phase stream after hydrogen and the second hydrogenation
Table 5
Embodiment 9
In the present embodiment, the first hydrogenation catalyst Rh-Sm/SiO is prepared using method same as Example 12(contain 5.0
Weight %Rh and 5.0 weight %Sm), unlike, the species of the corresponding composition and carrier for changing maceration extract.
Second hydrogenation catalyst Rh-Sm/SiO is prepared using method same as Example 12(containing 4.0 weight %Rh and
4.0 weight %Sm), unlike, the species of the corresponding composition and carrier for changing maceration extract.
3rd hydrogenation catalyst Ru-Eu/C is prepared using method same as Example 1 and (contains 0.9 weight %Ru and 0.3 weight
Measure %Eu), unlike, the corresponding composition for changing maceration extract.
The present embodiment prepares hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester using the method shown in Fig. 2, wherein, the first gas-liquid is mixed
The component for being used for abutting gas passage and fluid passage in clutch (it is public to be purchased from Tianyuan environment engineering finite in Beijing for void channels
Department), the average pore size in the hole on the tube wall of the void channels is 100nm, and 7 passages are evenly distributed with void channels；Second
The component for being used for abutting gas passage and fluid passage in air and liquid mixer is porous sieve plate, and the hole in the porous sieve plate is averaged
Aperture is 800nm；It is porous sieve plate to be used for abutting gas passage and the component of fluid passage in 3rd air and liquid mixer, and this is porous
The average pore size in the hole in sieve plate is 10 μm.Specific method is as described below.
(1) first hydrogenation step
By H2It is sent into the gas passage of the first air and liquid mixer, by hexamethylene -1 containing diisooctyl phthalate,
2- dioctyl phthalate didecyls ester solution (content of diisooctyl phthalate is 30 weight %) is sent into the liquid of the first air and liquid mixer
In body passage, so as to by hydrogen injection hexamethylene -1,2- dioctyl phthalate didecyl ester solution, form the first gas-liquid mixture.By
One gas-liquid mixture is sent into first reactor in a manner of flowing up, and is urged with the first hydrogenation being seated in first reactor
Agent contacts, and the logistics after the hydrogenation of output first from the first hydrogenation reactor.
(2) second hydrogenation steps
H is supplemented by first2It is sent into the gas passage of the second air and liquid mixer, the second gas is sent into logistics after the first hydrogenation
In the fluid passage of liquid mixer, so as to by logistics after the hydrogenation of the first hydrogen make-up injection first, form the second gas-liquid mixed
Thing.Second gas-liquid mixture is sent into second reactor in a manner of flowing up, be seated in second reactor
Two hydrogenation catalysts contact, and the logistics after the hydrogenation of output second from the second hydrogenation reactor.
(3) the 3rd hydrogenation steps
H is supplemented by second2It is sent into the gas passage of the 3rd air and liquid mixer, the 3rd gas is sent into logistics after the second hydrogenation
In the fluid passage of liquid mixer, so as to by logistics after the hydrogenation of the second hydrogen make-up injection second, form the 3rd gas-liquid mixed
Thing.3rd gas-liquid mixture is sent into a manner of flowing up in the 3rd reactor, be seated in the 3rd reactor
Three hydrogenation catalysts contact, and the logistics after the hydrogenation of output the 3rd from the 3rd hydrogenation reactor.
The reaction condition of each step is listed in table 6.The conversion of the composition, raw material of logistics after the hydrogenation of each reactor output
The selectivity of rate, the overall selectivity of product and cis-product is listed in table 7.
Table 6
1：The volume ratio of liquid phase stream after hydrogen and the second hydrogenation
Table 7
Embodiment 10
First hydrogenation catalyst Rh-Sm/SiO is prepared using method same as Example 52(containing 1.0 weight %Rh and
1.0 weight %Sm), unlike, the species of the corresponding composition and carrier for changing maceration extract.
Second hydrogenation catalyst Rh-Yb/SiO is prepared using method same as Example 52(containing 0.5 weight %Rh and
0.1 weight %Yb), unlike, the species of the corresponding composition and carrier for changing maceration extract.
3rd hydrogenation catalyst Ru-Eu/Al is prepared using method same as Example 52O3(containing 0.1 weight %Ru and
0.8 weight %Eu), unlike, the species of the corresponding composition and carrier for changing maceration extract.
The present embodiment prepares hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester using the method shown in Fig. 2, wherein, the first gas-liquid is mixed
It is perforated membrane (purchased from Jiangsu my limited public affairs of high-tech share long to be used for the component of abutting gas passage and fluid passage in clutch
Department), the average pore size in the hole in the perforated membrane is 500nm；It is used for abutting gas passage in second air and liquid mixer and liquid leads to
The component in road is porous sieve plate, and the average pore size in the hole in the porous sieve plate is 500nm；It is used to abut in 3rd air and liquid mixer
The component of gas passage and fluid passage is porous sieve plate, and the average pore size in the hole in the porous sieve plate is 800nm.Specific method
As described below.
(1) first hydrogenation step
By H2It is sent into the gas passage of the first air and liquid mixer, by hexamethylene -1 containing diisooctyl phthalate,
2- dioctyl phthalate di-isooctyls solution (content of diisooctyl phthalate is 10 weight %) is sent into the first air and liquid mixer
In fluid passage, so as to by hydrogen injection hexamethylene -1,2- dioctyl phthalate di-isooctyl solution, form the first gas-liquid mixture.
First gas-liquid mixture is sent into first reactor in a manner of flowing up, first with being seated in first reactor adds
Hydrogen catalyst contacts, and the logistics after the hydrogenation of output first from the first hydrogenation reactor.
(2) second hydrogenation steps
H is supplemented by first2It is sent into the gas passage of the second air and liquid mixer, the second gas is sent into logistics after the first hydrogenation
In the fluid passage of liquid mixer, so as to by logistics after the hydrogenation of the first hydrogen make-up injection first, form the second gas-liquid mixed
Thing.Second gas-liquid mixture is sent into second reactor in a manner of flowing up, be seated in second reactor
Two hydrogenation catalysts contact, and the logistics after the hydrogenation of output second from the second hydrogenation reactor.
(3) the 3rd hydrogenation steps
H is supplemented by second2It is sent into the gas passage of the 3rd air and liquid mixer, the 3rd gas is sent into logistics after the second hydrogenation
In the fluid passage of liquid mixer, so as to by logistics after the hydrogenation of the second hydrogen make-up injection second, form the 3rd gas-liquid mixed
Thing.3rd gas-liquid mixture is sent into a manner of flowing up in the 3rd reactor, be seated in the 3rd reactor
Three hydrogenation catalysts contact, and the logistics after the hydrogenation of output the 3rd from the 3rd hydrogenation reactor.
The reaction condition of each step is listed in table 8.The conversion of the composition, raw material of logistics after the hydrogenation of each reactor output
The selectivity of rate, the overall selectivity of product and cis-product is listed in table 9.
Embodiment 11
Hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester is prepared using method same as in Example 10, unlike, the 3rd hydrogenation
The carrier of catalyst is activated carbon, i.e. the 3rd hydrogenation catalyst is Ru-Eu/ activated carbons, containing 0.1 weight %Ru and 0.8 weight %
Eu。
Table 8
1：The volume ratio of liquid phase stream after hydrogen and the second hydrogenation
Table 9
Even if embodiment 1-11's as a result, it was confirmed that using the hydrogenation catalyst of the present invention by phthalic acid binary ester hydrogenation
Under the hydrogenation conditions more relaxed, higher feed stock conversion can be also obtained, it is often more important that, production can be effectively improved
Thing selectivity, particularly can obtain higher suitable inverse ratio.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (23)
1. a kind of hydrogenation catalyst, the catalyst contains the main active element and auxiliary agent of carrier and load on the carrier
Element, the main active element are Rh and/or Ru, and the auxiliary element is selected from Sm, Eu and Yb, the carrier be selected from activated carbon,
Al2O3And SiO2。
2. hydrogenation catalyst according to claim 1, wherein, on the basis of the total amount of the catalyst, the master in terms of element
The content of active element is 0.05-8 weight %, preferably 0.1-5 weight %, and the content of the auxiliary element in terms of element is
0.05-8 weight %, preferably 0.1-5 weight %.
3. hydrogenation catalyst according to claim 1 or 2, wherein, in terms of element, the auxiliary element and the main activity
The mol ratio of element is 0.01-8：1, preferably 0.03-6：1.
4. the hydrogenation catalyst in claim 1-3 described in any one is as phthalic acid dibasic ester Hydrogenation for hexamethylene
The catalyst application of alkane -1,2- cyclohexanedimethanodibasic dibasic esters.
5. a kind of preparation method of hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester, this method are included under hydrogenation conditions, will contained
The raw mixture of phthalic acid dibasic ester and hydrogen contacts in the reactor with hydrogenation catalyst, it is characterised in that described
Hydrogenation catalyst is the hydrogenation catalyst described in any one in claim 1-3.
6. according to the method for claim 5, wherein, this method also include provide the raw mixture the step of：By hydrogen
In material liquid of the gas injection containing phthalic acid dibasic ester, the raw mixture is obtained；
Preferably, hydrogen is injected in the material liquid by a kind of air and liquid mixer, so as to obtain the raw mixture, institute
State air and liquid mixer include it is at least one be used for accommodate the material liquid fluid passage and it is at least one be used for accommodate the hydrogen
The gas passage of gas, abutted between the fluid passage and the gas passage by a component, at least part of the component
To there is porose area, the hydrogen has porose area to be injected into the material liquid by described；
The hole having in porose area is preferably micron openings and/or nano-pore, more preferably nano-pore；
The component is preferably combination more than one or both of perforated membrane, porous plate and void channels；
It is highly preferred that the air and liquid mixer also includes housing, the housing has gas access, liquid inlet and liquid discharge
Mouthful, the housing is internally provided with least one component, and the inner space of the housing is separated into liquid by the component
Body passage and gas passage, the both ends of the fluid passage connect with the liquid inlet and the liquid outlet respectively, described
Gas passage connects with the gas access.
7. according to the method for claim 6, wherein, the air and liquid mixer is arranged on the arrival end of the reactor.
8. according to the method described in any one in claim 5-7, wherein, the mol ratio of hydrogen and phthalic acid dibasic ester
For 3-15：1, preferably 3.2-7：1, more preferably 3.5-5.5：1.
9. according to the method described in any one in claim 5-8, wherein, the contact is at 35-100 DEG C, preferably 40-85 DEG C
At a temperature of carry out.
10. according to the method described in any one in claim 5-9, wherein, the contact is carried out in fixed bed reactors.
11. the method according to claim 11, wherein, the heavy space-time of the raw mixture in terms of phthalic acid dibasic ester
Speed is 0.5-16h-1, preferably 1-12h-1；In terms of gauge pressure, the pressure in reactor is 0.4-9MPa, preferably 0.5-7MPa,
More preferably 3-5MPa.
12. the method according to claim 10 or 11, wherein, the raw mixture enters institute in a manner of flowing up
State reactor.
13. according to the method described in any one in claim 5-12, wherein, the phthalic acid dibasic ester is selected from formula
Shown in I more than one or both of compound：
In Formulas I, R1And R2Respectively C1-C12Alkyl, preferably respectively C4-C10Alkyl, more preferably respectively C6-C10Alkane
Base, respectively further preferably C7-C10Alkyl；
Preferably, the phthalic acid dibasic ester is diisooctyl phthalate, diisooctyl phthalate and adjacent benzene
Combination more than one or both of dioctyl phthalate dinonyl.
14. a kind of preparation method of hexamethylene -1,2- cyclohexanedimethanodibasic dibasic ester, this method comprise the following steps：
(1) first hydrogenation step, in the first hydrogenation step, hydrogen is sent into the material liquid containing phthalic acid dibasic ester
In, the first gas-liquid mixture is formed, first gas-liquid mixture is sent into the first reaction for being filled with the first hydrogenation catalyst
In device, and under the first hydrogenation conditions, first gas-liquid mixture is contacted with first hydrogenation catalyst, obtain
Reaction solution after first hydrogenation；
(2) second hydrogenation steps, in the second hydrogenation step, by reaction solution after the first hydrogen make-up feeding first hydrogenation
In, the second gas-liquid mixture is formed, second gas-liquid mixture is sent into the second reaction for being filled with the second hydrogenation catalyst
In device, and under the second hydrogenation conditions, second gas-liquid mixture is contacted with second hydrogenation catalyst, obtain
Reaction solution after second hydrogenation；
(3) the 3rd hydrogenation steps, in the 3rd hydrogenation step, by reaction solution after the second hydrogen make-up feeding second hydrogenation
In, the 3rd gas-liquid mixture is formed, the 3rd gas-liquid mixture is sent into the 3rd reaction for being filled with the 3rd hydrogenation catalyst
In device, and under the 3rd hydrogenation conditions, the 3rd gas-liquid mixture is contacted with the 3rd hydrogenation catalyst, obtain
Mixed liquor containing hexamethylene -1,2- cyclohexanedimethanodibasic dibasic esters；
Wherein, first hydrogenation catalyst, second hydrogenation catalyst and the 3rd hydrogenation catalyst are respectively right
It is required that the catalyst in 1-3 described in any one.
15. according to the method for claim 14, wherein, the carrier of first hydrogenation catalyst is SiO2And/or Al2O3,
Preferably Al2O3；
The carrier of second hydrogenation catalyst and the 3rd hydrogenation catalyst is respectively activated carbon and/or SiO2, second hydrogenation
The carrier of catalyst is preferably SiO2, the carrier of the 3rd hydrogenation catalyst is preferably activated carbon.
16. the method according to claims 14 or 15, wherein, the hydrogen be sent into the material liquid, the first hydrogen make-up
Mol ratio with phthalic acid dibasic ester in the material liquid is 0.8-3：0.5-2.5：1, preferably 1-2.8：0.8-2.2：
1, more preferably 1.1-2.5：1-2：1, more preferably 1.2-2.2：1.1-2：1, the second hydrogen make-up and the material liquid
Volume ratio be 3-80, preferably 5-60.
17. according to the method described in any one in claim 14-16, wherein, in the first hydrogenation step, the contact exists
Carry out at a temperature of 35-80 DEG C, carried out preferably at a temperature of 40-70 DEG C, in terms of gauge pressure, pressure of the contact in 0.4-9MPa
Carry out under power, preferably carried out under 0.5-7MPa pressure；
In second hydrogenation step, the contact is carried out at a temperature of 40-90 DEG C, is carried out preferably at a temperature of 50-85 DEG C, with
Gauge pressure meter, the contact are carried out under 0.4-9MPa pressure, preferably carried out under 0.5-7MPa pressure；
In 3rd hydrogenation step, the contact is carried out at a temperature of 50-100 DEG C, is carried out preferably at a temperature of 60-85 DEG C,
Carried out more preferably at a temperature of 70-85 DEG C, in terms of gauge pressure, the contact is carried out under 0.4-9MPa pressure, is preferably existed
Carried out under 0.5-7MPa pressure.
18. according to the method described in any one in claim 14-17, wherein, the temperature contacted in the first hydrogenation step
Degree is less than the temperature contacted in the second hydrogenation step, and the temperature contacted in the second hydrogenation step walks less than the 3rd hydrogenation
The temperature contacted in rapid.
19. according to the method described in any one in claim 14-18, wherein, with phthalic acid two in the material liquid
On the basis of the total amount of first ester, the weight (hourly) space velocity (WHSV) of first gas-liquid mixture and the second gas-liquid mixture is respectively 0.5-16h-1,
Preferably 0.8-12h-1, more preferably 1-10h-1, the weight (hourly) space velocity (WHSV) of the 3rd gas-liquid mixture is 2-16h-1, preferably 4-
15h-1, more preferably 5-9h-1。
20. according to the method described in any one in claim 14-18, wherein, the first hydrogenation step, the second hydrogenation step and
In 3rd hydrogenation step, forming the method for gas-liquid mixture includes：Hydrogen is injected into liquid phase stream by a kind of air and liquid mixer
In, so as to obtain gas-liquid mixture, the air and liquid mixer include at least one fluid passage for being used to accommodate liquid phase stream and
At least one gas passage for being used to accommodate hydrogen, is abutted between the fluid passage and the gas passage by a component,
The component at least partially has porose area, and the hydrogen has porose area to be injected into the material liquid by described；
The hole having in porose area is preferably micron openings and/or nano-pore, more preferably nano-pore；
The component is preferably combination more than one or both of perforated membrane, porous plate and void channels；
It is highly preferred that the air and liquid mixer also includes housing, the housing has gas access, liquid inlet and liquid discharge
Mouthful, the housing is internally provided with least one component, and the inner space of the housing is separated into liquid by the component
Body passage and gas passage, the both ends of the fluid passage connect with the liquid inlet and the liquid outlet respectively, described
Gas passage connects with the gas access.
21. the method according to claim 11, wherein, in entering for first reactor, second reactor and the 3rd reactor
Mouth end each sets at least one air and liquid mixer.
22. according to the method described in any one in claim 14-21, wherein, first reactor, second reactor and the 3rd
The feeding manner of reactor is from bottom to top.
23. according to the method described in any one in claim 14-22, wherein, the phthalic acid dibasic ester be selected from
Shown in Formulas I more than one or both of compound：
In Formulas I, R1And R2Respectively C1-C12Alkyl, preferably respectively C4-C10Alkyl, more preferably respectively C6-C10Alkane
Base, respectively further preferably C7-C10Alkyl；
Preferably, the phthalic acid dibasic ester is diisooctyl phthalate, diisooctyl phthalate and adjacent benzene
Combination more than one or both of dioctyl phthalate dinonyl.
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| CN110743540A (en) * | 2019-11-06 | 2020-02-04 | 中国天辰工程有限公司 | Catalyst for preparing cyclododecene through selective hydrogenation and preparation method and application thereof |
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