CN1800121A - Method for preparing cyclohexyl bezene through highly-selectively catalytic hydrogenation for biphenyl - Google Patents
Method for preparing cyclohexyl bezene through highly-selectively catalytic hydrogenation for biphenyl Download PDFInfo
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- CN1800121A CN1800121A CNA2006100456255A CN200610045625A CN1800121A CN 1800121 A CN1800121 A CN 1800121A CN A2006100456255 A CNA2006100456255 A CN A2006100456255A CN 200610045625 A CN200610045625 A CN 200610045625A CN 1800121 A CN1800121 A CN 1800121A
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- Prior art keywords
- biphenyl
- bezene
- highly
- catalytic hydrogenation
- reaction
- Prior art date
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Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims description 68
- 239000004305 biphenyl Substances 0.000 title claims description 34
- 235000010290 biphenyl Nutrition 0.000 title claims description 34
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims description 10
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 title claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000001257 hydrogen Chemical group 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 claims description 2
- 238000007037 hydroformylation reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000000956 alloy Substances 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 abstract 2
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 239000012847 fine chemical Substances 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 42
- 238000005984 hydrogenation reaction Methods 0.000 description 17
- 230000009466 transformation Effects 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- 238000005804 alkylation reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 230000029936 alkylation Effects 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- -1 phenylaniline fluoroform Chemical compound 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 238000003965 capillary gas chromatography Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OQXMLPWEDVZNPA-UHFFFAOYSA-N 1,2-dicyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1C1CCCCC1 OQXMLPWEDVZNPA-UHFFFAOYSA-N 0.000 description 1
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 229910000809 Alumel Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910018007 MmNi Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- YPPQDPIIWDQYRY-UHFFFAOYSA-N [Ru].[Rh] Chemical compound [Ru].[Rh] YPPQDPIIWDQYRY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 125000003917 carbamoyl group Chemical class [H]N([H])C(*)=O 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- SUCYXRASDBOYGB-UHFFFAOYSA-N cobalt rhodium Chemical compound [Co].[Rh] SUCYXRASDBOYGB-UHFFFAOYSA-N 0.000 description 1
- INILCLIQNYSABH-UHFFFAOYSA-N cobalt;sulfanylidenemolybdenum Chemical compound [Mo].[Co]=S INILCLIQNYSABH-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical group OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for using a dipheyl highly selective catalyst hydrogenated to prepare cyclohexyl benzene in the field of holder nickel applied technology. The method can use dipheyl highly selective catalyst hydrogenated to prepare the fine chemical cyclohexyl benzene with high annex value. The once-through return rate can achieve to 90%. The pioneer body of the main crystal is the alloy prepared by high temperature fusion technology; the constitute expression is NiAlM, wherein the quench component M is one or some of Fe, Mn, Mo, Cr. The pioneer body uses NaOH water solution to actively expel Al to form the holder nickel catalyst with high hydrogenated active and high selectivity.
Description
Technical field
The invention belongs to the applied technical field of shortening, is a kind of method of preparing cyclohexyl bezene through highly-selectively catalytic hydrogenation for biphenyl.This method can be under mild conditions be selected biphenyl the highly purified phenylcyclohexane of hydrogenation preparing.
Background technology
Phenylcyclohexane is a kind of important chemical intermediate, high boiling point and make it have special physical and chemical performance near the condensation point of room temperature.Characteristics such as the phenylcyclohexane liquid crystal material has high chemical stability, photochemical stability, viscosity is low and physical properties is good are one of ideal materials of indicating meter.Phenylcyclohexane also can be used for the additive of lithium secondary cell electrolyte, can improve the cyclicity of lithium ion battery, has anti-overcharge performance, can improve safety performance.The relevant information of phenylcyclohexane: colourless liquid, molecular formula: C
12H
16Molecular weight: 160.26, CAS registration number: 827-52-1 fusing point: 5～6 ℃ of boiling points: 235～236 ℃ of flash-points: the preparation of 92 ℃ of phenylcyclohexanes has caused people's attention very early.The preparation route mainly contains three: the alkylation process of benzene, the selection hydrogenation method of biphenyl, other various routes.The alkylation process Crone of benzene etc.
[1]Disclose that the ruthenium catalyst catalysis benzene alkylation of load prepares phenylcyclohexane on the acid carrier.Catalyzer can will at high temperature be used hydrogen reducing before the catalyzer use with the 8th family or the 6th family's metal or its mixture modification.The reaction conditions that an embodiment of this patent adopts is 192 ℃ of temperature, and hydrogen pressure is 3.5MPa, and the selectivity of phenylcyclohexane is no more than 60% with this understanding.The by product of this reaction is hexanaphthene, methylcyclopentane, dicyclohexyl benzene etc.Crone etc.
[2]Disclosing aluminium sesquioxide in 1976 or silicon dioxide carried nickel catalyzator is used for preparing phenylcyclohexane, is that 190 ℃ and pressure are under the reaction conditions of 3.5MPa in temperature of reaction, and the selectivity of phenylcyclohexane is 59% when the benzene transformation efficiency is 26%.This catalyzer does not obviously improve the phenylcyclohexane selectivity, is a much progress but substituted the catalyzer cost reduction that precious metal brings with cheap component.
Murtha etc.
[3-6]The benzene alkylation legal system is equipped with phenylcyclohexane compares careful research.Murtha etc.
[3]At first propose to adopt the supported catalyst of rhodium, at least a element of palladium, nickel or rare-earth metal modified crystalline zeolite are carrier.The Preparation of catalysts process is as follows: support of the catalyst is earlier wetting with the aqueous solution of rare earth element, nickel, ammoniate, vigorous stirring in the glass reaction still then, and cold filtration washing 6 times, low temperature is dry down; The zeolite of ion-exchange is with Palladous chloride or rhodium chloride aqueous solution dipping, dry in vacuum vessel, be warmed up to 205 ℃ then and keep 4h, slowly be warmed up to 524 ℃ and remain 8h then; Then in air, cool off and get final product.Be reflected in the fixed-bed reactor and carry out, temperature range is at 150～190 ℃, and the transformation efficiency of reaction is lower than 20%, and the selectivity of phenylcyclohexane is nearly all below 75%, and the actual recovery of phenylcyclohexane is very low.And then Murtha etc. propose to use the load platinum of this preparation method's preparation also to have suitable effect, and when the transformation efficiency of benzene was 10.4%, the selectivity of phenylcyclohexane was 75%.In 1978, Murtha proposed to prepare phenylcyclohexane with ruthenium nickel bimetal supported catalyst.Catalyst preparation process is similar to the above with hydroconversion condition, and selectivity is not significantly improved yet.Murtha has carried out modification to the noble metal support catalyzer, adds elements such as rhenium, lanthanum, cerium, praseodymium, niobium, gadolinium, apparent in view raising selectivity; The transformation efficiency of benzene is 10% o'clock, and the selectivity of phenylcyclohexane is 81.3%.
Ichiro etc.
[7]Disclosing and having adopted mass ratio is that 0.1% zeolite-loaded palladium catalyst is equipped with phenylcyclohexane by the benzene alkylation legal system, and batch reactor is adopted in reaction.In temperature is that 200 ℃ and pressure are under the condition of 5.0MPa, and the benzene transformation efficiency reaches 80%, and the selectivity of phenylcyclohexane is reached 56.5%.Though selectivity is not very high, yield is enhanced.Ichiro etc.
[8]Optimized Preparation of catalysts, adopted Palladous nitrate to replace the presoma of Palladous chloride, improved speed of response greatly, and the selectivity of reaction has increased also as catalyzer.Roman etc.
[9]Prepare phenylcyclohexane with noble metal catalyst (as ruthenium, rhodium, palladium, iridium etc.) the catalysis benzene alkylation that loads on the y-type zeolite, under the High Temperature High Pressure, the phenylcyclohexane selectivity is 83%.
From the above mentioned, the alkylation of benzene prepares phenylcyclohexane and adopts loaded noble metal catalyst mostly, and common is zeolite-loaded ruthenium rhodium palladium platinum catalyst; At 150～200 ℃, pressure concentrates on 3.0～5.0MPa to the temperature of reaction system mostly; The yield of phenylcyclohexane is no more than 50%.2, biphenyl selects hydrogenation method biphenyl to contain two identical phenyl ring, and the scientific worker wishes the high hydrogenation preparing phenylcyclohexane of selecting of catalysis biphenyl always.As far back as nineteen sixty-eight, Rylander etc.
[10]Disclosing and having adopted 5% palladium carbon is catalyzer, is solvent with the hexanaphthene, can obtain higher phenylcyclohexane yield; Simultaneously also disclose other noble metal support catalyzer (as ruthenium carbon, rhodium carbon, platinum carbon etc.) and also can be used as the Preparation of Catalyst phenylcyclohexane, but yield is lower.This is reflected under 100 ℃ and the 7.0MPa and carries out, and by product is the product connection hexanaphthene of the complete hydrogenation of biphenyl.Michel etc.
[11]Employing loads on that the cobalt molybdenum sulphide is a catalyzer on the aluminum oxide, but does not provide concrete data, only lays particular emphasis on the research of reaction mechanism.Gelman etc.
[12]Adopt the various aromatic hydrogenations of rhodium cobalt catalyst catalysis, wherein catalysis biphenyl is selected the phenylcyclohexane of hydrogenation acquisition 84% and 15% connection hexanaphthene.Its temperature of reaction is 60 ℃, and pressure is 1.4MPa, and the suitable gentleness of reaction conditions is the remarkable advantage of this catalyzer, and the loaded down with trivial details and catalyzer of catalyst preparation process is expensive to be the disadvantage of this catalyzer.
Takehito etc.
[13]Adopt the selection hydrogenation of industrial nickel catalyzator catalysis biphenyl commonly used, obtained phenylcyclohexane under the optimal conditions up to 95%; Temperature of reaction is 90 ℃, and pressure is normal pressure.Reaction conditions is relatively gentleer, the yield height of phenylcyclohexane, and this is a very big progress.This shows that biphenyl selects the hydrogenation preparing phenylcyclohexane to adopt various catalyst system.The yield that the selection hydrogenation method prepares phenylcyclohexane is generally than benzene alkylation method height, and this is a much progress.Select hydrogenation temperature scarcely to surpass 120 ℃, pressure is no more than 2.0MPa, and the reaction conditions of this reaction needed is than benzene alkylation method gentleness.3, other method Shinichi etc.
[14]Debrominate prepares phenylcyclohexane to 4-bromo biphenyl hydrogenation with chemical process to adopt hydrogen storage alloy, has obtained 95% yield.This catalyzer such as MmNi
3.5Co
0.7A
10.8H
4, wherein the lanthanum that consists of of Mm is 30%, and cerium is 52%, and praseodymium is 5%, and neodymium is 13% (mass ratio).Temperature of reaction is 160 ℃, reaction times 3h, and the product of reaction also comprises the connection hexanaphthene, the content distribution of product is subjected to the scale effect of alloy and biphenyl.
Tashiro etc.
[15]In the aqueous solution of 4-chlordiphenyl, add alumel; drip the aqueous solution of 1% cesium hydroxide then; allow the hydrogen that reacts generation as hydrogen source; skeleton nickel with generation is a catalyzer; realize the hydrodechlorination of 4-chlordiphenyl is prepared phenylcyclohexane under protection of nitrogen gas, the phenylcyclohexane yield is 91%.The hydrogen that relies on reaction to produce satisfies the hydrogenation needs, needs a large amount of alumeies, the production cost height.
Bibliographical information is arranged
[16]With 1-benzyl ring hexene is reactant, is that solvent has realized that under the katalysis of palladium catalyst the selection hydrogenation of two keys has obtained phenylcyclohexane with ethanol, and selectivity is up to 100%.The transformation efficiency height of reaction, but raw material is not easy to obtain, and does not possess industrial prospect.Wang Yan is wide etc.
[17]Adopting 4-benzyl carboxamide phenylaniline fluoroform sulphonate is catalyzer, research Friedel-Crafts benzylization and hexamethylene glycosylation reaction.Reactant is hexalin and benzene, the chloroform give solvent, and temperature of reaction is 80 ℃, reaction 2h, the phenylcyclohexane yield is 94%.Catalyzer uses through 5 times, and active not obviously reduction can recycle.The reactant that the method more than enumerated adopts has nothing in common with each other, and also each is different for catalyzer.The yield that reaction obtains is generally higher, but raw material is not easy to obtain or catalyst preparation technology is more loaded down with trivial details, and production cost is higher relatively, is not suitable for suitability for industrialized production.
Summary of the invention
Purpose of the present invention just provides a kind of simple and easy, repeated a kind of biphenyl good, the catalyzer long service life and selects the novel method of hydrogenation preparing phenylcyclohexane.
Technical solution of the present invention is, a kind of method of preparing cyclohexyl bezene through highly-selectively catalytic hydrogenation for biphenyl, this method are modified skeletal nickel catalyst to be used for biphenyl select to add hydroformylation step and prepare phenylcyclohexane, and its method steps is:
In still formula high-pressure reactor, add biphenyl, solvent, skeletal nickel catalyst, the mass ratio of solvent and biphenyl is 1: 2-20: 1, the skeletal nickel catalyst consumption is the 0.5-15wt% of biphenyl, airtight back hydrogen exchange, be pressurized to 0.1-1.0MPa then, H-H reaction takes place under the room temperature to inhale, put into oil bath and slowly be heated to temperature of reaction 30-150 ℃, adjust hydrogen valve, making system pressure reach pressure is 0.1-5MPa, stirring the following reaction times is 0.3-8h, and the once through yield of phenylcyclohexane reaches more than 99%
Described modified skeletal nickel catalyst, its precursor is made up of Primary Catalysts and promotor, and Primary Catalysts is a nickel, and promotor is made up of Al and M, and integral body is expressed as NiAlM, and wherein component M is one or more the mixture among Fe, Mn, Mo or the Cr; The pressed powder weight percent of Ni, Al, M is Ni:30-60%, Al:30-70%, M:0.1-10%, and catalyst precursor launches according to a conventional method; In temperature of reaction is 80-120 ℃, and system pressure is 0.5-3.5MPa, and the reaction times is that reaction effect is better under the condition of 0.3-4.5h.Solvent of the present invention is one or more the mixture in methyl alcohol, ethanol, Virahol, hexanaphthene, sherwood oil, tetrahydrofuran (THF), dioxane, the perhydronaphthalene.
The catalyst precursor alloy is made according to ordinary method, the fused alloy is cooled to room temperature in argon gas atmosphere, after the pulverizing, become fine particle with ball mill grinding, the catalyst fines of selecting the different grain size scope with sub-sieve is for standby, and normally used size range is the 10-60 micron;
The activation method of catalyst precursor alloy, powdered alloy is slowly joined in the 10-25%NaOH solution, launch to remove in 15-120 minute Al down, with the washing of deoxidation deionized water repeated multiple times at 70-100 ℃, be neutral to solution, form skeleton nickel based structures catalyzer.
The invention has the beneficial effects as follows that cost is low, the selectivity height, the once through yield of phenylcyclohexane reaches more than 99%, and catalyzer can be applied mechanically repeatedly, is fit to suitability for industrialized production.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
In being 50 milliliters still formula high-pressure reactor, puts into volume 5 gram biphenyl, 25 milliliters of solvents, and the skeletal nickel catalyst after the 0.5 gram activation, airtight rear substitution air charges into 20Kgcm then
-2Hydrogen, just take place under the room temperature to inhale H-H reaction, put into slowly heat temperature raising of oil bath, adjust hydrogen valve, make system pressure reach 20Kgcm
-2, after 40 minutes, reaction is finished.Capillary gas chromatography is carried out in the sampling of cooling back, transformation efficiency 100%, single benzene ring hydrogenation product yield 0.2%, full hydrogenation products yield 99%.
Embodiment 2
In being 50 milliliters still formula high-pressure reactor, puts into volume 3.5 gram biphenyl, 20 milliliters of solvents, and the skeletal nickel catalyst after the 0.5 gram activation, airtight rear substitution air charges into 10Kgcm then
-2Hydrogen, just take place under the room temperature to inhale H-H reaction, put into slowly heat temperature raising to 100 degree of oil bath, adjust hydrogen valve, make system pressure reach 10Kgcm
-2, kept then 1 hour.Capillary gas chromatography is carried out in the sampling of cooling back, and transformation efficiency 99.8%, the yield of product phenylcyclohexane are 99.4%.
Embodiment 3
In being the still formula high-pressure reactor of 1 liter, puts into volume 75 gram biphenyl, 0.5 liter of solvent, and the skeletal nickel catalyst after the 25 gram activation, airtight rear substitution air charges into 10Kgcm then
-2Hydrogen, just take place under the room temperature to inhale H-H reaction, put into slowly heat temperature raising to 100 degree of oil bath, adjust hydrogen valve, make system pressure reach 10Kgcm
-2, kept then 1 hour.Capillary gas chromatography is carried out in the sampling of cooling back, and transformation efficiency 99.9%, the yield of product phenylcyclohexane are 99.2%.
Embodiment 4
In being the still formula high-pressure reactor of 2 liters, puts into volume 150 gram biphenyl, 1 liter of solvent, and the skeletal nickel catalyst after the 50 gram activation, airtight rear substitution air charges into 10Kgcm then
-2Hydrogen, H-H reaction just takes place to inhale under the room temperature, slowly heat temperature raising to 90 degree is adjusted hydrogen valve, makes system pressure reach 20Kgcm
-2, keeping then 1 hour, capillary gas chromatography is carried out in the sampling of cooling back, and transformation efficiency 100%, the yield of product phenylcyclohexane are 99.0%.
Embodiment 5
In being the still formula high-pressure reactor of 5 liters, puts into volume 375 gram biphenyl, 2.5 liters of solvents, and the skeletal nickel catalyst after the 125 gram activation, airtight rear substitution air charges into 10Kgcm then
-2Hydrogen, H-H reaction just takes place to inhale under the room temperature, slowly heat temperature raising to 90 degree is adjusted hydrogen valve, makes system pressure reach 20Kgcm
-2, keeping then 1 hour, capillary gas chromatography is carried out in the sampling of cooling back, and transformation efficiency 100%, the yield of product phenylcyclohexane are 99.1%.
Claims (6)
1, a kind of method of preparing cyclohexyl bezene through highly-selectively catalytic hydrogenation for biphenyl is characterized in that, this method is modified skeletal nickel catalyst to be used for biphenyl select to add hydroformylation step and prepare phenylcyclohexane, and its method steps is:
In still formula high-pressure reactor, add biphenyl, solvent, modified skeletal nickel catalyst, the mass ratio of solvent and biphenyl is 1: 2-20: 1, the skeletal nickel catalyst consumption is the 0.5-15wt% of biphenyl, hydrogen exchange is used in airtight back, is pressurized to 0.1-1.0MPa then, and H-H reaction takes place under the room temperature to inhale, put into oil bath and slowly be heated to temperature of reaction 30-150 ℃, adjust hydrogen valve, making system pressure reach pressure is 0.1-5MPa, and stirring the following reaction times is 0.3-8h.
2, the method for a kind of preparing cyclohexyl bezene through highly-selectively catalytic hydrogenation for biphenyl according to claim 1, it is characterized in that: described modified skeletal nickel catalyst, its precursor is made up of Primary Catalysts and promotor, Primary Catalysts is a nickel, promotor is made up of Al and M, integral body is expressed as NiAlM, and wherein component M is one or more the mixture among Fe, Mn, Mo or the Cr; The pressed powder weight percent of Ni, Al, M is Ni:30-60%, Al:30-70%, M:0.1-10%, and catalyst precursor launches according to a conventional method.
3, the method for a kind of preparing cyclohexyl bezene through highly-selectively catalytic hydrogenation for biphenyl according to claim 2 is characterized in that, described temperature of reaction is 70-120 ℃.
4, the method for a kind of preparing cyclohexyl bezene through highly-selectively catalytic hydrogenation for biphenyl according to claim 2 is characterized in that, described system pressure is 0.5-3.5MPa.
5, the method for a kind of preparing cyclohexyl bezene through highly-selectively catalytic hydrogenation for biphenyl according to claim 2 is characterized in that, the described reaction times is 0.3-4.5h.
6, the method for a kind of preparing cyclohexyl bezene through highly-selectively catalytic hydrogenation for biphenyl according to claim 2, it is characterized in that described solvent is one or more the mixture in methyl alcohol, ethanol, Virahol, hexanaphthene, sherwood oil, tetrahydrofuran (THF), dioxane, the perhydronaphthalene.
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