CN101754940B - 制备环己基苯的方法 - Google Patents
制备环己基苯的方法 Download PDFInfo
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- CN101754940B CN101754940B CN2008800250033A CN200880025003A CN101754940B CN 101754940 B CN101754940 B CN 101754940B CN 2008800250033 A CN2008800250033 A CN 2008800250033A CN 200880025003 A CN200880025003 A CN 200880025003A CN 101754940 B CN101754940 B CN 101754940B
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- Prior art keywords
- benzene
- phenylcyclohexane
- mcm
- inorganic oxide
- metal hydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title claims abstract description 6
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 title abstract 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000002808 molecular sieve Substances 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 5
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 claims description 36
- 229910052987 metal hydride Inorganic materials 0.000 claims description 25
- 150000004681 metal hydrides Chemical class 0.000 claims description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 19
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 17
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 17
- OQXMLPWEDVZNPA-UHFFFAOYSA-N 1,2-dicyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1C1CCCCC1 OQXMLPWEDVZNPA-UHFFFAOYSA-N 0.000 claims description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 238000010555 transalkylation reaction Methods 0.000 claims description 8
- 238000005336 cracking Methods 0.000 claims description 7
- OECMNLAWCROQEE-UHFFFAOYSA-N cyclohexylbenzene;hydrogen peroxide Chemical compound OO.C1CCCCC1C1=CC=CC=C1 OECMNLAWCROQEE-UHFFFAOYSA-N 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- -1 molecular sieve compound Chemical class 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 description 11
- LTEQMZWBSYACLV-UHFFFAOYSA-N Hexylbenzene Chemical compound CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 230000007017 scission Effects 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 6
- 238000005804 alkylation reaction Methods 0.000 description 6
- 238000003776 cleavage reaction Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- NBIJDQIBCRZHFK-UHFFFAOYSA-N 1,3,5-trihydroxy-1,3,5-triazinane-2,4,6-trione Chemical compound ON1C(=O)N(O)C(=O)N(O)C1=O NBIJDQIBCRZHFK-UHFFFAOYSA-N 0.000 description 2
- GPEOILIUFBLQOG-UHFFFAOYSA-N 1-cyclopentyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C1CCCC1 GPEOILIUFBLQOG-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- BUXKULRFRATXSI-UHFFFAOYSA-N 1-hydroxypyrrole-2,5-dione Chemical compound ON1C(=O)C=CC1=O BUXKULRFRATXSI-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- ZKRXZOLGLXXMEA-UHFFFAOYSA-N dioxosilane zirconium Chemical compound [Zr].[Si](=O)=O ZKRXZOLGLXXMEA-UHFFFAOYSA-N 0.000 description 1
- TVUBDAUPRIFHFN-UHFFFAOYSA-N dioxosilane;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].O=[Si]=O TVUBDAUPRIFHFN-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 210000004124 hock Anatomy 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- HOGDNTQCSIKEEV-UHFFFAOYSA-N n'-hydroxybutanediamide Chemical compound NC(=O)CCC(=O)NO HOGDNTQCSIKEEV-UHFFFAOYSA-N 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UGQZLDXDWSPAOM-UHFFFAOYSA-N pyrrolo[3,4-f]isoindole-1,3,5,7-tetrone Chemical compound C1=C2C(=O)NC(=O)C2=CC2=C1C(=O)NC2=O UGQZLDXDWSPAOM-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/74—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition with simultaneous hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
在制备环己基苯的方法中,将苯和氢气进料入至少一个反应区。然后将苯和氢气在至少一个反应区中在加氢烷基化条件下与包含分子筛和至少一种氢化金属的催化剂体系接触以制备含有环己基苯的流出物,该分子筛具有包括在12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07埃处的d-间距最大值的X-射线衍射图。该催化剂体系具有约75-约750的酸/金属摩尔比。
Description
相关申请的交叉引用
本申请要求于2007年9月21日提交的美国临时专利申请No.60/974,312的优先权,该申请的披露内容全文在此引入作为参考。
技术领域
本发明涉及一种制备环己基苯和任选地将所得的环己基苯转化成苯酚和环己酮的方法。
背景技术
苯酚是化学工业中的重要产品,并且可用于例如酚醛树脂、双酚A、ε-己内酰胺、己二酸和增塑剂的制备。
目前,用于苯酚制备的最常用路径是Hock方法。其是一种三步方法,其中第一步骤涉及将苯用丙烯烷基化以制备异丙基苯,随后将异丙基苯氧化成相应的氢过氧化物,并且然后将氢过氧化物裂解以制得等摩尔量的苯酚和丙酮。然而,与丙酮相比,苯酚的世界需求增长更加迅速。另外,由于丙烯的开发短缺,因此丙烯的成本容易增加。因此,使用更高级烯烃代替丙烯作为进料并且共同制得更高级酮,而不是丙酮的方法可能是有吸引力的制备苯酚的替代性路径。
例如,环己基苯的氧化(与异丙基苯氧化类似)可以提供用于苯酚制备的替代性路径,而没有共同制得丙酮的问题。该替代性路径共同制得了环己酮,环己酮具有增长的市场并且被用作工业溶剂、氧化反应中的活化剂和用于制备己二酸、环己酮树脂、环己酮肟、己内酰胺和尼龙6。然而,该替代性路径需要开发商业上可行的制备环己基苯前体的方法。
已知可由苯通过加氢烷基化或者还原烷基化方法制备环己基苯许多年。在该方法中,在催化剂的存在下将苯与氢气一起加热以使得苯进行部分氢化以制得环己烯,环己烯然后将苯起始材料烷基化。因此,U.S.专利No s.4,094,918和4,177,165披露了芳族烃在包含镍-和稀土-处理的沸石以及钯促进剂的催化剂上加氢烷基化。类似地,U.S.专利No s.4,122,125和4,206,082披露了担载在稀土处理的沸石上的钌和镍化合物用作芳族加氢烷基化催化剂的应用。用于这些现有技术方法中的沸石是沸石X和Y。另外,U.S.专利No.5,053,571建议了担载在沸石β上的钌和镍用作芳族加氢烷基化催化剂的应用。然而,这些早期的用于苯加氢烷基化的建议遭受了环己基苯的选择性低(特别是在经济可行的苯转化率下)、并且制得大量不需要的副产物(特别是环己烷和甲基环戊烷)的问题。
近年来,U.S.专利No.6,037,513披露了通过使苯和氢气与包含至少一种氢化金属和MCM-22家族的分子筛的双功能催化剂接触,可以提高苯加氢烷基化中的环己基苯选择性。氢化金属优选选自钯、钌、镍、钴和它们的混合物,并且接触步骤在约50-350℃的温度、约100-7000kPa的压力、约0.01-100的苯/氢气摩尔比和约0.01-100的WHSV下进行。该‘513专利披露了然后可以将所得的环己基苯氧化成相应的氢过氧化物,并且使该过氧化物分解成所希望的苯酚和环己酮。
根据本发明,现已发现当将包含MCM-22家族的硅铝酸盐分子筛和氢化金属的双功能催化剂用于进行苯的加氢烷基化时,当催化剂的酸/金属摩尔比(定义为分子筛中铝的摩尔数/氢化金属的摩尔数)为约75-约750时,该催化剂表现出增强的单环己基苯选择性和降低的二环己基苯和环己烷的选择性。
发明内容
发明概述
在一个方面中,本发明涉及一种制备环己基苯的方法,该方法包括:
(a)将苯和氢气进料入至少一个反应区;
(b)在所述至少一个反应区中在加氢烷基化条件下使苯和氢气与包含硅铝酸盐分子筛和至少一种氢化金属的催化剂体系接触以制备含有环己基苯的流出物,该分子筛具有包括在12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07埃处的d-间距最大值的X-射线衍射图,其中该催化剂体系具有约75-约750的酸/金属摩尔比(定义为分子筛中铝的摩尔数/氢化金属的摩尔数)。
适宜地,催化剂体系具有约100-约300的酸/金属摩尔比。
适宜地,分子筛选自MCM-22、PSH-3、SSZ-25、ERB-1、ITQ-1、ITQ-2、MCM-36、MCM-49、MCM-56、UZM-8,和它们的任意两种或更多种的混合物,并且尤其为MCM-22、MCM-49、MCM-56和它们的同种型(isotype)。
适宜地,所述至少一种氢化金属选自钯、钌、镍、锌、锡和钴,尤其是钯。
在一个实施方案中,将至少50wt%,更优选至少75wt%,并且最优选基本上全部(甚至100wt%)的所述至少一种氢化金属担载在不同于所述分子筛的无机氧化物,例如元素周期表的第2、4、13和14族中的一种的氧化物上。该氧化物优选包括氧化铝和/或氧化钛和/或氧化锆。
适宜地,加氢烷基化条件包括约100-400℃的温度。适宜地,加氢烷基化压力为约100-7000kPaa。
在另一个方面中,本发明涉及一种共同制备苯酚和环己酮的方法,该方法包括通过本文中所述的方法制备环己基苯,将环己基苯氧化以制得环己基苯氢过氧化物,和将环己基苯氢过氧化物裂解以制得苯酚和环己酮。
发明详述
本文中描述一种将苯加氢烷基化以制备环己基苯并且然后以两步法将环己基苯转化成环己酮和苯酚的方法。在除了所希望的单环己基苯产物之外,就加氢烷基化步骤还制得二环己基苯来说,该方法可以包括将二环己基苯与另外的苯进行烷基转移以制得另外的单环己基苯产物的额外步骤。
苯加氢烷基化
本方法中的第一步骤包括在加氢烷基化条件下在加氢烷基化催化剂存在下使苯与氢气接触,从而苯进行以下反应以制得环己基苯(CHB):
竞争性反应包括苯的完全饱和以产生环己烷、苯的二烷基化以产生二环己基苯和苯的重组/烷基化反应以产生杂质,例如甲基环戊基苯(MCPB)。尽管可以将二环己基苯烷基转移以制得另外的CHB产物,但转化成环己烷表示有价值的进料的损失,而杂质例如甲基环戊基苯(MCPB)特别不希望,因为MCPB的沸点非常接近于CHB的沸点,使得非常难以将MCPB与CHB分离。因此,重要的是将加氢烷基化反应中环己基苯的选择性最大化。
任何可商购获得的苯进料可用于加氢烷基化步骤中,但优选地苯具有至少99wt%的纯度水平。类似地,尽管氢气源并不关键,但通常希望的是氢气为至少99wt%纯度的。
优选地,加氢烷基化步骤的总进料包含少于1000ppm,例如少于500ppm,例如少于100ppm的水。优选地,总进料通常包含少于100ppm,例如少于30ppm,例如少于3ppm的硫。优选地,总进料包含少于10ppm,例如少于1ppm,例如少于0.1ppm的氮。在特别优选的实施方案中,实现上述用于水、硫和氮的优选水平的至少两种,并且优选全部三种。
加氢烷基化反应可以在宽范围的反应器构造,包括固定床、淤浆反应器和/或催化蒸馏塔中进行。另外,加氢烷基化反应可以在单个反应区中或者在多个反应区中进行,其中至少将氢气分级地引入反应中。一般而言,进料入反应的氢气的总摩尔数与进料入反应的苯的摩尔数的比例为约0.15∶1-约15∶1,例如约0.3∶1-约1∶1,例如约0.4∶1-约0.9∶1。用于进行加氢烷基化反应的合适温度为约100℃-约400℃,例如约125℃-约250℃。合适的反应压力为约100-约7,000kPaa,例如约500-约5,000kPaa。
用于加氢烷基化反应的催化剂是包含MCM-22家族的硅铝酸盐分子筛和氢化金属的双功能催化剂。本文中使用的术语“MCM-22家族材料”(或者“MCM-22家族的材料”或“MCM-22家族的分子筛”)包括以下的一种或多种:
·由普通的第一度结晶构造单元(building block)晶胞制成的分子筛,所述晶胞具有MWW骨架拓扑结构。(晶胞是原子的空间排列,该空间排列如果以三维空间平铺其描述晶体结构。所述晶体结构论述于“Atlas of Zeolite Framework Types”,第五版,2001,该文献的整个内容引入作为参考);
·由普通的第二度构造单元制成的分子筛,此种MWW骨架拓扑结构晶胞的2-维平铺,形成“一个晶胞厚度的单层”,优选一个c-晶胞厚度;
·由普通的第二度构造单元制成的分子筛,是“一个或多于一个晶胞厚度的层”,其中多于一个晶胞厚度的层由将一个晶胞厚度的至少两个单层堆叠、填充或结合制成。此种第二度构造单元的堆叠可以按规则的方式,不规则的方式,随机方式或其任何组合;或
·通过具有MWW骨架拓扑结构的晶胞的任何规则或随机的2-维或3-维组合制造的分子筛。
MCM-22家族的分子筛通常具有以下X-射线衍射图:包括在12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07埃处的d-间距最大值。用于表征材料的X-射线衍射数据通过标准技术来获得:比如使用铜的K-α双峰作为入射辐射和装有闪烁计数器和作为收集系统的相关计算机的衍射计。MCM-22家族的分子筛包括MCM-22(描述于U.S.专利No.4,954,325)、PSH-3(描述于U.S.专利No.4,439,409)、SSZ-25(描述于U.S.专利No.4,826,667)、ERB-1(描述于欧洲专利No.0293032)、ITQ-1(描述于U.S.专利No.6,077,498)、ITQ-2(描述于国际专利公开No.WO 97/17290)、MCM-36(描述于U.S.专利No.5,250,277)、MCM-49(描述于U.S.专利No.5,236,575)、MCM-56(描述于U.S.专利No.5,362,697)、UZM-8(描述于U.S.专利No.6,756,030),和它们的任意两种或更多种的混合物。优选地,分子筛选自(a)MCM-49、(b)MCM-56和(c)MCM-49和MCM-56的同种型,例如ITQ-2。
任何已知的氢化金属可用于本发明的加氢烷基化催化剂中,尽管合适的金属包括钯、钌、镍、锌、锡和钴,钯是特别有利的。特别地,催化剂中存在的氢化金属的量被选择为使得分子筛中的铝与氢化金属的摩尔比为约75-约750,例如约100-约300。
氢化金属可以通过例如浸渍或离子交换直接担载在(MCM-22家族)分子筛上。然而,在更优选实施方案中,将至少50wt%,例如至少75wt%,并且通常基本上全部的氢化金属担载在与分子筛独立但与其复合的无机氧化物上。特别地,发现通过使氢化金属担载在无机氧化物上,与其中将氢化金属担载在分子筛上的等同催化剂相比,催化剂的活性和其对环己基苯和二环己基苯的选择性增加。
用于该复合加氢烷基化催化剂中的无机氧化物并未狭窄地限定,只要其在加氢烷基化反应条件下稳定并且惰性。合适的无机氧化物包括元素周期表的第2、4、13和14族的氧化物,例如氧化铝和/或氧化钛和/或氧化锆。本文中使用的用于周期表族的编号方案披露于Chemical and Engineering News,63(5),27(1985)中。当催化剂体系包含硅铝酸盐分子筛和不同于该分子筛的无机氧化物的复合物时,这两种组分适宜地以90∶10-10∶90,例如80∶20-20∶80,例如70∶30-30∶70或者60∶40-40∶60的重量比存在。
在上述优选实施方案中,在将含金属的无机氧化物与分子筛复合之前,适宜地通过浸渍使氢化金属沉积在无机氧化物上。通常,通过共同粒化(其中在高压(通常约350-约350,000kPa)下使分子筛和含金属的无机氧化物的混合物成型为粒料),或者通过共挤出(其中使分子筛和含金属的无机氧化物的淤浆任选地与单独的粘合剂一起通过模头)来制备催化剂复合物。如果必要,可以随后使另外的氢化金属沉积在所得的催化剂复合物上。
合适的粘合剂材料包括合成或天然存在的物质以及无机材料例如粘土、二氧化硅和/或金属氧化物。后者可以是天然存在的或者呈凝胶状沉淀物或凝胶,包括二氧化硅和金属氧化物的混合物的形式。可用作粘合剂的天然存在的粘土包括蒙脱土和高岭土家族的那些,该家族包括被普遍已知为Dixie、McNamee、Georgia和Florida粘土的变膨润土和高岭土,或者其中主要矿物组分为埃洛石、高岭石、地开石、珍珠陶土或富硅高岭石的其它物质。这些粘土可以原始状态作为原始开采的使用或者最初进行煅烧、酸处理或者化学改性。合适的金属氧化物粘合剂包括二氧化硅、氧化铝、氧化锆、氧化钛、二氧化硅-氧化铝、二氧化硅-氧化镁、二氧化硅-氧化锆、二氧化硅-氧化钍、二氧化硅-氧化铍、二氧化硅-氧化钛以及三元组合物例如二氧化硅-氧化铝-氧化钍、二氧化硅-氧化铝-氧化锆、二氧化硅-氧化铝-氧化镁和二氧化硅-氧化镁-氧化锆。
尽管加氢烷基化步骤对环己基苯是高度选择性的,但得自加氢烷基化反应的流出物将通常含有一些二烷基化产物,以及未反应的芳族进料和所希望的单烷基化类物质。未反应的芳族进料通常通过蒸馏回收并且再循环到烷基化反应器。将得自苯蒸馏的塔底物质进一步蒸馏以将单环己基苯产物与任何的二环己基苯和其它重质物质分离。取决于反应流出物中存在的二环己基苯的量,可能希望使二环己基苯与另外的苯进行烷基转移以使所希望的单烷基化类物质的制备最大化。
与另外的苯进行的烷基转移通常在与加氢烷基化反应器分开的烷基转移反应器中,在合适的烷基转移催化剂例如MCM-22家族的分子筛、沸石β、MCM-68(参见U.S.专利No.6,014,018)、沸石Y或丝光沸石上进行。烷基转移反应通常在至少部分液相条件下进行,该条件适宜地包括约100-约300℃的温度和/或约800-约3500kPa的压力和/或基于全部进料的约1-约10hr-1的重时空速和/或约1∶1-约5∶1的苯/二环己基苯重量比。
环己基苯氧化
为了使环己基苯转化成苯酚和环己酮,最初将环己基苯氧化成相应的氢过氧化物。这通过将含氧气体例如空气引入含有环己基苯的液相中来完成。与异丙基苯不同,在没有催化剂存在的情况下环己基苯的大气空气氧化非常缓慢,并且因此该氧化通常在催化剂的存在下进行。
用于环己基苯氧化步骤的合适催化剂是描述于U.S.专利No.6,720,462中并且在此引入作为参考的N-羟基取代的环状酰亚胺,例如N-羟基邻苯二甲酰亚胺、4-氨基-N-羟基邻苯二甲酰亚胺、3-氨基-N-羟基邻苯二甲酰亚胺、四溴-N-羟基邻苯二甲酰亚胺、四氯-N-羟基邻苯二甲酰亚胺、N-羟基hetimide、N-羟基himimide、N-羟基偏苯三酸酰亚胺、N-羟基苯-1,2,4-三碳酰亚胺、N,N’-二羟基(均苯四酸二酰亚胺)、N,N’-二羟基(二苯甲酮-3,3’,4,4’-四羧酸二酰亚胺)、N-羟基马来酰亚胺、吡啶-2,3-二碳酰亚胺、N-羟基琥珀酰亚胺、N-羟基(酒石酸酰亚胺)、N-羟基-5-降冰片烯-2,3-二碳酰亚胺、exo-N-羟基-7-氧杂双环[2.2.1]庚-5-烯-2,3-二碳酰亚胺、N-羟基-顺式-环己烷-1,2-二碳酰亚胺、N-羟基-顺式-4-环己烯-1,2-二碳酰亚胺、N-羟基萘二甲酰亚胺钠盐或者N-羟基-邻-苯二磺酰亚胺。优选地,催化剂是N-羟基邻苯二甲酰亚胺。另一种合适的催化剂是N,N’,N”-三羟基异氰脲酸。
这些材料可以单独或者在自由基引发剂的存在下使用,并且可以作为液相、均相催化剂使用或者可以担载在固体载体上以提供多相催化剂。一般而言,N-羟基取代的环状酰亚胺或者N,N’,N”-三羟基异氰脲酸以环己基苯的0.0001mol%-15wt%,例如0.001-5wt%的量使用。
用于氧化步骤的合适条件包括约70℃-约200℃,例如约90℃-约130℃的温度和/或约50-10,000kPa的压力。任何含氧气体,优选空气可以用作氧化介质。反应可以在间歇反应器或连续流动反应器中进行。可以加入碱性缓冲剂以与在氧化期间可能形成的酸性副产物反应。另外,可以引入水相,其可以有助于溶解碱性化合物例如碳酸钠。
氢过氧化物裂解
在环己基苯转化成苯酚和环己酮中的最后反应步骤涉及到环己基苯氢过氧化物的裂解,其适宜地通过在液相中使氢过氧化物与催化剂接触来进行。这适宜地在约20℃-约150℃,例如约40℃-约120℃的温度和/或约50-约2,500kPa,例如约100-约1000kPa的压力下进行。优选将环己基苯氢过氧化物稀释在对裂解反应惰性的有机溶剂例如甲基乙基酮、环己酮、苯酚或环己基苯中以有助于除热。裂解反应适宜地在催化蒸馏装置中进行。
用于裂解步骤的催化剂可以是均相催化剂或多相催化剂。
合适的均相裂解催化剂包括硫酸、高氯酸、磷酸、盐酸和对-甲苯磺酸。氯化铁、三氟化硼、二氧化硫和三氧化硫也是有效的均相裂解催化剂。优选的均相裂解催化剂是硫酸,优选浓度为0.05-0.5wt%。对于均相酸催化剂,在裂解步骤之后优选为中和步骤。该中和步骤通常涉及与碱性组分接触,随后将富含盐的水相滗析。
用于环己基苯氢过氧化物裂解的合适的多相催化剂包括绿土粘土(smectite clay),例如描述于U.S.专利No.4,870,217中的酸性蒙脱土二氧化硅-氧化铝粘土,该专利的整个披露内容在此引入作为参考。
得自裂解步骤的粗制环己酮和粗制苯酚可以进行进一步纯化以制得纯化的环己酮和苯酚。合适的纯化方法包括,但不限于,一系列蒸馏塔以使环己酮和苯酚与其它物质分离。
给出以下实施例用于解释目的,并且不限制本发明的范围。
实施例1
为了说明在MCM-22家族分子筛上的加氢烷基化中酸/金属比例的重要性,在除了酸/金属比例之外相同制备的两种催化剂上进行背靠背实验。这两种催化剂含有担载在γ氧化铝上的2g0.3wt%Pd。然后将Pd/Al2O3氢化催化剂与HMCM-49硅铝酸盐分子筛(二氧化硅/氧化铝摩尔比18)共同粒化。催化剂A与催化剂B之间的主要差异(参见表1)为前者含有1.6g MCM-49催化剂,而后者含有4.8g MCM-49。对于催化剂A,MCM-49中铝与Pd的摩尔比为50。对于催化剂B,相应比例为150。
催化剂A和B在标称相同的条件下测试。苯进料速率为0.08cc/min,而氢气进料速率为10cc/min。反应温度为150℃,而压力为1034kPag(150psig)。结果概述于表1中。
表1
催化剂 | A | B |
酸/金属摩尔比 | 50 | 150 |
转化率,wt% | 43.5 | 42.5 |
选择性,wt% | ||
环己烷 | 7.1 | 3.2 |
环己基苯 | 70.8 | 78.0 |
二环己基苯 | 17.3 | 13.8 |
其它 | 4.8 | 5.0 |
可从表1中看出,催化剂B的性能优于催化剂A的性能。两种催化剂的转化率类似(42wt%/43wt%转化率),但对于催化剂B,对环己基苯和二环己基苯的总选择性接近92wt%,这显著高于催化剂A的88%选择性。另外,与催化剂A相比,催化剂B对单环己基苯明显更有选择性(78wt%/70.8wt%)。
尽管已经参照特定实施方案描述和解释了本发明,但本领域那些普通技术人员将理解本发明适用于不一定在本文中说明的变型。出于该原因,为了确定本发明的真实范围的目的,则应该仅仅参考附属的权利要求。
Claims (16)
1.一种制备环己基苯的方法,该方法包括:
(a)将苯和氢气进料入至少一个反应区;
(b)在所述至少一个反应区中在加氢烷基化条件下使苯和氢气与包含硅铝酸盐分子筛和至少一种氢化金属的催化剂体系接触以制备含有环己基苯的流出物,该分子筛具有包括在12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07埃处的d-间距最大值的X-射线衍射图,其中该催化剂体系具有75-750的酸/金属摩尔比。
2.权利要求1的方法,其中该催化剂体系具有100-300的酸/金属摩尔比。
3.权利要求1的方法,其中该分子筛选自MCM-22、PSH-3、SSZ-25、ERB-1、I TQ-1、I TQ-2、MCM-36、MCM-49、MCM-56、UZM-8,和它们的任意两种或更多种的组合。
4.权利要求3的方法,其中该分子筛选自MCM-22、MCM-49、MCM-56,和它们的任意两种或更多种的组合。
5.权利要求1的方法,其中该至少一种氢化金属选自钯、钌、镍、锌、锡和钴。
6.权利要求5的方法,其中该氢化金属包括钯。
7.任一项前述权利要求的方法,其中将至少50wt%的氢化金属担载在不同于该分子筛的无机氧化物上。
8.权利要求7的方法,其中将至少75wt%的氢化金属担载在该无机氧化物上。
9.权利要求8的方法,其中将基本上全部的氢化金属担载在该无机氧化物上。
10.权利要求7的方法,其中在将该无机氧化物与该分子筛复合之前,将该至少一种氢化金属施加到该无机氧化物上。
11.权利要求7的方法,其中该无机氧化物包括元素周期表的第2、4、13和14族中的至少一种元素的氧化物。
12.权利要求11的方法,其中该无机氧化物包括氧化铝和/或氧化钛和/或氧化锆。
13.权利要求1-6中任一项的方法,其中该加氢烷基化条件包括100-400℃的温度和/或100-7000kPaa的压力。
14.权利要求1-4中任一项的方法,其中进料入所述接触的氢气的总摩尔数与进料入所述接触的苯的摩尔数的比例为0.15∶1-15∶1。
15.权利要求1-6中任一项的方法,其中该流出物还包含二环己基苯,并且将该二环己基苯的至少一部分与苯在烷基转移条件下接触以制得另外的环己基苯。
16.一种共同制备苯酚和环己酮的方法,该方法包括通过权利要求1-6中任一项的方法制备环己基苯,将该环己基苯氧化以制得环己基苯氢过氧化物,和将该环己基苯氢过氧化物裂解以制得苯酚和环己酮。
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2008
- 2008-08-12 KR KR1020107006151A patent/KR101151978B1/ko not_active IP Right Cessation
- 2008-08-12 WO PCT/US2008/072843 patent/WO2009038900A1/en active Application Filing
- 2008-08-12 CN CN2008800250033A patent/CN101754940B/zh not_active Expired - Fee Related
- 2008-08-12 DE DE602008006438T patent/DE602008006438D1/de active Active
- 2008-08-12 JP JP2010521924A patent/JP5192546B2/ja not_active Expired - Fee Related
- 2008-08-12 AT AT08797656T patent/ATE506335T1/de not_active IP Right Cessation
- 2008-08-12 EP EP08797656A patent/EP2200955B1/en not_active Not-in-force
- 2008-08-12 US US12/663,303 patent/US7847128B2/en active Active
- 2008-08-18 TW TW097131436A patent/TWI465289B/zh not_active IP Right Cessation
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2010
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Also Published As
Publication number | Publication date |
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KR20100044906A (ko) | 2010-04-30 |
WO2009038900A1 (en) | 2009-03-26 |
KR101151978B1 (ko) | 2012-06-01 |
JP2010536862A (ja) | 2010-12-02 |
CN101754940A (zh) | 2010-06-23 |
ATE506335T1 (de) | 2011-05-15 |
US20110028762A1 (en) | 2011-02-03 |
TWI465289B (zh) | 2014-12-21 |
US7847128B2 (en) | 2010-12-07 |
EP2200955B1 (en) | 2011-04-20 |
TW200922689A (en) | 2009-06-01 |
US7910779B2 (en) | 2011-03-22 |
DE602008006438D1 (de) | 2011-06-01 |
US20100179351A1 (en) | 2010-07-15 |
EP2200955A1 (en) | 2010-06-30 |
JP5192546B2 (ja) | 2013-05-08 |
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