TWI465289B - 製造環己基苯的方法 - Google Patents
製造環己基苯的方法 Download PDFInfo
- Publication number
- TWI465289B TWI465289B TW097131436A TW97131436A TWI465289B TW I465289 B TWI465289 B TW I465289B TW 097131436 A TW097131436 A TW 097131436A TW 97131436 A TW97131436 A TW 97131436A TW I465289 B TWI465289 B TW I465289B
- Authority
- TW
- Taiwan
- Prior art keywords
- mcm
- cyclohexylbenzene
- benzene
- molecular sieve
- oxide
- Prior art date
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- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 39
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 239000002808 molecular sieve Substances 0.000 claims abstract description 33
- 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 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [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 17
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 16
- OQXMLPWEDVZNPA-UHFFFAOYSA-N 1,2-dicyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1C1CCCCC1 OQXMLPWEDVZNPA-UHFFFAOYSA-N 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000010555 transalkylation reaction Methods 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- OECMNLAWCROQEE-UHFFFAOYSA-N cyclohexylbenzene;hydrogen peroxide Chemical compound OO.C1CCCCC1C1=CC=CC=C1 OECMNLAWCROQEE-UHFFFAOYSA-N 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 229910052707 ruthenium Inorganic materials 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
- LTEQMZWBSYACLV-UHFFFAOYSA-N Hexylbenzene Chemical compound CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 claims 2
- 238000013329 compounding Methods 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000010544 hydroalkylation process reaction Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 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
- 239000000203 mixture Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000004821 distillation Methods 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
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052902 vermiculite Inorganic materials 0.000 description 5
- 239000010455 vermiculite Substances 0.000 description 5
- 235000019354 vermiculite Nutrition 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 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
- 230000007017 scission Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- -1 cyclic quinone imine Chemical class 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 241000894007 species Species 0.000 description 3
- NBIJDQIBCRZHFK-UHFFFAOYSA-N 1,3,5-trihydroxy-1,3,5-triazinane-2,4,6-trione Chemical group ON1C(=O)N(O)C(=O)N(O)C1=O NBIJDQIBCRZHFK-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-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
- 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
- 239000005084 Strontium aluminate Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 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
- 239000013078 crystal 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
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 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
- 229910018072 Al 2 O 3 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
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 102000001708 Protein Isoforms Human genes 0.000 description 1
- 108010029485 Protein Isoforms Proteins 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 238000013480 data collection Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 210000004124 hock Anatomy 0.000 description 1
- 238000007037 hydroformylation reaction Methods 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 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
- 239000007858 starting material Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
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Description
本申請案主張2007年9月21日提出之美國臨時專利申請案第60/974,312號的優先權,其全部揭示內容併為此文之參考資料。
本發明關於用於製造環己基苯及選擇性地將所產生之環己基苯轉化成酚及環己酮之方法。
酚為化學工業中之重要產物且用於,例如:製造酚類樹脂、雙酚A、ε-己內醯胺、己二酸及塑化劑。
目前,最常用於製造酚之路徑為哈克(Hock)方法。此為一種三步驟方法,其中第一個步驟涉及以丙烯將苯烷基化以製造異丙苯,再將該異丙苯氧化成對應之氫過氧化物,然後將該氫過氧化物裂解以製造等莫耳量之酚及丙酮。然而,全世界對酚之需求較對丙酮之需求的成長更為快速。另外,由於丙烯逐漸短缺,丙烯之成本似乎增加。因此,使用較多鏈烯來取代丙烯作為進料並共同產製較高酮類而非丙酮之方法可能為具吸引力之製造酚的替換路徑。
例如:環己基苯之氧化(類似於異丙苯氧化作用)可提供用於製造酚之替代路徑,但無共同產製丙酮的問題。此替換路徑可共同產製環己酮(其市場在成長中且係作為
工業溶劑),其可作為氧化反應和產製己二酸、環己酮樹脂、環己酮肟、己內醯胺及尼龍6中的活化劑。然而,此替換路徑需要發展用於製造環己基苯先質之在商業上可實行的方法。
多年來已知環己基苯可藉由氫烷基化或還原性烷基化方法自苯製造。在此方法中,苯係於催化劑之存在下與氫一起加熱,如此,苯可經過部分氫化來產生環己烯,其再將該苯起始物質烷基化。因此,美國專利案第4,094,918及4,177,165號中揭示芳族烴在催化劑(其包含經鎳及稀土金屬處理過之沸石和鈀促進劑)上之氫烷基化作用。類似地,美國專利案第4,122,125及4,206,082號中揭示使用支撐在經稀土金屬處理過之沸石上的釕及鎳化合物作為芳族氫烷基化催化劑。這些先前技藝之方法中所使用之沸石為沸石X及Y。另外,美國專利案第5,053,571號中提出使用支撐在β沸石上的釕及鎳作為芳族氫烷基化催化劑。然而,這些用於苯之氫烷基化作用的稍早提案受困於對環己基苯之選擇性低,尤其是在經濟上可行之苯轉化率方面,以及製造大量不欲有之副產物(尤其是環己烷及甲基環戊烷)的問題。
最近,美國專利案第6,037,513號中揭示在苯之氫烷基化反應中的環己基苯選擇性可經由將苯和氫與雙官能性催化劑(其包含至少一種氫化金屬及MCM-22族之分子篩)接觸來改良。該氫化金屬宜選自鈀、釕、鎳、鈷及其混合物且該接觸步驟係在約50℃至350℃之溫度、約100至
7000kPa之壓力、苯對氫之莫耳比為約0.01至100及約0.01至100之WHSV下進行。'513號專利案中揭示所產生之環己基苯可再氧化成對應之氫過氧化物,然後將該過氧化物分解成所需之酚和環己酮。
根據本發明,現已發現當使用包含MCM-22族之鋁矽酸鹽分子篩及氫化金屬的雙官能性催化劑進行苯之氫烷基化作用時,當該催化劑之酸對金屬的莫耳比(定義為分子篩中之鋁的莫耳數對氫化金屬的莫耳數)為約75至約750時,該催化劑顯示出對單環己基苯之選擇性增加而對二環己基苯和環己烷之選擇性降低。
於一種觀點中,本發明關於用於製造環己基苯之方法,該方法包含:(a)將苯及氫饋入至少一個反應區中;(b)在具有催化劑系統之氫烷基化條件下將苯和氫在該至少一個反應區內接觸,以產生含有環己基苯之流出液,該催化劑系統包含鋁矽酸鹽分子篩(其X-射線繞射圖包含在12.4±0.25、6.9±0.15、3.57±0.07及3.42±0.07埃()處之d-間距峰值)及至少一氫化金屬,其中該催化劑系統之酸對金屬的莫耳比為約75至約750。
較合宜地,該催化劑系統之酸對金屬的莫耳比為約100至約300。
較合宜地,該分子篩係選自MCM-22、PSH-3、SSZ-
25、ERB-1、ITQ-1、ITQ-2、MCM-36、MCM-49、MCM-56、UZM-8及任何其二或多者之混合物,尤其是MCM-22、MCM-49、MCM-56及其同型。
較合宜地,該至少一種氫化金屬係選自鈀、釕、鎳、鋅、錫及鈷,尤其是鈀。
於一較佳體系中,至少50重量%,更宜為至少75重量%,最宜為大體上全部(甚至是100重量%)之該至少一種氫化金屬係支撐在與該分子篩不同之無機氧化物上,諸如元素週期表第2、4、13和14族之一種元素的氧化物。這類氧化物宜包含鋁氧及/或氧化鈦及/或鋯氧。
較合宜地,該氫烷基化條件包括在約100至400℃之範圍內的溫度。較合宜地,該氫烷基化壓力係在約100至7000 kPaa之範圍內。
於另一觀點中,本發明關於用於共同產製酚及環己酮之方法,該方法包含藉由此處所描述之方法製造環己基苯,將該環己基苯氧化以製造環己基苯氫過氧化物,再將該環己基苯氫過氧化物裂解,以製造酚及環己酮。
本文描述一種用於將苯氫烷基化以製造環己基苯,再將環己基苯於二步驟過程中轉化成環己酮及酚的方法。目前為止,由於該氫烷基化步驟除了製造所需之單環己基苯產物外還製造二環己基苯,該方法可進一步包括以另外之苯將二環己基苯進行烷基轉移的步驟來進一步製造單環己
基苯產物的步驟。
苯氫烷基化
本方法中之第一個步驟包含在氫烷基化條件下,於氫烷基化作用之催化劑的存在下將苯與氫接觸,藉此,苯可經過下列反應來產生環己基苯(CHB):
競爭性反應包括苯之完全飽和,以產生環己烷,將其二烷基化以產生二環己基苯,再經重組/烷基化反應以產生不純物(諸如甲基環戊基苯(MCPB))。雖然二環己基苯可經過烷基轉移以產生另外之CHB產物,但轉化成環己烷代表損失有用之進料,而存在不純物(諸如甲基環戊基苯(MCPB))特別不利,因MCPB之沸點非常接近CHB之沸點,因此,將MCPB與CHB分開十分困難。因此,在氫烷基化反應中將環己基苯之選擇性達到最高很重要。
任何市面上可購得之苯進料均可用於氫烷基化步驟中,較佳地,苯之純度至少為99%。類似地,雖然氫之來源並無嚴格規定,但一般而言,氫宜具有至少99重量%之純度。
較佳地,該氫烷基化步驟中之全部進料含有少於1000ppm(諸如少於500ppm,例如:少於100ppm)之水。較佳地,該全部進料通常含有少於100 ppm(諸如少於30ppm,例如:少於3ppm)之硫。較佳地,該全部進料含有少於10 ppm(諸如少於1ppm,例如:少於0.1ppm)之氮。於一特佳之實施態樣中係取得至少二種,宜為全部三種上述之水、硫及氮的較佳含量。
氫烷基化反應可在多種反應器構造(包括固定床、漿體反應器及/或催化性蒸餾塔)中進行。另外,氫烷基化反應可在單一反應區或數個反應區中進行,其中至少該氫係分階段引入反應中。一般而言,該饋入反應之氫總莫耳數對該饋入反應之苯莫耳數之比例為約0.15:1至約15:1,例如約0.3:1至約1:1,諸如:約0.4:1至約0.9:1。用於進行氫烷基化反應之合適溫度係在約100℃至約400℃,諸如約125℃至約250℃。合適之反應壓力係在約100至約7,000kPaa,諸如約500至約5,000kPaa。
氫烷基化反應中所使用之催化劑為一種雙官能性催化劑,其包含MCM-22族之鋁矽酸鹽分子篩及氫化金屬。此處所使用之“MCM-22族物質”(或“MCM-22族之物質”或“MCM-22族之分子篩”)一詞包括下列之一或多項:.自共通性第1級結晶型建構塊單位晶格製成之分子篩,該單位晶格具有MWW骨架拓撲。(單位晶格為原子之空間排列,若以三次元空間堆疊則可描繪
結晶構造。這類結晶構造討論於“Atlas of Zeolite Framework Types”,Fifth edition,2001中,其全部內容併為此文之參考資料);.自共通性第2級建構塊製成之分子篩,其為這類MWW骨架拓撲單位晶格之2-次元堆疊,形成具有一單位晶格厚度之單層(宜為一c-單位晶格厚);.自共通性第2級建構塊製成之分子篩,其為具有一或超過一個單位晶格厚度之層,其中該超過一單位晶格厚之層係經由將至少二層具有一單位晶格厚之單層堆疊、裝填或黏結來製得。這類第二級建構塊之堆疊可以規律方式、不規律方式、任意方式或其任何組合進行;及.自具有MWW骨架拓撲之單位晶格的任何規律或任意之2-次元或3-次元組合製成的分子篩。
一般而言,MCM-22族之分子篩具有之X-射線繞射圖包含在12.4±0.25、6.9±0.15、3.57±0.07及3.42±0.07埃()處之d-間距峰值。用來描述物質之特徵的X-射線繞射數據係藉由標準技術取得,諸如使用銅之K-α雙線作為入射輻射線,配備閃爍計數器的繞射儀和作為資料收集系統之聯結電腦。MCM-22族之分子篩包括MCM-22(描述於美國專利案第4,954,325號中)、PSH-3(描述於美國專利案第4,439,409號中)、SSZ-25(描述於美國專利案第4,826,667號中)、ERB-1(描述於歐洲專利案第0293032號中)、ITQ-1(描述於美國專利案第6,077,498號中)、
ITQ-2(描述於國際專利刋物第WO 97/17290號中)MCM-36(描述於美國專利案第5,250,277號中)、MCM-49(描述於美國專利案第5,236,575號中)、MCM-56(描述於美國專利案第5,362,697號中)、UZM-8(描述於美國專利案第6,756,030號中)及其任何二或多者之組合。較佳地,該分子篩係選自(a)MCM-49、(b)MCM-56及(c)MCM-49及MCM-56之同型,諸如ITQ-2。
本氫烷基化反應之催化劑中可使用任何已知之氫化金屬,但合適之金屬包括鈀、釕、鎳、鋅、錫及鈷,鈀為特佳者。一般而言,存在於催化劑中之氫化金屬的量係經過選擇使分子篩中之鋁對氫化金屬的莫耳比為約75至約750,諸如約100至約300。
該氫化金屬可藉由,例如浸透或離子交換而直接支撐在(MCM-22族)分子篩上。然而,於更佳之體系中,至少50重量%(例如:至少75重量%),一般而言,大體上全部之氫化金屬係支撐在與分子篩分開但與其複合之無機氧化物上。尤其是現已發現:與其中該氫化金屬係支撐在分子篩上之同等催化劑相較下,經由將氫化金屬支撐在無機氧化物上可增加催化劑之活性及其對環己基苯和二環己基苯之選擇性。
這類複合之氫烷基化催化劑中所使用之無機氧化物並無嚴格界定,惟其其在氫烷基化反應之條件下穩定且無作用。合適之無機氧化物包括元素週期表第2、4、13和14族的元素之氧化物,諸如鋁氧及/或氧化鈦及/或鋯氧。此
處所使用之元素週期表的編號方案揭示於Chemical and Engineering News,63(5),27(1985)中。當該催化劑系統包含矽鋁酸鹽分子篩及與分子篩不同之無機氧化物的複合物時,較合宜地,此二種成分之重量比係在90:10至10:90之範圍內,諸如80:20至20:80,例如70:30至30:70或60:40至40:60。
於上述之較佳體系中,該氫化金屬係置放於無機氧化物上,較合宜的為該氫化金屬係在該含金屬之無機氧化物與分子篩複合前藉由浸透置放在無機氧化物上。通常,該催化劑複合物係藉由共同製粒法製造(其中該分子篩與含金屬之無機氧化物的混合物係在高壓下(通常約350至約350,000kPa)形成丸粒)或藉由共同-擠出法製造(其中該分子篩與含金屬之無機氧化物的漿體及隨意加上之分開的結合劑係被用力推過模具)。若需要時可接著將另外之氫化金屬置於所產生之催化劑複合物上。
合適之結合劑物質包括合成或天然物質以及無機物質,諸如黏土、矽石及/或金屬氧化物。後者可為天然產生或為包含矽石與金屬氧化物之混合物的膠狀沈澱物或凝膠之形式。可作為結合劑之天然黏土包括屬於蒙脫土及高嶺土族者,該族包括變膨潤石(subbentonite)和通稱為狄西(Dixie)、麥納米(McNamee)、喬治亞(Georgia)和佛羅里達(Florida)黏土之高嶺土,或其中該主要之礦物組成為敘永石(halloysite)、高嶺石(kaolinite)、狄克石(dickite)、珍珠石(nacrite)或富矽高嶺石(
anauxite)的其他物質。這類黏土可以原始開採出或最初進行鍛燒、酸性處理或化學修飾之未加工狀態使用。合適之金屬氧化物結合劑包括矽石、鋁氧、鋯氧、氧化鈦、矽石-鋁氧、矽石-鎂氧、矽石-鋯氧、矽石-釷氧、矽石-鈹氧、矽石-氧化鈦以及三元組成物,諸如矽石-鋁氧-釷氧、矽石-鋁氧-鋯氧、矽石-鋁氧-鎂氧及矽石-鎂氧-鋯氧。
雖然氫烷基化步驟對環己基苯具高度選擇性,但來自氫烷基化反應之流出液通常含有一些二烷基化之產物以及未反應之芳香族進料和所需之單烷基化物種。該未反應之芳香族進料通常藉由蒸餾回收並再循環入烷基化反應器中。來自苯蒸餾作用之底液再進一步蒸餾以將單環己基苯產物自任何二環己基苯和其他大型物質分離出。根據存於反應流出液中之二環己基苯的量可能需要以另外之苯將二環己基苯進行烷基轉移,以使所需之單烷基化物種的產製最佳。
以另外之苯進行烷基轉移通常係在烷基轉移反應器(與氫烷基化反應器分開)中,於合適之烷基轉移催化劑(諸如MCM-22族、β沸石、MCM-68(見美國專利第6,014,018號)、沸石Y或絲光沸石之分子篩)上作用。烷基轉移反應通常係在至少部分液相之條件下進行,較合適地,該條件包括約100℃至約300℃之溫度及/或約800至約3500kPa之壓力及/或在總進料上重量時空速率約1至約10小時-1
及/或苯/二環己基苯之重量比約1:1至約5:1。
環己基苯氧化作用
為了將環己基苯轉化成酚及環己酮,先將環己基苯氧化成對應之氫過氧化物。此可經由將含氧氣體(諸如空氣)引入含有該環己基苯之液相中來完成。不像異丙苯,無催化劑存在時環己基苯之大氣氧化作用非常緩慢,因此,氧化作用通常係在催化劑之存在下進行。
用於環己基苯之氧化步驟的合適催化劑為美國專利案第6,720,462號(其併為此文之參考資料)中描述之N-羥基取代之環形醯亞胺,諸如N-羥基酞醯亞胺、4-胺基-N-羥基酞醯亞胺、3-胺基-N-羥基酞醯亞胺、四溴-N-羥基酞醯亞胺、四氯-N-羥基酞醯亞胺、N-羥基喜太醯亞胺(N-hydroxyhetimide)、N-羥基喜米醯亞胺(N-hydroxyhimimide)、N-羥基苯偏三酸醯亞胺、N-羥基苯-1,2,4-三羧醯亞胺、N,N'-二羥基(苯均四酸二醯亞胺)、N,N'-二羥基(二苯甲酮-3,3',4,4'-四羧酸二醯亞胺)、N-羥基馬來醯亞胺、吡啶-2,3-二羧醯亞胺、N-羥基琥珀醯亞胺、N-羥基(酒石酸醯亞胺)、N-羥基-5-降莰烯-2,3-二羧醯亞胺、外-N-羥基-7-氧雜二環[2.2.1]庚-5-烯-2,3-二羧醯亞胺、N-羥基-順式-環己烷-1,2-二羧醯亞胺、N-羥基-順式-4-環己烯-1,2-二羧醯亞胺、N-羥基萘醯亞胺鈉鹽或N-羥基-鄰-苯二磺醯亞胺。較佳地,該催化劑為N-羥基酞醯亞胺。另一合適之催化劑為N,N',N"-三羥基異氰尿酸。
這些物質可單獨使用或在自由基引發劑之存在下使用
,且可以液相之同相催化劑形式使用或可支撐在固態載體上以提供異相催化劑。通常,N-羥基取代之環形醯亞胺或N,N',N"-三羥基異氰尿酸之使用量係在環己基苯之0.0001莫耳%至15重量%(諸如0.001至5重量%)。
用於氧化步驟之合適條件包括約70℃至約200℃之溫度,諸如約90℃至約130℃及/或約50至10,000kPa之壓力。任何含氧氣體(宜為空氣)均可作為氧化介質。此反應可在批式反應器或連續流動式反應器中發生。可加入鹼性緩衝劑以與可能在氧化期間形成之酸性副產物反應。另外,可引入水相,此可協助溶解鹼性化合物(諸如碳酸鈉)。
氫過氧化物之裂解
在環己基苯轉化成酚及環己酮之反應中的最終反應步驟涉及環己基苯氫過氧化物之裂解,較合宜地,其係經由將氫過氧化物與催化劑在液相中接觸來作用。此可合宜地在約20℃至約150℃(諸如約40℃至約120℃)之溫度及/或約50至約2,500kPa(諸如約100至約1000kPa)之壓力下進行。該環己基苯氫過氧化物宜在對裂解反應無反應之有機溶劑(諸如甲基乙基酮、環己酮、酚或環己基苯)中稀釋,以協助將熱移除。較方便地,該裂解反應係在催化性蒸餾單位中進行。
在裂解步驟中所使用之催化劑可為同相催化劑或異相催化劑。
合適之同相裂解催化劑包括硫酸、過氯酸、磷酸、氫氯酸及對-甲苯磺酸。三氯化鐵、三氟化硼、二氧化硫及三氧化硫亦為有效之同相裂解催化劑。較佳之同相裂解催化劑為硫酸,其濃度宜在0.05至0.5重量%之範圍內。在同相酸性催化劑方面,裂解步驟後宜接續中和步驟。這類中和步驟通常涉及與鹼性成分接觸,再接著傾析富含鹽之水相。
用於環己基苯氫過氧化物之裂解中的合適之異相催化劑包括膨潤石黏土,諸如美國專利案第4,870,217號(其全部揭示內容併為此文之參考資料)中所描述之酸性蒙脫土矽石-鋁氧黏土。
該來自裂解步驟之未加工的環己酮及未加工之酚可被進一步純化來製造純化之環己酮及酚。合適之純化方法包括,但不限於一系列之蒸餾塔,以將環己酮及酚自其他物種分開。
下列實例僅用於說明而非限制本發明之範圍。
實例1
為了說明酸/金屬比在MCM-22族分子篩上進行之氫烷基化反應中的重要性,在二種以同等方式製備(酸/金屬比除外)之催化劑上進行背對背(back-to-back)實驗。此二種催化劑均含有2克之支撐在γ鋁氧上的0.3重量%Pd。然後,將Pd/Al2
O3
氫化催化劑與HMCM-49矽鋁酸
鹽分子篩(矽石對鋁之莫耳比為18)共同粒化。催化劑A與催化劑B間之主要差異(見表1)為前者含有1.6克MCM-49催化劑,後者含有4.8克MCM-49。催化劑A中,MCM-49中之鋁對Pd的莫耳比為50。催化劑B之對應的莫耳比為150。
催化劑A和B係在標稱同等之條件下測試。苯之進料速率為0.08cc/分鐘,而氫之進料速率為10cc/分鐘。反應溫度為150℃,而壓力為1034kPag(150psig)。結果摘要於表1中。
由表1中可知,催化劑B之效能優於催化劑A之效能。二種催化劑之轉化率相當(42對43重量%轉化率),但催化劑B對環己基苯和二環己基苯之總選擇性接近92重量%,其明顯高於催化劑A之選擇性88%。另外,催化劑B對單環己基苯較催化劑A明顯更具選擇性(78重量%對70.8重量%)。
雖然本發明經由參考特殊較佳體系加以描述及說明,
本技藝之一般技術人士可察知不侷限於此處所說明之本發明的變體。為此,參考應僅限於後附之申請專利範圍,以供決定本發明之真正範圍。
Claims (16)
- 一種用於製造環己基苯之方法,該方法包含:(a)將苯及氫饋入至少一反應區;(b)在具有催化劑系統之氫烷基化條件下將苯和氫在該至少一反應區內接觸,以產生含有環己基苯之流出液,該催化劑系統包含鋁矽酸鹽分子篩(其X-射線繞射圖包含在12.4±0.25、6.9±0.15、3.57±0.07及3.42±0.07埃(Å)處之d-間距峰值)及至少一氫化金屬,其中該催化劑系統之酸對金屬的莫耳比為約75至約750。
- 如申請專利範圍第1項之方法,其中該催化劑系統之酸對金屬的莫耳比為100至300。
- 如申請專利範圍第1項之方法,其中該分子篩係選自MCM-22、PSH-3、SSZ-25、ERB-1、ITQ-1、ITQ-2、MCM-36、MCM-49、MCM-56、UZM-8及其任何二或多者之組合。
- 如申請專利範圍第3項之方法,其中該分子篩係選自MCM-22、MCM-49、MCM-56及其任何二或多者之組合。
- 如申請專利範圍第1項之方法,其中該至少一種氫化金屬係選自鈀、釕、鎳、鋅、錫及鈷。
- 如申請專利範圍第5項之方法,其中該氫化金屬包含鈀。
- 如申請專利範圍第1至6項中任一項之方法,其中至少50重量%之氫化金屬係支撐在與該分子篩不同之無 機氧化物上。
- 如申請專利範圍第7項之方法,其中至少75重量%之氫化金屬係支撐在無機氧化物上。
- 如申請專利範圍第8項之方法,其中實質上全部氫化金屬係支撐在無機氧化物上。
- 如申請專利範圍第7項之方法,其中該至少一種之氫化金屬係在無機氧化物與分子篩複合前施放在該無機氧化物上。
- 如申請專利範圍第7項之方法,其中該無機氧化物包含至少一種元素週期表第2、4、13和14族的元素之氧化物。
- 如申請專利範圍第11項之方法,其中該無機氧化物包含鋁氧及/或氧化鈦及/或鋯氧。
- 如申請專利範圍第1至6項中任一項之方法,其中該氫烷基化條件包括100至400℃之溫度及/或100至7000kPaa之壓力。
- 如申請專利範圍第1至4項中任一項之方法,其中饋入該接觸之氫的總莫耳數對饋入該接觸之苯的莫耳數之比例為0.15:1至15:1。
- 如申請專利範圍第1至6項中任一項之方法,其中該流出液亦含有二環己基苯且該二環己基苯至少有部分在烷基轉移條件下與苯接觸,以製造另外的環己基苯。
- 一種用於共同產製酚及環己酮之方法,該方法包含藉由申請專利範圍第1至6項中任一項之方法製造環己 基苯,將該環己基苯氧化以製造環己基苯氫過氧化物並將該環己基苯氫過氧化物裂解,以製造酚及環己酮。
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- 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 EP EP08797656A patent/EP2200955B1/en not_active Not-in-force
- 2008-08-12 US US12/663,303 patent/US7847128B2/en active Active
- 2008-08-12 AT AT08797656T patent/ATE506335T1/de not_active IP Right Cessation
- 2008-08-12 KR KR1020107006151A patent/KR101151978B1/ko not_active IP Right Cessation
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US7910779B2 (en) | 2011-03-22 |
DE602008006438D1 (de) | 2011-06-01 |
US7847128B2 (en) | 2010-12-07 |
WO2009038900A1 (en) | 2009-03-26 |
EP2200955A1 (en) | 2010-06-30 |
ATE506335T1 (de) | 2011-05-15 |
US20100179351A1 (en) | 2010-07-15 |
JP5192546B2 (ja) | 2013-05-08 |
US20110028762A1 (en) | 2011-02-03 |
KR20100044906A (ko) | 2010-04-30 |
CN101754940A (zh) | 2010-06-23 |
CN101754940B (zh) | 2013-05-08 |
TW200922689A (en) | 2009-06-01 |
JP2010536862A (ja) | 2010-12-02 |
KR101151978B1 (ko) | 2012-06-01 |
EP2200955B1 (en) | 2011-04-20 |
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