TWI448445B - 製造環己基苯之方法 - Google Patents
製造環己基苯之方法 Download PDFInfo
- Publication number
- TWI448445B TWI448445B TW098106184A TW98106184A TWI448445B TW I448445 B TWI448445 B TW I448445B TW 098106184 A TW098106184 A TW 098106184A TW 98106184 A TW98106184 A TW 98106184A TW I448445 B TWI448445 B TW I448445B
- Authority
- TW
- Taiwan
- Prior art keywords
- mcm
- cyclohexylbenzene
- benzene
- weight
- molecular sieve
- Prior art date
Links
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 title claims description 55
- 238000000034 method Methods 0.000 title claims description 50
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 174
- 239000003054 catalyst Substances 0.000 claims description 53
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 38
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 32
- 239000002808 molecular sieve Substances 0.000 claims description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- OQXMLPWEDVZNPA-UHFFFAOYSA-N 1,2-dicyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1C1CCCCC1 OQXMLPWEDVZNPA-UHFFFAOYSA-N 0.000 claims description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 17
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000003776 cleavage reaction Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 230000007017 scission Effects 0.000 claims description 8
- GPEOILIUFBLQOG-UHFFFAOYSA-N 1-cyclopentyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C1CCCC1 GPEOILIUFBLQOG-UHFFFAOYSA-N 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
- 238000010555 transalkylation reaction Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- WNHVCSSHUXISLD-UHFFFAOYSA-N 1-cyclohexyl-2-cyclopentyl-3-methylbenzene Chemical compound Cc1cccc(C2CCCCC2)c1C1CCCC1 WNHVCSSHUXISLD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002441 X-ray diffraction Methods 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
- 230000000737 periodic effect Effects 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 229960003742 phenol Drugs 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000010544 hydroalkylation process reaction Methods 0.000 description 12
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000005804 alkylation reaction Methods 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 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
- 230000029936 alkylation Effects 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 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 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- -1 cyclic quinone imine Chemical class 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910021647 smectite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-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
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- NDYYRETYXBJDGQ-UHFFFAOYSA-N [O-2].[Ce+3].[O-2].[Ce+3] Chemical compound [O-2].[Ce+3].[O-2].[Ce+3] NDYYRETYXBJDGQ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 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
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 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
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004575 stone 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
- PPKHLPLHAGPKOJ-UHFFFAOYSA-N 1-cyclohexyl-2-pentylbenzene Chemical compound C(CCCC)C1=C(C=CC=C1)C1CCCCC1 PPKHLPLHAGPKOJ-UHFFFAOYSA-N 0.000 description 1
- BUXKULRFRATXSI-UHFFFAOYSA-N 1-hydroxypyrrole-2,5-dione Chemical compound ON1C(=O)C=CC1=O BUXKULRFRATXSI-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- AJBAWYJIQDVDEM-UHFFFAOYSA-N C=1(C(=C(C(N(C(=O)O)C(=O)O)=CC=1)C(=O)O)C(=O)O)C1=CC=C(N)C=C1 Chemical compound C=1(C(=C(C(N(C(=O)O)C(=O)O)=CC=1)C(=O)O)C(=O)O)C1=CC=C(N)C=C1 AJBAWYJIQDVDEM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229940100389 Sulfonylurea Drugs 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- NGPPDZPTIUGPEM-UHFFFAOYSA-N [Y+3].[O-2].[Mg+2] Chemical compound [Y+3].[O-2].[Mg+2] NGPPDZPTIUGPEM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- HQYOWPDUMCBSLQ-UHFFFAOYSA-L barium(2+);2,3-dihydroxybutanedioate Chemical compound [Ba+2].[O-]C(=O)C(O)C(O)C([O-])=O HQYOWPDUMCBSLQ-UHFFFAOYSA-L 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
- 150000001555 benzenes Chemical class 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
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- TZIBOXWEBBRIBM-UHFFFAOYSA-N cerium(3+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Ce+3] TZIBOXWEBBRIBM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 238000000605 extraction 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
- 150000002431 hydrogen 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
- 229910052500 inorganic mineral Inorganic materials 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
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 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
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing 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
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
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Description
本申請案主張2008年4月14日申請之USSN 61/044,678號之權益,其揭示內容以引用方式完全併入本文。
本發明關於一種製造環己基苯之方法,及隨意地將該所得之環己基苯轉化為苯酚及環己酮之方法。
苯酚是化學工業中的重要產品,例如,其可用來製造酚醛樹脂、雙酚A、ε-己內醯胺、己二酸、及增塑劑。
近來,苯酚製造最常用的路徑係Hock方法。此為三步驟方法,其中第一步驟包含使用丙烯將苯烷基化以產生異丙基苯,接著將異丙基苯氧化為相應之氫過氧化物,然後使該氫過氧化物裂解以產生等莫耳的苯酚和丙酮。然而,業界對苯酚的需求成長得比丙酮還快速。此外,由於丙烯開發上的不足,所以丙烯的成本可能會增加。因此,使用高級烯烴替代丙烯作為進料而共同產生高級酮類(而非丙酮)的方法可能是吸引人的製造苯酚之選擇性路徑。
例如,將環己基苯氧化(類似於異丙基苯之氧化作用)可提供製造苯酚的選擇性路徑,但不會有丙酮共同產生的問題。此選擇性路徑係共同生產環己酮,環己酮的市場正成長中,其可用作為工業溶劑、氧化反應中之活化劑及用於己二酸、環己酮樹脂、環己酮肟、己內醯胺及尼龍6之製造中。然而,此選擇性路徑需要開發製造環己基苯前驅物的商業上可用之方法。
多年來已知悉,環己基苯可藉由加氫烷基化方法或還原性烷基化方法自苯中製得。在此方法中,苯係在觸媒存在下與氫反應以使苯進行部份氫化而生成環己烯,然後該環己烯會將苯起始物質烷基化。因此,美國專利4,094,918號及4,177,165號揭示在含有經鎳-及稀土元素-處理之沸石及鈀促進劑的觸媒上將芳族烴加氫烷基化。類似地,美國專利4,122,125號及4,206,082號揭示使用釕及鎳化合物(其承載於經稀土元素處理之沸石上)作為芳族化合物加氫烷基化的觸媒。在這些先前技藝之方法中所用的沸石有沸石X和Y。此外,美國專利5,053,571號提出使用承載於貝它沸石上之釕及鎳作為芳族加氫烷基化的觸媒。然而,這些關於苯之加氫烷基化的早先提案卻遭受到一些問題,即對環己基苯之選擇率很低,特別是在經濟上可行的苯轉化率,以及產生大量不想要之副產物。
近來,美國專利6,037,513號已揭示在苯之加氫烷基化中環己基苯選擇率可藉由將苯和氫與一含有至少一種氫化金屬及MCM-22族之分子篩的雙功能觸媒接觸而增進。該氫化金屬較佳地係選自鈀、釕、鎳、鈷及其混合物,且該接觸步驟係在溫度約50至350℃、壓力約100至7000 kPa、苯對氫之莫耳比約0.01至100、及WHSV約0.01至100下進行。此‘513號專利也揭示該所得之環己基苯可接著被氧化為相應之氫過氧化物,及將該過氧化物分解為所欲之苯酚及環己酮。
然而,儘管近來的進展,將苯加氫烷基化以產生環己基苯卻仍未商業化。問題之一係該加氫烷基化反應所涉及的化學相當複雜,且除了所欲之環己基苯外還易於產生環己烷、甲基環戊烷、甲基環戊基苯、甲基環戊基-環己基苯、及二環己基苯。雖然二環己基苯可利用苯來進行轉烷基化而產生額外的環己基苯,但商業上可用之方法係需要使低價值之雜質的產生減至最少,因為要將這些雜質除去及/或處理是很昂貴的。在這些雜質中,甲基環戊烷及甲基環戊基苯特別不為人喜愛,因為彼等接近的沸點(各別地,相對於環己烷/苯及環己基苯)使得彼等非常難與環己基苯分離。而且,雖然環己烷可藉由脫氫作用而轉化回苯,但此舉代表一個昂貴且迂迴的進料提取路徑。
除了這些複雜性,還有關於經由將苯加氫烷基化而生成環己基苯以製造苯酚是否可為替代習知經由異丙基苯路徑的商業上可用之選擇性方案的明顯問題。然而,由於廣泛的研究,目前己建立觸媒組成物與方法參數之組合,以提供具有高環己基苯產率及低產量之不想要雜質的苯加氫烷基化方法。
在一方面中,本發明關於一種製造環己基苯之方法,該方法包含在加氫烷基化條件下使苯及氫與含有MCM-22族分子篩及至少一種氫化金屬之觸媒系統接觸,其中該條件包括溫度為約140℃至約175℃,壓力約135 psig至約175 psig(931 kPag,1032 kPa至1207 kPag,1308 kPa),氫對苯之莫耳比約0.30至約0.65及苯的每小時重量空間速度約0.26至約1.05 hr-1
。
合宜的是,該條件包括溫度為約150℃至約160℃及/或壓力為約145 psig至約155 psig(1000 kPag至1069 kPag)及/或氫對苯之莫耳比為約0.45至約0.64及/或苯的每小時重量空間速度為約0.3至約0.6 hr-1
。
合宜的是,該MCM-22族分子篩具有包含在12.4±0.25、6.9±0.15、3.57±0.07及3.42±0.07埃之晶格面距最大值的X-射線繞射圖式。在一具體實施例中,該MCM-22族分子篩係選自MCM-22、PSH-3、SSZ-25、ERB-1、ITQ-1、ITQ-2、MCM-36、MCM-49、MCM-56、UZM-8及彼等中任何二或多個之混合物,特別係選自MCM-22、MCM-49、MCM-56及彼等中任何二或多個之組合。
合宜的是,該至少一種氫化金屬係選自鈀、釕、鎳、鋅、錫、及鈷,而以鈀較佳。一般而言,該至少一種氫化金屬係以該觸媒系統重量計約0.05至約10重量%之量存在,例如介於約0.1至約5重量%之間。
在一具體實施例中,至少50重量%,如至少75重量%,及較佳地幾乎全部(亦即大於95、98、或99重量%)的該氫化金屬係承載在與該分子篩不同的無機氧化物上。合宜的是,該無機氧化物包括元素週期表中第2、4、13及14族之至少一種元素的氧化物,例如氧化鋁及/或氧化鈦及/或氧化鋯。
在另一方面中,本發明關於一種共同生產苯酚及環己酮之方法,該方法包含藉由本文所述之製程製造環己基苯,將環己基苯氧化以產生環己基苯氫過氧化物,並將該環己基苯氫過氧化物裂解以產生苯酚及環己酮。在較佳具體實施例中,該方法進一步包含將該環己酮脫氫以產生另外之苯酚。
本文揭示一種將苯加氫烷基化以產生環己基苯之方法,且在本發明之較佳具體實施例中,於第二步驟中將環己基苯轉化為環己酮及苯酚。目前此加氫烷基化方法除了產生所欲之一環己基苯產物外還產生二環己基苯,所以該方法可包含另一步驟,即以額外之苯將該二環己基苯轉烷基化而生成另外的一環己基苯產物。
本發明方法(其包含上述較佳具體實施例中之第一製程步驟)涉及在加氫烷基化條件下及加氫烷基化觸媒存在下使苯與氫接觸,依此,苯係進行下述之部份氫化/烷基化反應以產生環己基苯(CHB):
競爭性反應包括使苯完全飽和而生成環己烷(CH)、將苯二烷基化以產生二環己基苯(DCHB)及使苯進行重組/烷基化反應而產生雜質如甲基環戊烷(MCP)、甲基環戊基苯(MCPB)、及甲基環戊基-環己基苯(MCPCHB)。雖然可將二環己基苯轉烷基化以生成額外之CHB產物,但環己烷之轉化卻表示有價值之進料的損失,然而,如甲基環戊烷(MCP)及甲基環戊基苯(MCPB)之雜質則特別為人所不喜歡,因彼等之沸點和CHB非常接近,所以很難將MCP及MCPB與CHB分離。所以,在加氫烷基化反應中最重要的是使DCHB、MCP、及MCPB雜質之產生減至最低,以使這些物質在加氫烷基化產物混合物(本文中也稱為加氫烷基化流出物)中之濃度維持在可接受的低量。
根據本發明提供一種經最佳化的苯加氫烷基化方法,其係以高選擇率及在高產率下有效地將苯轉化為環己基苯(CHB),其中所產生之環己烷以加氫烷基化總流出物計較佳為小於或等於3重量%,及/或所產生之MCP、MCPB及MCPCHB加總起來較佳為小於或等於5重量%。典型地,所產生之二環己基苯(DCHB)以加氫烷基化總流出物計係小於15重量%。
任何市售之苯進料都可用於加氫烷基化步驟中,但較佳地係這些苯要具有至少99重量%之純度。同樣地,雖然氫來源也不受限制,但通常較喜歡的是該氫有至少99重量%純度。
合宜的是,加氫烷基化步驟之總進料含有小於1000 ppm,如小於500 ppm,例如小於100 ppm重量份之水,及/或小於100 ppm,如小於30 ppm,例如小於3 ppm重量份之硫,及/或小於10 ppm,如小於1 ppm,例如小於0.1 ppm重量份的氮。
加氫烷基化反應可在寬廣範圍的反應器結構中進行,包括固定床、漿體反應器、及/或催化蒸餾塔。再者,加氫烷基化反應可在單個反應區或數個反應區中進行,其中至少係將氫分階段地導入反應中。不論氫是連續地或分階段地送入反應中,重要的是送入反應之氫總莫耳數對送入反應之苯莫耳數的比介於0.30:1與0.65:1之間,例如介於約0.45:1與約0.64:1之間。尤其,從隨後之實施例中可明顯得知的是,將氫對苯之莫耳比控制在這些範圍內將可使環己基苯之產量增至最大且不會顯著地增加二環己基苯之產量。
該加氫烷基化反應所用之觸媒係為含有MCM-22族之分子篩及氫化金屬的雙功能觸媒。如本文所用之“MCM-22族物質”(或“MCM-22族之物質”或“MCM-22族之分子篩”)包括下述之一或多者:.由普通第一級結晶結構塊單位晶胞(該單位晶胞具有MWW型架構拓撲)所製得的分子篩。(單位晶胞係原子的空間排列,其若在三維空間中鋪陳即描述晶體構造。此晶體構造係揭示於〝Atlas of Zeolite Framework Types〞,Fifth edition,2001年,其全部內容以引用方式併入本文);.由普通第二級結構塊單位所製得的分子篩,其為此類MWW型架構拓撲之單位晶胞的二維鋪陳而形成一個單位晶胞厚度之單層(較佳為一個c-單位晶胞厚度);.由普通第二級結構塊單位所製得的分子篩,其為一或一個以上單位晶胞厚度之層,其中一個以上單位晶胞厚度之層係從堆疊、填密、或結合至少兩個具一個單位晶胞厚度的單層而製造。此第二級結構塊單位之堆疊可為規則方式、不規則方式、無規方式、或其任何組合;以及.由具有MWW型架構拓撲之單位晶胞的任何規則或無規之2維或3維組合所製得的分子篩。
MCM-22族之分子篩通常具有包含在12.4±0.25、6.9±0.15、3.57±0.07及3.42±0.07埃之晶格面距最大值的X-射線繞射圖式。用來特徵化該物質(b)之X-射線繞射數據係藉由標準技術獲得,例如利用銅之K-α二重線作為入射輻射及配備閃光計數器且連結電腦作為收集系統之繞射儀。MCM-22族之分子篩包括MCM-22(揭示於美國專利4,954,325號)、PSH-3(揭示於美國專利4,439,409號)、SSZ-25(揭示於美國專利4,826,667號)、ERB-1(揭示於歐洲專利0293032號)、ITQ-1(揭示於美國專利6,077,498號)、ITQ-2(揭示於國際專利公告WO97/17290號)、MCM-36(揭示於美國專利5,250,277號)、MCM-49(揭示於美國專利5,236,575號)、MCM-56(揭示於美國專利5,362,697號)、UZM-8(揭示於美國專利6,756,030號)、及彼等中二或多者的混合物。較佳的是,該分子篩係選自(a)MCM-49、(b)MCM-56及(c)MCM-49與MCM-56之同型物,如ITQ-2。
雖然適當之金屬包括鈀、釕、鎳、鋅、錫、及鈷,但任何已知之氫化金屬都可用於本發明之加氫烷基化觸媒中,且以鈀特別有利。通常,存在於觸媒中之氫化金屬的數量以該觸媒系統計,較佳地介於約0.05至約10重量%之間,例如介於約0.1至約5重量%之間。在一具體實施例中,若MCM-22族分子篩為鋁矽酸鹽之情況,則存在之氫化金屬的量係使該分子篩內之鋁對該氫化金屬之莫耳比在約1.5至約1500,例如約75至約750,如約100至約300。
氫化金屬可藉由例如浸漬或離子交換而直接承載在MCM-22族分子篩上。然而,在更多較佳具體實施例中,有至少50重量%,例如至少75重量%,及特別佳地為實質上全部(亦即至少95、98或99重量%)的該氫化金屬承載在與該分子篩複合但和分子篩分開(亦即不同)的無機氧化物上。尤其發現藉由將氫化金屬承載於無機氧化物上,當與等量之氫化金屬承載在分子篩上的觸媒比較時,則觸媒之活性及其對環己基苯及二環己基苯的選擇率將提高。
在此複合之加氫烷基化觸媒中所用的無機氧化物只要具安定性且在加氫烷基化反應之條件下呈惰性,就不需予以嚴格定義。適當之無機氧化物包括元素週期表中第2、4、13及14族之氧化物,例如氧化鋁、氧化鈦、及/或氧化鋯。如本文所用,週期表各族之編碼制係如Chemical and Engineering News,63(5),27(1985)中所揭示。
氫化金屬係在含金屬之無機氧化物與該分子篩複合之前,合宜地藉由浸漬而沉積在無機氧化物上。典型地,該觸媒複合物係藉由共粒化而製得,其中分子篩與含金屬之無機氧化物之混合物係在高壓下(通常為約350至約350,000 kPa)成形為顆粒,或藉由共擠壓而製得,其中分子篩與含金屬之無機氧化物的漿料將隨意地與各別之黏合劑一起而被強制通過模具。若需要時,可隨後地將額外之氫化金屬沉積在該所得之觸媒複合物上。
不論分開的無機氧化物是否配合著分子篩使用,該觸媒系統可額外地與黏合劑組合以促進其在本發明方法中之用途。適當之黏合劑包括合成或天然發生之物質及無機物質,如黏土、二氧化矽及/或金屬氧化物。金屬氧化物可為天然發生或凝膠狀沉澱物或凝膠之形式,包括二氧化矽與金屬氧化物之混合物。可用作為黏合劑之天然發生的黏土包括那些蒙脫石及高嶺士族的黏土,這些族群包括已知為Dixie、McNamee、Georgia及Florida黏土之亞膨潤土及高嶺土,或主要礦物組成為埃洛石、高嶺石、地開石、珍珠陶土或富矽高嶺石之其他者。此類黏土可依原始開採或最初鍛燒、酸處理或化學改質之原物料狀態使用。適當之金屬氧化物黏合劑包括二氧化矽、氧化鋁、氧化鋯、氧化鈦、二氧化矽-氧化鋁、二氧化矽-氧化鎂、二氧化矽-氧化鋯、二氧化矽-氧化釷、二氧化矽-氧化鈹及二氧化矽-氧化鈦,以及三元組成物如二氧化矽-氧化鋁-氧化釷、二氧化矽-氧化鋁-氧化鋯、二氧化矽-氧化鋁-氧化鎂及二氧化矽-氧化鎂-氧化鋯。
本發明方法中所用之條件在達成所欲之環己基苯選擇率上很重要,且包括溫度為約140℃至約175℃,特別是約150℃至約160℃,壓力為約931 kPag至1207 kPag(135 psig至約175 psig),特別是約1000 kPag至1069 kPag(145 psig至約155 psig),氫對苯之莫耳比約0.30至約0.65,特別是約0.45至約0.64,及苯之每小時重量空間速度約0.26至約1.05 hr-1
,特別是約0.3至約0.6 hr-1
。
經由使用這些條件及MCM-22族沸石,本發明之加氫烷基化方法可有效地將苯轉化為下表1所示之產物混合物(重量%)。
雖然此加氫烷基化步驟對環己基苯有很高的選擇率,但從表1中看出,來自加氫烷基化反應之流出物通常含有某些二烷基化產物,及未反應之芳族進料和所欲之一烷基化物質。未反應之芳族進料通常係藉由蒸餾回收並再循環至烷基化反應器中。將來自苯蒸餾之底部物進一步蒸餾以便將一環己基苯產物與任何二環己基苯及其他重質份分離。視存在於反應流出物之二環己基苯的數量而定,所希望的是以額外之苯將二環己基苯轉烷基化以使所欲之一烷基化物質的產量增至最大。
以額外之苯進行的轉烷基化通常係在不同於加氫烷基化反應器的轉烷基化反應器內及在適當之轉烷基化觸媒上進行,轉烷基化觸媒為諸如MCM-22族之分子篩、貝它沸石、MCM-68(參考美國專利6,014,018號)、沸石Y或發光沸石。轉烷基化反應典型地係在至少部份液相條件下進行,該條件適當地包括溫度為約100至約300℃、壓力約800至約3500 kPa、總進料之每小時重量空間速度約1至約10 hr-1
、及苯/二環己基苯重量比約1:1至約5:1。
在較佳具體實施例中,經由本發明之方法所產生的環己基苯係進一步轉化。因此,為了將環己基苯轉化為苯酚及環己酮,最初係將環己基苯氧化為相應之氫過氧化物。此舉係藉由將含氧氣體如空氣導入含有環己基苯之液相中而達成。和異丙基苯不同,沒有觸媒存在下之環己基苯的大氣氧化作用非常緩慢,因此該氧化作用普遍係在觸媒存在下進行。
用於環己基苯氧化步驟之適當觸媒為揭示於美國專利6,720,462號(其全部內容藉由引用方式併入本文)中之經N-羥基取代的環狀醯亞胺類,諸如N-羥基苯鄰二甲醯亞胺、4-胺基-N-羥基苯鄰二甲醯亞胺、3-胺基-N-羥基苯鄰二甲醯亞胺、四溴基-N-羥基苯鄰二甲醯亞胺、四氯基-N-羥基苯鄰二甲醯亞胺、N-羥基黑醯亞胺(N-hydroxyhetimide)、N-羥基腐植醯亞胺、N-羥基苯偏三甲醯亞胺、N-羥基苯-1,2,4-三甲醯亞胺、N,N’-二羥基(苯均四甲酸二醯亞胺)、N,N’-二羥基(二苯基酮-3,3’,4,4’-四甲酸二醯亞胺)、N-羥基馬來醯亞胺、吡啶-2,3-二甲醯亞胺、N-羥基琥珀醯亞胺、N-羥基(酒石酸醯亞胺)、N-羥基-5-原冰片烯-2,3-二甲醯亞胺、外-N-羥基-7-氧雜二環〔2.2.1〕庚-5-烯-2,3-二甲醯亞胺、N-羥基-順式-環己烷-1,2-二甲醯亞胺、N-羥基-順式-4-環己烯-1,2-二甲醯亞胺、N-羥基萘二甲醯亞胺鈉鹽或N-羥基-o-苯二磺醯亞胺。較佳地,該觸媒為N-羥基苯鄰二甲醯亞胺。另一適當之觸媒為N,N’,N”-三羥基三聚異氰酸。
這些觸媒物質可單獨使用或在自由基引發劑存在下使用,並可用作為液相、均質觸媒或經承載在固體載體上以提供異質觸媒。典型地,該經N-羥基取代之環狀醯亞胺或N,N’,N”-三羥基三聚異氰酸之使用量以環己基苯計為0.0001至15重量%,如0.001至5重量%。
氧化步驟的適當條件包括溫度介於約70至約200℃之間,如約90至約130℃,及壓力約50至10,000 kPa。任何含氧氣體(以空氣為較佳)都可用作為氧化介質。反應可在批次反應器或連續流動反應器中進行。可添加鹼性緩衝劑以與氧化期間所形成之酸性副產物反應。此外,也可導入水相,其可幫助使鹼性化合物(如碳酸鈉)溶解。
在將環己基苯轉化為苯酚及環己酮中的最終反應步驟涉及環己基苯氫過氧化物之裂解,合宜的是,此步驟係藉由在約20至約150℃溫度,如約40至約120℃及/或壓力約50至約2,500 kPa,如約100至約1000 kPa下,於液相中使該氫過氧化物與觸媒接觸來進行。環己基苯氫過氧化物較佳地係稀釋於對裂解反應呈惰性之有機溶劑中以協助熱之去除,溶劑為例如甲基乙基酮、環己酮、苯酚或環己基苯。裂解反應可合宜地在催化蒸餾裝置中進行。
裂解步驟中所用之觸媒可為均質觸媒或異質觸媒。
適當之均質性裂解觸媒包括硫酸、高氯酸、磷酸、鹽酸及對-甲苯磺酸。氯化鐵、三氟化硼、二氧化硫及三氧化硫也是有效的均質性裂解觸媒。較佳的均質性裂解觸媒為硫酸,且較佳濃度在0.05至0.5重量%範圍內。對均質性酸觸媒而言,較佳地是在裂解步驟後接著中和步驟。典型地此中和步驟包含與鹼性組分接觸,隨後傾析富含鹽之水相。
用於環己基苯氫過氧化物之裂解的適當之異質觸媒包括綠土黏土,如揭示於美國專利4,870,217號之酸性蒙脫石二氧化矽-氧化鋁黏土,該專利之全部內容在此以引用方式併入本文。
來自裂解步驟之粗製環己酮及粗製酚可進行另外之純化以製得純苯酚及環己酮。適當之純化過程包括,但不受限於,連續的蒸餾塔以便將該環己酮及苯酚與其他物質中分離。粗製或純的環己酮本身可進行脫氫作用以便轉化為苯酚。此脫氫作用可例如在觸媒如鉑、鎳或鈀上進行。
下述之實施例係為了說明之目的,故並不限制本發明之範圍。
觸媒係藉由將Pd觸媒與MCM-49觸媒共粒化而製備。該Pd觸媒係藉由將5公克γ氧化鋁浸漬在硝酸鈀溶液中,然後在空氣中及350℃下鍛燒該經Pd浸漬之氧化鋁3小時而製得。在氧化鋁上之Pd裝填量為0.3重量%。該MCM-49觸媒係藉由將一具有80重量% MCM-49及20重量%氧化鋁之壓出物碾碎至0.042cm(1/60”)或更細之顆粒而製得。接著將該Pd/Al2
O3
觸媒與碾碎之MCM-49/Al2
O3
以1:3重量比混合,接著使用在138 MPag(20,000 psig)下之手壓機將之製成顆粒以形成該共粒化之觸媒。然後將該觸媒分級至0.250 mm至0.149mm(60-100網目)之網孔以供試驗。
將8公克實施例1所製備之觸媒放在不銹鋼固定床式微反應器中。此反應器具有1.27cm(1/2英吋)之內直徑且在整個觸媒床的中央有一0.32cm(1/8英吋)的熱電偶套管。在300℃及1atm下以100cc/min之氫氣預處理該觸媒2小時。在氫氣中冷卻至155℃後,透過注射泵在60cc/小時下將苯送進反應器內達1小時,同時將反應器壓力增加至1034 kPag(150 psig)。然後將苯進料速率減小至0.52 WHSV並將氫/苯莫耳比調整至1.28。在冷凝產物阱中收集液體產物並離線分析。藉由改變四種方法變數並使用各種試驗條件來評估觸媒性能。表2顯示這些方法變數及其範圍。總共使用36個試驗條件來研究CHB之製造。
觸媒性能之結果顯示在表3至表6中,其中CHB表示環己基苯,DCHB表示二環己基苯,MCPB表示甲基環戊基苯及MCP-CHB表示甲基環戊基-環己基苯。表3顯示在試驗條件1至條件10下所得之試驗結果;表4、5及6各別顯示在試驗條件11至19、20至28、及29至36下所得之試驗結果。
利用表2至5中之數據,可評估方法變數對觸媒性能之影響。方法變數如溫度(縮寫為temp)、壓力(縮寫為press)、H2
/苯(Bz)莫耳比、及苯WHSV都顯示對觸媒性能有顯著的影響。圖1顯示彼等對苯轉化率之影響,及對環己烷(CH)、CHB及DCHB選擇率的影響。圖2顯示彼等對其他副產物如MCP(甲基環戊烷)、MCPB(甲基環戊基苯)、及MCP-CHB(甲基環戊基-環己基苯)之生成的影響。以這些結果為基礎,顯現出利用MCM-22族觸媒及一組經控制之方法條件,可製造高產率之環己基苯及非常低產量的不想要之雜質(特別是環己烷、MCP、MCPB及MCP-CHB)。
本發明已藉由參考特定具體實施例闡明解說,熟諳此藝者將明瞭本發明適合於本文中並不需要解說的變異。基於此理由,為了確定本發明之真正範圍起見,應僅參考隨附之申請專利範圍。
圖1(a)至(d)為方法變數溫度、壓力、氫對苯之莫耳比及苯之每小時重量空間速度對苯轉化率重量%(圖1(a))、環己烷(CH)選擇率(圖1(b))、環己基苯(CHB)選擇率(圖1(c))、及二環己基苯(DCHB)選擇率(圖1(d))之影響的圖表。
圖2(a)至(d)為方法變數溫度、壓力、氫對苯之莫耳比及苯之每小時重量空間速度對非CH及DCHB之雜質的總選擇率(圖2(a))、甲基環戊烷(MCP)選擇率(圖2(b))、甲基環戊基苯(MCPB)選擇率(圖2(c))、及甲基環戊基-環己基苯(MCPCHB)選擇率(圖2(d))之影響的圖表。
Claims (19)
- 一種製造環己基苯之方法,該方法包含在加氫烷基化條件下使苯及氫與含有MCM-22族分子篩及至少一種氫化金屬之觸媒系統接觸,其中該條件包括溫度為140℃至175℃,壓力為931kPag至1207kPag(135psig至175psig),氫對苯之莫耳比為0.30至0.65及苯的每小時重量空間速度為0.26至1.05hr-1 。
- 如申請專利範圍第1項之方法,其中該條件包括溫度為150℃至160℃及/或壓力為1000kPag至1069kPag(145psig至155psig)及/或氫對苯之莫耳比為0.45至0.64及/或苯的每小時重量空間速度為0.3至0.6hr-1 。
- 如申請專利範圍第1項之方法,其中該MCM-22族分子篩具有包含在12.4±0.25、6.9±0.15、3.57±0.07及3.42±0.07埃之晶格面距最大值的X-射線繞射圖式。
- 如申請專利範圍第1項之方法,其中該MCM-22族分子篩係選自MCM-22、PSH-3、SSZ-25、ERB-1、ITQ-1、ITQ-2、MCM-36、MCM-49、MCM-56、UZM-8及彼等中任何二或多個之混合物。
- 如申請專利範圍第4項之方法,其中該MCM-22族分子篩係選自MCM-22、MCM-49、MCM-56及彼等中任 何二或多個之組合。
- 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6項之方法,其中該氫化金屬包括鈀。
- 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以該觸媒系統重量計0.05至10重量%之量存在。
- 如申請專利範圍第8項之方法,其中該氫化金屬係以該觸媒系統重量計0.1至5重量%之量存在。
- 如申請專利範圍第1-9項中任一項之方法,其中至少50重量%之該氫化金屬係承載在與該分子篩不同的無機氧化物上。
- 如申請專利範圍第10項之方法,其中至少75重量%之該氫化金屬係承載在該無機氧化物上。
- 如申請專利範圍第11項之方法,其中實質上所有的該氫化金屬係承載在該無機氧化物上。
- 如申請專利範圍第10項之方法,其中該無機氧化物係與分子篩複合,且該氫化金屬係在該無機氧化物與分子篩複合之前施加在該無機氧化物上。
- 如申請專利範圍第10項之方法,其中該無機氧化物包括元素週期表中第2、4、13及14族之至少一種元素的氧化物。
- 如申請專利範圍第14項之方法,其中該無機氧 化物包括氧化鋁及/或氧化鈦及/或氧化鋯。
- 如申請專利範圍第1-9項中任一項之方法,其產生一含有環己基苯產物之流出物,該流出物還含有二環己基苯,且在轉烷基化條件下使至少一部份之該二環己基苯與苯接觸以生成另外之環己基苯。
- 如申請專利範圍第1-9項中任一項之方法,其中該加氫烷基化條件係經選擇以產生一含有不超過3重量%之環己烷及/或加總不超過5重量%之甲基環戊烷、甲基環戊基苯及甲基環戊基-環己基苯的加氫烷基化總流出物。
- 一種共同生產苯酚及環己酮之方法,該方法包含藉由申請專利範圍第1-9項中任一項之方法產生環己基苯,將該環己基苯氧化以產生環己基苯氫過氧化物,並使該環己基苯氫過氧化物裂解以產生苯酚及環己酮。
- 如申請專利範圍第18項之方法,其進一步包含將該環己酮脫氫以產生另外之苯酚。
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- 2009-02-24 WO PCT/US2009/034976 patent/WO2009128984A1/en active Application Filing
- 2009-02-24 US US12/920,383 patent/US8178728B2/en active Active
- 2009-02-24 CN CN200980112852.7A patent/CN101998942B/zh not_active Expired - Fee Related
- 2009-02-26 TW TW098106184A patent/TWI448445B/zh not_active IP Right Cessation
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CN101998942B (zh) | 2016-02-03 |
EP2297071B1 (en) | 2016-03-30 |
US20110015457A1 (en) | 2011-01-20 |
US8178728B2 (en) | 2012-05-15 |
WO2009128984A1 (en) | 2009-10-22 |
US20120178969A1 (en) | 2012-07-12 |
ES2573261T3 (es) | 2016-06-06 |
US8329956B2 (en) | 2012-12-11 |
EP2297071A1 (en) | 2011-03-23 |
CN101998942A (zh) | 2011-03-30 |
TW201000432A (en) | 2010-01-01 |
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