TWI460148B - 烷基化芳香族化合物之製造方法及酚之製造方法 - Google Patents
烷基化芳香族化合物之製造方法及酚之製造方法 Download PDFInfo
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- TWI460148B TWI460148B TW099107954A TW99107954A TWI460148B TW I460148 B TWI460148 B TW I460148B TW 099107954 A TW099107954 A TW 099107954A TW 99107954 A TW99107954 A TW 99107954A TW I460148 B TWI460148 B TW I460148B
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- Taiwan
- Prior art keywords
- producing
- aromatic compound
- zeolite
- cumene
- solid acid
- Prior art date
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- 150000001491 aromatic compounds Chemical class 0.000 title claims description 54
- 238000000034 method Methods 0.000 title description 64
- 230000008569 process Effects 0.000 title description 5
- 150000002989 phenols Chemical class 0.000 title description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 110
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 97
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 90
- 239000003054 catalyst Substances 0.000 claims description 69
- 229910021536 Zeolite Inorganic materials 0.000 claims description 49
- 239000010457 zeolite Substances 0.000 claims description 49
- 239000011973 solid acid Substances 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 238000004519 manufacturing process Methods 0.000 claims description 47
- 229910052709 silver Inorganic materials 0.000 claims description 44
- 239000004332 silver Substances 0.000 claims description 40
- 239000000126 substance Substances 0.000 claims description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 36
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 28
- -1 zeolite compound Chemical class 0.000 claims description 24
- 150000002576 ketones Chemical class 0.000 claims description 19
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 229910052680 mordenite Inorganic materials 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000011144 upstream manufacturing Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 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
- 239000006227 byproduct Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- LGXAANYJEHLUEM-UHFFFAOYSA-N 1,2,3-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1C(C)C LGXAANYJEHLUEM-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- OQXSRALAOPBHPM-UHFFFAOYSA-N 2-hydroxypropanoic acid;silver Chemical compound [Ag].CC(O)C(O)=O OQXSRALAOPBHPM-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000010555 transalkylation reaction Methods 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052614 beryl Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- OECMNLAWCROQEE-UHFFFAOYSA-N cyclohexylbenzene;hydrogen peroxide Chemical compound OO.C1CCCCC1C1=CC=CC=C1 OECMNLAWCROQEE-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- CLDWGXZGFUNWKB-UHFFFAOYSA-M silver;benzoate Chemical compound [Ag+].[O-]C(=O)C1=CC=CC=C1 CLDWGXZGFUNWKB-UHFFFAOYSA-M 0.000 description 1
- FTNNQMMAOFBTNJ-UHFFFAOYSA-M silver;formate Chemical compound [Ag+].[O-]C=O FTNNQMMAOFBTNJ-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000008096 xylene Substances 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
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/867—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an aldehyde or a ketone
-
- 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
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- 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
- B01J29/7007—Zeolite Beta
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Description
本發明係關於將芳香族化合物與酮及氫反應製造對應之烷基化芳香族化合物的方法,以及於一部分步驟中包含該方法之酚的製造方法。詳言之,係關於使用特定之觸媒,以單一反應步驟,使酮與芳香族化合物與氫反應製造烷基化芳香族化合物的方法,以及於步驟的一部分中包含該方法之酚的製造方法。
將苯與丙烯反應製造異丙苯的方法、將異丙苯氧化製造氫過氧化異丙苯的方法、將氫過氧化異丙苯酸解製造酚與丙酮的方法,分別為已知,組合該等反應之方法為一般被稱為異丙苯法的酚製造方法,係為現在酚製造法的主流。
此異丙苯法其特徵為合併產生丙酮,於同時期望丙酮的情況為長處,但在所得之丙酮比其所需更加過剩的情況,則與原料丙烯之價格差朝向不利的方向,使經濟性惡化。於是為了將與原料烯烴併產之酮的價格差導向有利方向,例如已提案將正丁烯與苯所得之第二丁基苯予以氧化、酸解,取得酚之同時取得甲基乙基酮的方法(參照專利文獻1、專利文獻2)。此方法中以第二丁基苯的氧化,目標氫過氧化第二丁基苯的選擇率僅為80%左右,且另外副生成15%以上的乙醯苯,故作為酚製造法的產率並不及異丙苯法。
更且亦已提案將環乙烯與苯所得的環己基苯予以氧化、酸解,取得酚與環己酮的方法。此方法中經由將所得的環己酮脫氫,取得酚,故於形式上可迴避酮的副生成。但是,以環己基苯之氧化反應,使目標氫過氧化環己基苯的產率低,且工業價值低。
於是,關於氧化及酸解產率最高的異丙苯法,為了依舊保持其優異性並且迴避與原料丙烯併產之丙酮的上述缺點,乃提案將併產的丙酮使用各式各樣的方法,以異丙苯法之原料型式再使用的方法。
丙酮經由氫化可輕易變換成異丙醇,提案將此異丙醇進一步經由脫水反應作成丙烯後,與苯反應取得異丙苯的步驟,即,以丙酮作為異丙苯法的原料予以再使用的步驟(參照專利文獻3)。但是,此方法具有增加氫化步驟和脫水步驟2步驟的問題點。
於是,提案將丙酮氫化所得之異丙醇直接與苯反應取得異丙苯的方法(參照專利文獻4~6)。特別於專利文獻6中,記載將併產的丙酮作成異丙醇,使用與苯反應所得之異丙苯製造酚的步驟性方法。但是於此方法中,亦比原來的異丙苯法增加氫化步驟。
因應此情況,作為不會增加先前異丙苯法的步驟並且將併產的丙酮再使用的方法,即丙酮與苯與氫直接反應的方法,已揭示使用固體酸物質與Cu化合物所構成的觸媒系統,在氫共存下反應的方法(參照專利文獻7)。
專利文獻1:日本專利特開昭57-91972號公報
專利文獻2:美國專利申請公開2004/0162448號說明書
專利文獻3:日本專利特開平2-174737號公報
專利文獻4:日本專利特開平2-231442號公報
專利文獻5:日本專利特開平11-35497號公報
專利文獻6:日本專利特表2003-523985號公報
專利文獻7:日本專利特表2005-513116號公報
但是專利文獻7中記載的方法,於取得異丙苯時具有副生成丙烷的傾向。
本發明係以提供將丙酮與苯與氫直接反應取得異丙苯之工業上、實用的製造方法為其目的。具體而言,係以提供以單一反應步驟,並以丙酮等之酮、苯等之芳香族化合物及氫作為起始物質,以高產率取得異丙苯等之烷基化芳香族化合物之新穎烷基化芳香族化合物的製造方法為其目的。更且,係以提供於一部分步驟中包含該方法,且比先前之異丙苯法不會伴隨步驟增加之酚的製造方法為其目的。
本發明者等人,為了解決上述問題致力檢討之結果,發現使用固體酸物質、和含銀觸媒作為觸媒,以單一反應步驟,並以丙酮等之酮、苯等之芳香族化合物及氫作為起始物質,可以高產率取得異丙苯等之烷基化芳香族化合物。
即,本發明之烷基化芳香族化合物之製造方法,其特徵為在固體酸物質、和含銀觸媒之存在下,使芳香族化合物與酮與氫反應。
本發明以上述芳香族化合物為苯,上述酮為丙酮為佳。
本發明以上述固體酸物質為沸石化合物為佳,且具有氧10~16員環細孔的沸石化合物為更佳,以具有氧10或12員環細孔的沸石化合物為特佳。
本發明以上述固體酸物質係由β沸石、絲光沸石、ZSM-5沸石、ZSM-12沸石、及Y型沸石所組成群中選出至少1種之沸石化合物為佳,且以β沸石為更佳。
本發明以上述含銀觸媒為包含載體上載持銀的載持觸媒為佳。
上述固體酸物質、與上述含銀觸媒以混合之狀態進行反應為佳。
本發明之酚之製造方法,係包含下列步驟之酚之製造方法,
(a) 將異丙苯氧化變換成氫過氧化異丙苯的步驟、
(b) 將氫過氧化異丙苯酸解合成酚與丙酮的步驟、
(c) 將上述步驟(b)中生成的丙酮與氫及苯反應合成異丙苯的步驟、
(d) 將上述步驟(c)所得之異丙苯循環至步驟(a)的步驟,其特徵以上述烷基化芳香族化合物之製造方法進行步驟(c)。
若根據本發明之烷基化芳香族化合物的製造方法,則可以單一反應步驟,以丙酮等之酮、苯等之芳香族化合物及氫作為起始物質,取得異丙苯等之烷基化芳香族化合物。如上述,上述製造方法為工業上實用的方法。又,於一部分步驟中包含該烷基化芳香族化合物之製造方法之酚的製造方法,不會增加先前的異丙苯法步驟數,且併產的丙酮可再使用。但是,根據該烷基化芳香族化合物之製造方法所得的異丙苯,與得自丙烯或異丙醇和苯的異丙苯於品質上無任何差異。因此,本發明為了不起的技術,可生產步驟上及經濟上顯著優異的酚。
本發明之烷基化芳香族化合物之製造方法,其特徵為在固體酸物質、與含銀觸媒之存在下,使芳香族化合物與酮與氫反應。
於本發明中,若使用上述固體酸物質和上述含銀觸媒二成分即可,關於其利用方法並無特別限制,將酸觸媒成分之上述固體酸物質、與上述含銀觸媒以公分尺寸之觸媒粒子程度予以物理混合即可,亦可將兩者微細化混合後改變成型為公分尺寸的觸媒粒子,更且將作用為酸觸媒之上述固體酸物質作為載體並於其上載持上述含銀觸媒亦可,且亦可相反地以上述含銀觸媒作為載體並於其上載持上述固體酸物質。
又,將上述固體酸物質、與含銀觸媒以混合狀態進行上述反應為更佳。
本發明所用之固體酸物質,係具有作為酸機能的觸媒,若為一般稱為固體酸者即可,可使用沸石化合物、二氧化矽氧化鋁、氧化鋁、硫酸離子載持氧化鋯、WO3
載持氧化鋯等。
特別,主要由矽和鋁所構成之無機結晶性多孔質化合物的沸石化合物,由耐熱性、和目的烷基化芳香族化合物之選擇率方面而言,為適當的烷基化觸媒。作為沸石化合物,根據使用作為原料的芳香族化合物及目的烷基化芳香族化合物的分子徑,使適當的沸石化合物為不同。
例如使用苯作為芳香族化合物,使用丙酮作為酮,製造作為烷基化芳香族化合物之異丙苯之情況,使用具有氧10~16員環細孔的沸石化合物作為沸石化合物為佳。
作為具有氧10~16員環細孔的沸石化合物,可列舉鎂鹼沸石、片沸石、ZSM-5沸石、ZSM-11沸石、ZSM-12沸石、NU-87沸石、θ沸石、方柱石、X型沸石、Y型沸石、USY型沸石、絲光沸石、脫鋁絲光沸石、β沸石、鈉菱沸石、矽鉀鋁石、loverite、VPI-5沸石、UTD-1沸石等。另外,所謂氧10員環,係表示細孔徑的大小,意指構成細孔之環構造中所含之氧原子數為10的大小。
該等沸石化合物中,亦以具有與異丙苯分子徑相同程度細孔者為適當,使用具有氧10或12員環細孔之沸石化合物為更佳。作為具有氧10或12員環細孔之沸石化合物,可列舉Y型沸石、USY型沸石、絲光沸石、脫鋁絲光沸石、β沸石、ZSM-12沸石、ZSM-5沸石等。其中由異丙苯選擇性方面而言,以β沸石、絲光沸石、ZSM-5沸石;ZSM-12沸石、Y型沸石為更佳,且以β沸石為特佳。
該等沸石化合物中之矽與鋁之組成比(矽/鋁)若為2/1~200/1之範圍即可,特別由活性和熱安定性方面而言,以5/1~100/1者為佳。更且,亦可使用將沸石骨架中所含之鋁原子,以Ga、Ti、Fe、Mn、B等之鋁以外的金屬更換之所謂的同型取代的沸石化合物。
固體酸物質的形狀並無特別限制,可為球狀、圓柱狀、擠出狀、破碎狀之任一種,其粒子大小亦以0.01m~100mm之範圍根據反應器大小選定即可。
另外,該等固體酸物質可使用單獨一種,且亦可使用2種以上。
作為本發明所用之含銀(Ag)觸媒(觸媒組成物),可列舉含有Ag金屬本身者、以金屬化合物型式含有者等。
例如,可列舉Ag2
O等之氧化銀、AgCl、AgBr、AgI等之鹵化銀、Pt-Ag、Pd-Ag等之簇金屬型式含有者。
作為其他例,可列舉硝酸銀、乳酸銀、醋酸銀、苯甲酸銀、碳酸銀、鉻酸銀、甲酸銀、氰化銀等。
含銀觸媒若具有可將羰基官能基氫化至醇能力者即可,並無特別限制,所謂以氫化觸媒型式販售者可直接使用,且在各種載體上載持的載持觸媒等可在市場上取得。
如此,含銀觸媒,包含載體上載持銀的載持觸媒(Ag在載體上載持者)為佳。
作為載體,例如可使用二氧化矽、氧化鋁、二氧化矽-氧化鋁、二氧化鈦、氧化鎂、二氧化矽-氧化鎂、氧化鋯、碳、酸性白土、矽藻土。其中,亦由二氧化矽、氧化鋁、二氧化矽-氧化鋁、二氧化鈦、氧化鎂、二氧化矽-氧化鎂、氧化鋯、碳之中選出至少1種為佳。
另外,該等含銀觸媒可使用單獨一種,且亦可使用二種以上,含銀觸媒之形狀並無特別限制,可為球狀、圓柱狀、擠出狀、破碎狀之任一種,其粒子大小亦以0.01mm~100mm之範圍,根據反應器大小選定即可。
該等含銀觸媒,亦可被載持至上述固體酸物質,具體而言,根據固體酸物質於Ag之硝酸鹽水溶液中含浸、煅燒之方法、和作成使Ag於有機溶劑中可溶之配位基結合有機分子的錯合物型式,於有機溶劑中添加,調整溶液,並將固體酸物質於該溶液中含浸、煅燒的方法則可取得。更且,將錯合物中某物質於真空下汽化蒸鍍等之方法載持至固體酸物質亦可。又,由對應固體酸物質之金屬鹽取得時,亦可採用使作為氫化觸媒的Ag鹽共存,同時進行載體合成和含金屬觸媒之載持的共沉法。
於本發明中,作為芳香族化合物,可例示碳數6~20之化合物,可列舉例如苯、甲苯、二甲苯等之苯同族體、該等之取代基衍生物、萘、甲基萘等之萘同族體、該等之取代基衍生物等。又,作為酮,可例示碳數3~20之化合物,可利用對象物和非對象物。作為結合至羰基之基,可例示烷基、芳基,具體而言,可列舉丙酮、甲基乙基酮、乙醯苯等。
該等之中亦以使用苯作為芳香族化合物、使用丙酮作為酮,製造異丙苯的反應於工業上為最重要的。此時,苯與丙酮之莫耳比(苯/丙酮)以1~20為佳。若低於上述範圍,則二異丙基苯、三異丙基苯的生成量有變大之傾向。二異丙基苯、三異丙基苯在異丙苯步驟中,經由與苯的轉烷基化而可能恢復成異丙苯,但轉烷基化為反應溫度高,若剩餘的二異丙基苯、三異丙基苯的份量多,則蒸氣費用增大且有時不經濟。又,若高於上述範圍,則以反應器的後步驟回收過剩的苯時,因為對蒸餾塔造成負荷,故有時不經濟。
本發明之芳香族化合物與酮的反應,係以氫共存下進行為其特徵。此處所謂之氫,可為分子狀的氫氣,亦可為反應條件下發生氫之由環己烷等烴類所發生的氫。丙酮與苯與氫反應時,原理上,氫若與丙酮等莫耳以上即可,由分離回收方面而言,適當範圍為相對於丙酮,以1~50倍莫耳、較佳為1~30倍莫耳。欲將丙酮轉換率抑制於未滿100%時,將所用之氫量由1倍莫耳減低即可因應。又,於本發明反應中供給的氫,與丙酮所具有的氧原子反應變成水並伴隨異丙苯可由反應器出口取出。又,丙酮當量以上的氫只要不進行不欲的副反應,於本質上不被消耗。
對於反應系統添加氫氣之情況,通常連續供給,但並非特別限定於此方法,亦可在反應開始時添加氫氣後停止反應中供給,並且於某一定時間後再度供給的間歇性供給,且在液相反應時使氫氣溶解於溶劑並供給亦無妨。又,在再循環步驟中,將輕沸餾分與自塔頂回收之氫氣同時供給亦可。添加氫的壓力一般與反應器壓力同等,但若根據氫的供給方法適當變更即可。
進行本反應時,其方法、條件並無特別限制,例如,可採用下列所示之條件、方法。
反應原料丙酮與苯與氫氣的接觸,可為氣液向流、氣液併流等任一者,又,氣體的方向可為液下降-氣體上升、液上升-氣體下降、液氣上升、液氣下降之任一者。
關於反應溫度於本發明中亦無特別限定,較佳為50~300℃、更佳為60~200℃之範圍。又,通常較佳的實施壓力範圍為0.1~500氣壓、更佳為0.5~100氣壓。
又,實施本發明時,使用之觸媒量(固體酸物質與含銀觸媒之合計量)並無特別限定,例如,使用固定床流通裝置進行反應時,若以每時間之原料(酮+芳香族化合物)供給量(重量),除以觸媒重量(固體酸物質與含銀觸媒之合計量)之值,即WHSV表示,則期望為0.01~100/h之範圍,更佳為0.05~50/h之範圍為適當。
另外,上述固體酸物質、與含銀觸媒之使用量比並無特別限定,通常固體酸物質:上述含銀觸媒(重量比)為1:0.01~1:100,較佳為1:0.05~1:50。剩餘之固體酸物質的重量比若小,則無法充分進行烷基化反應,異丙苯等之烷基化芳香族化合物的產率降低,故有時不經濟。又,剩餘之固體酸物質的重量比若大,則丙酮的轉換率降低,其有時亦不經濟。
於本發明之烷基化芳香族化合物之製造方法中,經由上述含銀觸媒之作用,酮被氫化生成醇後,該醇、與芳香族化合物,經由固體酸物質的作用而被烷基化成為烷基化芳香族化合物。即,本發明之製造方法中,階段性引起氫化及烷基化。
本發明中反應形式為固定床反應之情況,固體酸物質與上述含銀觸媒之填充方法有時對反應成績造成大影響。如上述,本發明中氫化與烷基化為階段性引起。因此,根據反應各階段依序填充適當的觸媒種,以有效率使用觸媒的意義、和抑制非目的之副反應的意義為佳。
特別為了提高反應速度而增大氫壓和溫度之情況,於一般的化學反應中經常看見引起低氫壓和低反應溫度所未見之不佳的副反應舉動,於此種情況中,觸媒的填充方法特別對於反應成績有造成大影響的可能性。
作為根據反應之各階段依序填充適當觸媒種的方法,可列舉例如,(1)將固體酸物質及上述含銀觸媒均勻混合、填充之方法、(2)將上述含銀觸媒的濃度由觸媒層的上游側往下游側以一定比例減少,同時將固體酸物質的濃度由上游側往下游側以一定比例增大般填充的方法、(3)填充載持上述含銀觸媒之固體酸物質的方法、(4)以形成上述含銀觸媒所構成之層(上游側)、和固體酸物質及上述含銀觸媒所構成之層(下游側)般填充的方法、(5)以形成上述含銀觸媒所構成之層(上游側)、和載持上述含銀觸媒之固體酸物質所構成之層(下游側)般填充的方法、(6)以形成固體酸物質及上述含銀觸媒所構成之層(上游側)、和固體酸物質所構成之層(下游側)般填充的方法、(7)以形成載持上述含銀觸媒之固體酸物質所構成之層(上游側)、和固體酸物質所構成之層(下游側)般填充的方法等。另外,所謂上游側,係表示反應器的入口側,即原料通過反應前半層,所謂下游側,係表示反應器的出口側,即通過反應後半之層。
實施本發明時,亦可在反應系統內添加對於觸媒及反應試劑為惰性的溶劑或氣體、並以稀釋的狀態進行。
實施本發明時,此方法可於批次式、半批次式、或連續流通式之任一種方法中實施。於液相、氣相、氣-液混合相之任一種形態中亦可實施。作為觸媒的填充方式,可採用固定床、流動床、懸浮床、棚段固定床等各種方式,且以任一種方式實施均無妨。
實施本發明時,期望以公知方法將固體酸物質及含銀觸媒予以脫水。於固定床反應方式之情況,一邊對填充固體酸物質及含金屬觸媒之反應器流通氮、氦等惰性氣體,一邊於300℃以上之溫度保持10分鐘以上即可。更且為了使氫化觸媒之含銀觸媒表現活性,亦可在脫水處理後,於氫氣流下進行處理。
於某經過時間中觸媒活性降低之情況,以公知方法進行再生並可恢復固體酸物質及含銀觸媒的活性。
為了維持異丙苯等之烷基化芳香族化合物的生產量,亦可採取將2個或3個反應器並列,且在一個反應器再生之間,以剩餘的1個或2個反應器實施反應的旋轉方式亦無妨。更且於反應器為3個之情況,亦可採用將其他反應器以2個直列連接,生產量變動少的方法。又,以流動床流通反應方式和移動床反應方式實施之情況,由反應器中連續或斷續抽出一部分或全部觸媒,並且經由補充相當部分則可維持一定的活性。
如上處理,根據本發明之烷基化芳香族化合物之製造方法,例如可由酚製造時之副生成的丙酮直接取得異丙苯。
如上述處理所得之異丙苯可利用作為酚與丙酮的製造原料。具體而言,上述製造方法包含下列步驟(a)~(d),可利用於將異丙苯氧化,其次分解製造酚的步驟等,更且提供各種改良法亦無問題。另外,步驟(c)可根據上述之烷基化芳香族化合物之製造方法實施。
(a) 將異丙苯氧化變換成氫過氧化異丙苯的步驟
(b) 將氫過氧化異丙苯酸解合成酚與丙酮的步驟
(c) 將上述步驟(b)生成的丙酮與氫及苯反應合成異丙苯的步驟
(d) 將上述步驟(c)所得之異丙苯於步驟(a)循環的步驟。
換言之,本發明之酚之製造方法包含
(a) 將異丙苯氧化變換成氫過氧化異丙苯的步驟;
(b) 將氫過氧化異丙苯酸解合成酚與丙酮的步驟;
(c) 將上述步驟(b)生成的丙酮與氫及苯反應合成異丙苯的步驟、及
(d) 將上述步驟(c)所得之異丙苯循環至步驟(a)的步驟;並以上述之烷基化芳香族化合物之製造方法進行步驟(c)。即,步驟(c)中,在固體酸物質,與含銀觸媒之存在下,將芳香族化合物與酮與氫反應。
若根據此種步驟(c),可以單一反應步驟,將副生成的丙酮變換成異丙苯,且該異丙苯可使用作為製造酚的原料。
另外,於上述酚之製造方法中,步驟(a)只要可取得氫過氧化異丙苯則無特別限制,可依先前方法進行,且步驟(b)只要可取得酚與丙酮則無特別限制,可依先前方法進行。
又,步驟(a)中最初裝入的異丙苯,可為根據先前方法所得者,且亦可根據上述烷基化芳香族化合物之製造方法所得者。
[實施例]
其次示出實施例進一步詳細說明本發明,但本發明不被限定於此。
[實施例1]
[觸媒之調製]
於300毫升之茄型燒瓶中裝入矽膠粉末(富士Silicia化學公司製、Carriacut Q-15)30.0克,並加入乳酸銀0.5水合物(和光純藥製)6.4克溶解於離子交換水100毫升的溶液。於10mmHg之減壓下,以40~50℃餾除水,並於氮氣流下乾燥一晚。其次於氫環境氣體下,由100℃歷5小時升溫至320℃進行還原處理。放冷後,取得黑色粉末型式的32.9克10%Ag/矽膠觸媒(載持觸媒)。
[異丙苯之製造]
使用設置高壓用餵料泵、高壓用氫質量流、高壓用氮質量流、電爐、具有觸媒填充部分之反應器、設有背壓閥的固定床反應裝置,並以向下流動進行加壓液相流通反應。
於內徑1公分的SUS 316製反應器中,將上述10% Ag/矽膠觸媒以20MPa壓縮成型後,將分級至250~500μm者:6.0g與β沸石(觸媒化成公司製、以20MPa壓縮成型後,分級至250~500μ者)1.0克混合作成觸媒層並填充。
以氫加壓至4.5MPa後,於8.3ml/分鐘之氫氣流下,以175℃將苯/丙酮(5/1莫耳)之混合液以0.50g/h(WHSV=0.07/h、氫/丙酮莫耳比=20)之比例流通。
於反應器之出口採樣反應物,並以氣相層分別分析氣相、液相。
反應結果如表1所示般,與後述之比較例1相比較,可知可高選擇性生成異丙苯。
[比較例1]
於實施例1中,除了使用亞鉻酸銅(SudChemie公司製、製品名G99b、元素質量% Cu 35%、Cr31%、Ba2%、Mn3%)1.0克代替10% Ag/矽膠觸媒以外,同樣進行反應。反應結果如表1所示般,副生成許多丙烷。
若根據本發明,使酮與芳香族化合物直接反應,可取得單一反應步驟對應之烷基化芳香族化合物。如此,本發明於工業上為實用的。若使用此方法,可由異丙苯法製造酚時之副生成的丙酮直接取得異丙苯。如此處理所得之異丙苯可利用作為酚與丙酮的製造原料,可利用於將異丙苯氧化其次分解的步驟等。
Claims (10)
- 一種烷基化芳香族化合物之製造方法,其特徵為,在固體酸物質與含銀觸媒之存在下,將芳香族化合物與酮與氫反應。
- 如申請專利範圍第1項之烷基化芳香族化合物之製造方法,其中,上述芳香族化合物為苯,上述酮為丙酮。
- 如申請專利範圍第1項之烷基化芳香族化合物之製造方法,其中,上述固體酸物質為沸石化合物。
- 如申請專利範圍第1項之烷基化芳香族化合物之製造方法,其中,上述固體酸物質為具有氧10~16員環細孔的沸石化合物。
- 如申請專利範圍第1項之烷基化芳香族化合物之製造方法,其中,上述固體酸物質為具有氧10或12員環細孔的沸石化合物。
- 如申請專利範圍第1項之烷基化芳香族化合物之製造方法,其中,上述固體酸物質係由β沸石、絲光沸石、ZSM-5沸石、ZSM-12沸石、及Y型沸石所組成群中選出之至少1種的沸石化合物。
- 如申請專利範圍第1項之烷基化芳香族化合物之製造方法,其中,上述固體酸物質為β沸石。
- 如申請專利範圍第1項之烷基化芳香族化合物之製造方法,其中,上述觸媒包含載持觸媒,該載持觸媒係在載體上 載持銀者。
- 如申請專利範圍第1項之烷基化芳香族化合物之製造方法,其中,在上述固體酸物質與含銀觸媒混合之狀態下進行反應。
- 一種酚之製造方法,其包含下列步驟:(a)將異丙苯氧化而變換成氫過氧化異丙苯的步驟;(b)將氫過氧化異丙苯予以酸解而合成酚與丙酮的步驟;(c)將上述步驟(b)中生成的丙酮與氫及苯反應而合成異丙苯的步驟;以及(d)將上述步驟(c)所得之異丙苯循環至步驟(a)的步驟;其中,以申請專利範圍第1項之烷基化芳香族化合物之製造方法進行步驟(c)。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040111001A1 (en) * | 2002-12-06 | 2004-06-10 | Dandekar Ajit Bhaskar | Aromatic alkylation process |
JP2004250430A (ja) * | 2002-12-24 | 2004-09-09 | Sumitomo Chem Co Ltd | クメンの製造方法 |
EP1456154A1 (en) * | 2001-12-20 | 2004-09-15 | Polimeri Europa S.p.A. | Process for the alkylation of aromatic compounds |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5148477B2 (zh) | 1974-04-03 | 1976-12-21 | ||
US4092372A (en) * | 1975-04-03 | 1978-05-30 | Takeda Chemical Industries, Ltd. | Catalyst for the production of isoprene |
US4276438A (en) | 1980-05-27 | 1981-06-30 | Mobil Oil Corporation | Shape selective reactions with group IB modified zeolite catalysts |
JPS5791972A (en) | 1980-11-27 | 1982-06-08 | Sumitomo Chem Co Ltd | Preparation of hydroperoxide |
US4480134A (en) * | 1983-04-05 | 1984-10-30 | General Electric Company | Process for preparing phenol and acetone from cumene |
US4550218A (en) * | 1984-03-05 | 1985-10-29 | Mobil Oil Corporation | Hydrocarbon synthesis with zeolite catalyst of improved hydrothermal stability |
JP2774607B2 (ja) | 1988-09-30 | 1998-07-09 | 三井化学株式会社 | フェノールの製造方法およびその製造時の副生アセトンからプロピレンを得る方法 |
US5017729A (en) | 1988-09-30 | 1991-05-21 | Mitsui Petrochemical Industries, Ltd. | Phenol preparation process and propylene recovery therefrom |
JPH02231442A (ja) | 1988-11-28 | 1990-09-13 | Mitsui Petrochem Ind Ltd | フェノールの製造方法 |
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JPH1135497A (ja) | 1997-07-15 | 1999-02-09 | Mitsui Chem Inc | クメンの製造方法 |
DE10008924A1 (de) | 2000-02-25 | 2001-09-06 | Phenolchemie Gmbh & Co Kg | Verfahren zur Herstellung von Phenol |
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ES2363571T3 (es) * | 2007-02-23 | 2011-08-09 | Mitsui Chemicals, Inc. | Proceso para preparar un compuesto aromático alquilado. |
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