CN106179338B - 用于制备邻苯基苯酚的催化剂组合物及用该催化剂组合物制备邻苯基苯酚的方法 - Google Patents
用于制备邻苯基苯酚的催化剂组合物及用该催化剂组合物制备邻苯基苯酚的方法 Download PDFInfo
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- CN106179338B CN106179338B CN201510309001.9A CN201510309001A CN106179338B CN 106179338 B CN106179338 B CN 106179338B CN 201510309001 A CN201510309001 A CN 201510309001A CN 106179338 B CN106179338 B CN 106179338B
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- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 235000010292 orthophenyl phenol Nutrition 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims description 42
- 239000000203 mixture Substances 0.000 title abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 93
- 239000002184 metal Substances 0.000 claims abstract description 93
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 14
- 239000011651 chromium Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 10
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 10
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 10
- 239000010948 rhodium Substances 0.000 claims abstract description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052713 technetium Inorganic materials 0.000 claims abstract description 10
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 65
- 229910052799 carbon Inorganic materials 0.000 claims description 63
- 239000003426 co-catalyst Substances 0.000 claims description 41
- JHIVVAPYMSGYDF-PTQBSOBMSA-N cyclohexanone Chemical class O=[13C]1CCCCC1 JHIVVAPYMSGYDF-PTQBSOBMSA-N 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 9
- 235000011151 potassium sulphates Nutrition 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910008253 Zr2O3 Inorganic materials 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 31
- 229910052741 iridium Inorganic materials 0.000 abstract description 17
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 17
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- -1 1- cyclohexenyl Chemical group 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds 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
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 150000004690 nonahydrates Chemical class 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- KSQXVLVXUFHGJQ-UHFFFAOYSA-M Sodium ortho-phenylphenate Chemical compound [Na+].[O-]C1=CC=CC=C1C1=CC=CC=C1 KSQXVLVXUFHGJQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical class CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- UQPLZHUFLPDORW-UHFFFAOYSA-N 2-phenylphenol;sodium Chemical compound [Na].OC1=CC=CC=C1C1=CC=CC=C1 UQPLZHUFLPDORW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UZXDEYWUHSZPLQ-UHFFFAOYSA-N ClC1=CC=CC=C1.[S] Chemical compound ClC1=CC=CC=C1.[S] UZXDEYWUHSZPLQ-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- OOOYJJANGWVIRW-UHFFFAOYSA-N chlorobenzene;phenol Chemical compound OC1=CC=CC=C1.ClC1=CC=CC=C1 OOOYJJANGWVIRW-UHFFFAOYSA-N 0.000 description 1
- LUJMWSICLDRZJO-UHFFFAOYSA-N chromium(3+) nonahydrate Chemical compound [Cr+3].O.O.O.O.O.O.O.O.O LUJMWSICLDRZJO-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000004687 hexahydrates Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XULHHXCGBHJODI-UHFFFAOYSA-N iridium(3+);hydrate Chemical compound O.[Ir+3] XULHHXCGBHJODI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- XRQVVFIEYAHKBV-OGYJWPHRSA-N opp protocol Chemical compound CNNCC1=CC=C(C(=O)NC(C)C)C=C1.O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1.C([C@H](C[C@]1(C(=O)OC)C=2C(=C3C([C@]45[C@H]([C@@]([C@H](OC(C)=O)[C@]6(CC)C=CCN([C@H]56)CC4)(O)C(=O)OC)N3C=O)=CC=2)OC)C[C@@](C2)(O)CC)N2CCC2=C1NC1=CC=CC=C21 XRQVVFIEYAHKBV-OGYJWPHRSA-N 0.000 description 1
- 239000004306 orthophenyl phenol Substances 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000010294 sodium orthophenyl phenol Nutrition 0.000 description 1
- 239000004307 sodium orthophenyl phenol Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali 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
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
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Abstract
一种用于制备邻苯基苯酚的催化剂组合物,包括:载体;以及承载于该载体上的第一活性金属、第二活性金属、助催化剂。该第一活性金属为铂,且该第二活性金属选自铬、锰、铁、钴、镍、钼、锝、钌、铑、钯、钨、铼、锇或铱。本发明通过将该第一活性金属、第二活性金属、助催化剂承载于载体上,得以提升邻苯基苯酚的选择率并延长催化剂寿命。
Description
技术领域
本发明有关一种催化剂组合物,尤指一种用于制备邻苯基苯酚的催化剂组合物。
背景技术
邻苯基苯酚(ortho-Phenylphenol,OPP)是一种用途极为广泛的化工产品,不仅可作为蔬果的防腐剂,亦可进一步使用于合成作为磷系阻燃剂中间体的9,10-二氢-9-氧杂-磷杂菲-10-氧化物(9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,DOPO)、作为防腐杀菌剂及染色载体的邻苯基苯酚钠盐(Sodium ortho-phenylphenol,SOPP)、作为光学材料的邻苯基苯氧乙基丙烯酸酯(ortho-Phenyl phenoxy ethyl acrylate,OPPEA),还可应用于热稳定剂及表面活性剂等其他领域。
邻苯基苯酚有许多种合成工艺,主要分为分离法及合成法。分离法是在以氯苯磺化生产苯酚时,分离纯化蒸馏残余物而得到邻苯基苯酚,但因苯酚生产方式逐渐改变,且此方法的反应条件较为严苛及得到的产量有限,现已不适用。
因此,生产邻苯基苯酚以合成法最广为使用,其中,合成法又依据使用的原料不同细分为联苯磺化(卤化)水解法、氯苯苯酚偶合法等多种方式。目前工业上大多采用取得容易且价格便宜的环己酮作为原料,先进行缩合反应生成二聚物(2-(1-环己烯基)环己酮或2-环己亚烷基环己酮),接着再进行脱氢反应得到产物邻苯基苯酚,其反应如下式(Ⅰ)所示。
以环己酮二聚物制备邻苯基苯酚的反应中,所使用的催化剂大致可分为金属合金催化剂、负载型非贵金属催化剂以及负载型贵金属催化剂三种类型,其中,金属合金催化剂相较于其他种类催化剂,于反应时容易有烧结现象产生,且对产物邻苯基苯酚的选择率较低、稳定性较差、合成工艺较为复杂。举例而言,如US 3,932,536A使用镍-铜-铝-铬合金催化剂,初始邻苯基苯酚选择率为81%,反应1,000小时后,选择率降至70%。
再者,负载型催化剂一般使用氧化铝、活性碳、氧化硅或其他金属氧化物等单一物或复合物作为载体,非贵金属催化剂因未使用贵金属作为活性组份,可有效降低成本。然而,前述负载型非贵金属催化剂经反应300小时后,该转化率及收率虽无变化,但该负载型非贵金属催化剂的催化剂活性及反应性仍无法满足工业化生产的标准。
显然前述金属合金催化剂与负载型非贵金属催化剂存在催化剂寿命、催化剂活性及反应性不足以应用于工业化生产的缺失。
贵金属催化剂常使用铂、钯作为活性组份,此类型催化剂为最早应用在生产邻苯基苯酚,如CN 1371897A所示,使用含钯的分子筛催化剂,虽二聚体的初始转化率达98%,邻苯基苯酚的选择率为100%。但是,在反应200小时后,二聚体的转化率降至92%,邻苯基苯酚的选择率则降至97%。
除此之外,为了提升催化剂活性,通常会再加入其他助催化剂进行催化剂改性。如中国石油大学学报:自然科学版,2012,36(3):165-174所示,使用铂负载于氧化铝的催化剂,研究助催化剂碳酸钾加入的时机及用量,有效地使选择率提升至94%。然而,如化工进展,2004,23(1):59-61所示,使0.3重量%的铂负载于γ-氧化铝上,并加入助催化剂硫酸钾,虽于反应初始二聚体的转化率达98.7%,邻苯基苯酚的选择率为96.8%。但经反应50小时后,转化率降至88.1%,邻苯基苯酚收率降至84%,于反应100小时后,该收率更降至80%以下。再如JP 51-149248A所示,该催化剂是一种由铂、铱(VIII族)与碱金属氧化物负载于载体上的催化剂,其中,铂的含量为0.1至5.0重量%、铱与铂重量比为0.1至0.4、碱金属氧化物的含量为0.5至8.0重量%,以该载体中的三氧化二铁的总重计,该载体最高含有0.1%的铁或含有≧90重量%的氧化铝的氧化铝-氧化硅复合载体。但该催化剂的二聚体转化率仅有92%,邻苯基苯酚的选择率为93%。
另外,CN 101524643B使用以氧化铝为载体,铂为活性金属,柠檬酸为竞争吸附剂,并加入助催化剂硫酸钠制备的催化剂,虽初始的转化率达100%,选择率95%,但经过2,000小时后,该转化率则降至为99.8%。
由前可知,负载型贵金属催化剂虽有较高的转化率及选择率,然而其催化剂寿命不足以应付长时间的反应,导致催化剂活性无法有效维持,致使催化剂稳定性不佳。
如何增加催化剂整体稳定性,并延长催化剂寿命,时为业界迫切待解的课题。
发明内容
为了克服上述的缺点,本发明提供一种用于制备邻苯基苯酚的催化剂组合物,包括:载体;以及承载于该载体上的第一活性金属、第二活性金属、及选自金属盐或金属氢氧化物的助催化剂,其中,该第一活性金属为铂,且该第二活性金属选自铬、锰、铁、钴、镍、钼、锝、钌、铑、钯、钨、铼、锇或铱。
本发明还提供一种制备邻苯基苯酚的方法,包括:在本发明的催化剂组合物的存在下,使环己酮二聚物进行脱氢反应。
于本发明的催化剂组合物及方法的一具体实施例中,该第二活性金属与第一活性金属的重量比介于0.03至0.38。于另一具体实施例中,该第二活性金属与第一活性金属的重量比介于0.08至0.3。
于本发明的催化剂组合物及方法的一具体实施例中,该第一活性金属与载体的重量比介于0.004至0.006。
在前述具体实施例中,该第二活性金属与载体的重量比介于0.0002至0.0015。于另一具体实施例中,该第二活性金属与载体的重量比介于0.0005至0.0012。
于本发明的催化剂组合物及方法的一具体实施例中,该第二活性金属选自铬、钌、铱或镍。
于本发明的催化剂组合物及方法的一具体实施例中,该金属盐是碱金属硫酸盐、碱金属碳酸盐或碱金属硝酸盐,该助催化剂的具体实例可选自硫酸钾、碳酸钾及硝酸钠所组成组的至少一个。
于本发明的催化剂组合物及方法的另一具体实施例中,该金属氢氧化物是碱金属氢氧化物,该助催化剂的具体实例可选自氢氧化钾所组成组的至少一个。
于本发明的催化剂组合物及方法的一具体实施例中,该助催化剂与载体的重量比介于0.02至0.15。
于本发明的催化剂组合物及方法的一具体实施例中,该载体选自SiO2、Al2O3或Zr2O3所组成组的至少一个。
于本发明的方法的一具体实施例中,该脱氢反应的重时空速(WHSV)介于0.2至2.0。
本发明通过于承载有第一活性金属铂的该载体上承载选自铬、锰、铁、钴、镍、钼、锝、钌、铑、钯、钨、铼、锇或铱的第二活性金属的催化剂组合物,以提高活性金属铂的分散度,再于该载体上承载助催化剂,使用本发明的催化剂组合物制备邻苯基苯酚时能维持环己酮二聚物的转化率为99.97%至100%,能有效提升催化剂寿命,以利应用于工业化生产。
由前可知,本发明的催化剂组合物通过将第一活性金属铂、与选自铬、锰、铁、钴、镍、钼、锝、钌、铑、钯、钨、铼、锇或铱的第二活性金属与助催化剂承载于载体上,不仅具有高环己酮二聚物的转化率,且能在经过较长反应时间后,在维持环己酮二聚物的转化率的情况下,具有良好的邻苯基苯酚的选择率。
再者,本发明的催化剂组合物,不仅具有较长的催化剂寿命,更适用于不同反应温度,具有更广的反应物重时空速,能满足不同工业制程上需求。
具体实施方式
以下通过特定的具体实施例说明本发明的实施方式,该领域技术人员可由本说明书所揭示的内容轻易地了解本发明的优点及功效。本发明亦可通过其它不同的实施方式加以施行或应用,本说明书中的各项细节亦可基于不同观点与应用,在不悖离本发明所揭示的精神下赋予不同的修饰与变更。
于本说明书中所记载的转化率、选择率根据下列方式计算:
转化率(%)={[环己酮二聚物添加量(mol)-反应后环己酮二聚物剩余量(mol)]/环己酮二聚物添加量(mol)}×100%。
选择率(%)={产物中所含邻苯基苯酚的量(mol)/[环己酮二聚物添加量(mol)-反应后环己酮二聚物剩余量(mol)]}×100%。
反应初始=反应开始后6小时。
于本说明书中所记载的重时空速(Weight Hourly Space Velocity,WHSV)根据下式定义:
重时空速(WHSV)=环己酮二聚物(毫克(mg)/小时(h))/触媒(mg)
另外,该催化剂组合物中该第一活性金属:第二活性金属:载体:助催化剂的重量比是以Varian 220FS原子吸收光谱仪(Atomic absorption spectrometer,AAS)分析而得,其中,第一活性金属、第二活性金属与助催化剂在载体上的承载率皆大于92%。
本发明提供一种用于由环己酮二聚物制备邻苯基苯酚的催化剂组合物,该催化剂组合物包括载体;以及承载于该载体上的第一活性金属、第二活性金属、及选自金属盐或金属氢氧化物的助催化剂。
此外,该催化剂组合物的制备上,是以铂作为第一活性金属、以选自铬、锰、铁、钴、镍、钼、锝、钌、铑、钯、钨、铼、锇或铱作为第二活性金属,并将第一活性金属和第二活性金属先承载于例如SiO2、Al2O3或Zr2O3的载体上,接着在溶液环境下,使选自金属盐或金属氢氧化物的助催化剂承载于该载体上,如下式(II)所示。
[Pt+M+助催化剂]/γ-Al2O3 (II)
式中,M选自铬、锰、铁、钴、镍、钼、锝、钌、铑、钯、钨、铼、锇或铱。
于一具体实施例中,将铂及铬、锰、铁、钴、镍、钼、锝、钌、铑、钯、钨、铼、锇或铱承载于γ-氧化铝上,经除水、煅烧处理后,再于溶液环境下,使选自金属盐或金属氢氧化物的助催化剂承载于该载体上,以得到的催化剂,用以制备邻苯基苯酚。
于本发明的催化剂组合物中,第一活性金属铂与载体的重量比介于0.004至0.006的范围内。铬、锰、铁、钴、镍、钼、锝、钌、铑、钯、钨、铼、锇或铱的第二活性金属与载体的重量比介于0.0002至0.0015的范围内,更优选介于0.0005至0.0012。助催化剂与载体的重量比介于0.02至0.15的范围内,更优选介于0.05至0.10。
本发明还提供一种制备邻苯基苯酚的方法,包括:在本发明的催化剂组合物的存在下,使环己酮二聚物进行脱氢反应。
于本发明的制备邻苯基苯酚的方法的一具体实施例中,该第二活性金属与第一活性金属的重量比介于0.03至0.38。于另一实施例中,该第二活性金属与第一活性金属的重量比介于0.08至0.3。
于本发明的制备邻苯基苯酚的方法的一具体实施例中,该第一活性金属与载体的重量比介于0.004至0.006。
在前述具体实施例中,该第二活性金属与载体的重量比介于0.0002至0.0015。于另一具体实施例中,该第二活性金属与载体的重量比介于0.0005至0.0012。
于本发明的制备邻苯基苯酚的方法的一具体实施例中,该第二活性金属选自铬、钌、铱或镍。
于本发明的制备邻苯基苯酚的方法的一具体实施例中,该金属盐是碱金属硫酸盐、碱金属碳酸盐或碱金属硝酸盐,该助催化剂的具体实例可选自硫酸钾、碳酸钾及硝酸钠所组成组的至少一个。
于本发明的制备邻苯基苯酚的方法的另一具体实施例中,该金属氢氧化物是碱金属氢氧化物,该助催化剂的具体实例可选自氢氧化钾所组成组的至少一个。
于本发明的制备邻苯基苯酚的方法的一具体实施例中,该助催化剂与载体的重量比介于0.02至0.15。
于本发明的制备邻苯基苯酚的方法的一具体实施例中,该载体选自SiO2、Al2O3或Zr2O3所组成组的至少一个。
于本发明的制备邻苯基苯酚的方法的一具体实施例中,该脱氢反应的重时空速(WHSV)介于0.2至2.0。
制备例1 本发明的催化剂组合物的制备
将1.335克六氯白金酸、0.619克硝酸铬(III)九水合物溶于300克去离子水中,再将经250℃下煅烧3小时的100克γ-氧化铝加入前述金属盐类水溶液,于70℃超音波震荡下含浸至干,烘干、除水。接着于30单位时间标准毫升数(standard-state cubic centimeterper minute,sccm)氮气,450℃的条件下煅烧5小时,再于30sccm氮气与10sccm氢气,360℃的条件下还原5小时,得到尚未承载助催化剂的催化剂。
将6.316克硫酸钾溶于300克去离子水中,再将还原后的催化剂加入该硫酸钾水溶液中,于70℃超音波震荡下含浸至干,烘干、除水,得到制备例1的催化剂组合物,其中,该第一活性金属:第二活性金属:载体:助催化剂的重量比为0.5:0.08:100:6。
制备例2至4 使用不同第二活性金属制备本发明的催化剂组合物
使用与制备例1相同的方法制备催化剂组合物,差别仅在于制备例2至4是将制备例1中的0.619克硝酸铬(III)九水合物分别以0.208克氯化钌(III)三水合物、0.153克氯化铱(III)水合物、0.326克氯化镍(II)六水合物替代,于制备例2至4中该第一活性金属:第二活性金属:载体:助催化剂的重量比为0.5:0.08:100:6。
制备例5至8 使用不同含量的第二活性金属制备本发明的催化剂组合物
使用与制备例1相同的方法制备催化剂组合物,差别仅在于制备例5至8是将该硝酸铬(III)九水合物的添加量分别改为0.155克、0.388克、0.930克、1.161克,藉以改变该催化剂组合物中该第一活性金属:第二活性金属:载体:助催化剂的重量比分别为0.5:0.02:100:6、0.5:0.05:100:6、0.5:0.12:100:6、0.5:0.15:100:6。
制备例9至11 使用不同助催化剂制备本发明的催化剂组合物
使用与制备例1相同的方法制备催化剂组合物,差别仅在于制备例9至11是将制备例1中的硫酸钾分别以碳酸钾、氢氧化钾、硝酸钠取代,于制备例9至11中该第一活性金属:第二活性金属:载体:助催化剂的重量比为0.5:0.08:100:6。
制备例12至15 使用不同含量的助催化剂制备本发明的催化剂组合物
使用与制备例1相同的方法制备,差别仅在于制备例12至15是将制备例1中的6.316克硫酸钾添加量分别调整为2.105克、8.421克、11.579克、15.789克,藉以改变该催化剂组合物中该第一活性金属:第二活性金属:载体:助催化剂的重量比分别为0.5:0.08:100:2、0.5:0.08:100:8、0.5:0.08:100:11、0.5:0.08:100:15。
比较例1 不含第二活性金属的催化剂组合物及邻苯基苯酚的制备
将1.335克六氯白金酸溶于300克去离子水中,再将经250℃下煅烧3小时的100克γ-氧化铝加入前述金属盐类水溶液,于70℃超音波震荡下含浸至干,烘干、除水。接着于30sccm氮气下450℃煅烧5小时,再于30sccm氮气与10sccm氢气下360℃还原5小时。将6.316克硫酸钾溶于300克去离子水中,再将还原后的催化剂加入溶液中,于70℃超音波震荡下含浸至干,烘干、除水。
将20克由前制得的催化剂组合物填充于固定床反应器,使用连续式操作进行反应,以0.33sccm的流速馈入环己酮二聚物,并通以氢气作为载气,于汽化温度240℃、反应温度360℃、反应压力1atm条件下进行环己酮二聚物的脱氢反应。并于反应后6小时取样,以Shimadzu GC-2010Plus气相色谱仪(gas chromatography)分析产物,并将结果记录于表1。
实施例1至15 本发明的制备邻苯基苯酚的方法
分别将20克由制备例1至15所制得的催化剂组合物填充于固定床反应器,使用连续式操作进行反应,以0.33单位时间标准毫升数(standard-state cubic centimeter perminute,sccm)的流速馈入环己酮二聚物,并通以氢气作为载气,于汽化温度240℃、反应温度360℃、反应压力1atm条件下进行环己酮二聚物的脱氢反应。并于反应后6小时取样,以Shimadzu GC-2010Plus气相色谱仪(gas chromatography)分析产物,并将结果记录于表1至4。
表1
参阅表1可知,相较于比较例1的催化剂,本发明的催化剂组合物通过于载体上承载第一与第二活性金属,于反应6小时后具有环己酮二聚物转化率为100%的优异的特性,且本发明的催化剂组合物在转化率为100%的条件下更具有90%以上的选择率。
表2
于制备例1、5至8的催化剂组合物中,是于第一活性金属:载体:助催化剂的重量比固定为0.5:100:6的条件下改变第二活性金属的含量,各该制备例中该第二活性金属的重量比如表2所示。
参阅表2,相较于比较例1(参阅表1),本发明的催化剂组合物的第二活性金属与载体的重量比介于0.0002至0.0015时,不仅不会降低反应物的转化率,更在反应物转化率维持在100%的条件下维持一定的产物选择率。
比较例2 不含助催化剂的催化剂组合物
将1.335克六氯白金酸、0.619克硝酸铬(III)九水合物溶于300克去离子水中,再将经250℃下煅烧3小时的100克γ-氧化铝加入前述金属盐类水溶液,于70℃超音波震荡下含浸至干,烘干、除水。接着将催化剂于30sccm氮气下450℃煅烧5小时,再于30sccm氮气与10sccm氢气下360℃还原5小时。
将20克由前制得的催化剂组合物填充于固定床反应器,使用连续式操作进行反应,以0.33单位时间标准毫升数(standard-state cubic centimeter per minute,sccm)的流速馈入环己酮二聚物,并通以氢气作为载气,于汽化温度240℃、反应温度360℃、反应压力1atm条件下进行环己酮二聚物的脱氢反应。并于反应后6小时取样,以Shimadzu GC-2010Plus气相色谱仪(gas chromatography)分析产物,并将结果记录于表3。
表3
于制备例1、9至11的催化剂组合物中,是在第一活性金属:载体:助催化剂的重量比固定为0.5:0.08:100:6的条件下改变助催化剂的含量,各该制备例中的助催化剂如表3所示。
如表3所示,比较例2不含有助催化剂的催化剂组合物在反应6小时内,即反应初始时选择率已低于80%。不同于比较例2,本发明的催化剂组合物在使用不同的助催化剂的各实施例中皆具有99.97%以上的反应物转化率,维持一定的催化剂活性。
另外,由表3可知,鉴于实施例10、11,当助催化剂为碱金属硫酸盐或碱金属碳酸盐(实施例1、9)时,本发明的催化剂组合物更可在反应物转化率维持于100%的情况下,达到85.5%以上的产物选择率。
表4
于制备例1、12至15的催化剂组合物中,是在第一活性金属:第二活性金属:载体的重量比固定为0.5:0.08:100的条件下改变助催化剂的重量比为2、6、8、11、15,各该制备例中的助催化剂如表4所示。
如表4所示,相较于比较例2(参阅表3),本发明的催化剂组合物的助催化剂与载体的重量比介于0.02至0.15时,不仅不会降低反应物的转化率,且在反应物转化率为100%的条件下更具有一定的产物选择率。
实施例16至20 本发明的制备邻苯基苯酚的方法
将20克由制备例1所制得的催化剂组合物填充于固定床反应器,使用连续式操作进行反应,以0.33sccm的流速馈入环己酮二聚物,并通以氢气作为载气,于汽化温度240℃、反应压力1atm条件下,分别在不同反应温度下进行环己酮二聚物的脱氢反应,各该实施例的反应温度如下表5所示。并于反应后6小时取样,以Shimadzu GC-2010Plus气相色谱仪(gas chromatography)分析产物,并将结果记录于表5。
表5
反应温度(℃) | 转化率(%) | 选择率(%) | |
实施例16 | 330 | 100.00 | 92.16 |
实施例17 | 345 | 100.00 | 91.25 |
实施例1 | 360 | 100.00 | 91.89 |
实施例18 | 370 | 100.00 | 91.58 |
实施例19 | 380 | 100.00 | 92.00 |
实施例20 | 400 | 100.00 | 91.34 |
如表5所示,使用本发明的催化剂组合物制备邻苯基苯酚时,适用的反应温度自330至400℃,皆具有高选择率、高转化率,在较广的反应温度范围下皆能有高反应物转化率,且在反应物转化率为100%的条件下还能有一定的产物选择率,在不同的反应温度范围下皆能有良好的催化剂活性。
由前可知,于本发明的制备邻苯基苯酚的方法中,该环己酮二聚物脱氢反应温度范围介于330至400℃之间。
实施例21至27 本发明的制备邻苯基苯酚的方法
将20克由制备例1所制得的催化剂组合物填充于固定床反应器,使用连续式操作进行反应,以不同的单位时间标准毫升数(standard-state cubic centimeter perminute,sccm)流速馈入环己酮二聚物,并通以氢气作为载气,于汽化温度240℃、反应温度为360℃、反应压力1atm条件下,进行环己酮二聚物的脱氢反应。更详而言,实施例21至27分别以0.10sccm、0.20sccm、0.26sccm、0.40sccm、0.46sccm、0.56sccm、0.66sccm,换算为重时空速(Weight Hourly Space Velocity,WHSV)分别为0.3h-1、0.6h-1、0.8h-1、1.2h-1、1.4h-1、1.7h-1、2.0h-1,各该实施例的馈入环己酮二聚物的流速记载于表6。并于反应后6小时取样,以Shimadzu GC-2010Plus气相色谱仪(gas chromatography)分析产物,并将结果记录于表6。
表6
WHSV(h<sup>-1</sup>) | 转化率(%) | 选择率(%) | |
实施例21 | 0.3 | 100.00 | 93.87 |
实施例22 | 0.6 | 100.00 | 93.69 |
实施例23 | 0.8 | 100.00 | 93.82 |
实施例1 | 1.0 | 100.00 | 91.89 |
实施例24 | 1.2 | 100.00 | 89.65 |
实施例25 | 1.4 | 100.00 | 86.25 |
实施例26 | 1.7 | 100.00 | 86.66 |
实施例27 | 2.0 | 99.99 | 82.24 |
如表6所示,使用本发明的催化剂组合物制备邻苯基苯酚时,适用的重时空速范围较广,反应皆具高转化率,且在反应物转化率为99.99%的条件下,能维持一定的产物选择率。在较广反应物重时空速下,本发明的催化剂组合物仍能维持良好的催化剂活性。
于本发明的制备邻苯基苯酚的方法中,该脱氢反应重时空速介于0.3至2.0,更优选介于0.3至1.4。
另外,以实施例21为例,经过连续反应2400小时后,进行取样并以气相色谱仪分析产物,更发现该环己酮二聚物的转化率仍维持在100%,且在该环己酮二聚物的转化率为100%的条件下,该邻苯基苯酚的选择率为90.69%。
由此结果可知,本发明的催化剂组合物于反应2400小时后,转化率维持100%,选择率为90%以上,在反应2400小时后仍具有高催化剂活性。
综上所述,相较于先前技术中的种种缺失,本发明的催化剂组合物通过于载体上同时承载铂、选自铬、锰、铁、钴、镍、钼、锝、钌、铑、钯、钨、铼、锇或铱与助催化剂,能有效地增加活性金属铂于催化剂上的分散性,维持长时间的高转化率,确实提升催化活性。
再者,本发明的催化剂组合物通过特定第一活性金属、第二活性金属与助催化剂的含量组合,透过调整助催化剂用量,有效降低催化剂酸性,使使用本发明的催化剂组合物进行脱氢反应时,不仅有效且显著地延长催化剂寿命,更使本发明的催化剂组合物具有一定的稳定性,以利应用于工业化生产。
此外,本发明的制备邻苯基苯酚的方法,使反应物与催化剂重量比具有较大的范围,能适用于不同规格的固定床反应器或制程条件,于工业上的应用范围极广。
上述实施例以例示性说明本发明的原理及其功效,而非用于限制本发明。任何该领域技术人员均可在不违背本发明的精神及范畴下,对上述实施例进行修改。因此本发明的权利保护范围,应如权利要求书所列。
Claims (12)
1.一种用于制备邻苯基苯酚的催化剂组合物,包括:
载体;以及
承载于该载体上的第一活性金属、第二活性金属、及选自金属盐或金属氢氧化物的助催化剂,其特征在于,该第一活性金属为铂,该第二活性金属选自铬、锰、铁、钴、镍、钼、锝、钌、铑、钯、钨、铼或锇,该金属盐是碱金属硫酸盐、碱金属碳酸盐或碱金属硝酸盐,且该金属氢氧化物是碱金属氢氧化物;其中,该第一活性金属与载体的重量比介于0.004至0.006,且该第二活性金属与载体的重量比介于0.0002至0.0015,且该助催化剂与载体的重量比介于0.02至0.15。
2.如权利要求1所述的用于制备邻苯基苯酚的催化剂组合物,其特征在于,该第二活性金属与第一活性金属的重量比介于0.03至0.38。
3.如权利要求1所述的用于制备邻苯基苯酚的催化剂组合物,其特征在于,该第二活性金属与载体的重量比介于0.0005至0.0012。
4.如权利要求1所述的用于制备邻苯基苯酚的催化剂组合物,其特征在于,该第二活性金属选自铬、钌或镍。
5.如权利要求1所述的用于制备邻苯基苯酚的催化剂组合物,其特征在于,该金属盐选自硫酸钾及碳酸钾所组成组中的至少一个。
6.如权利要求1所述的用于制备邻苯基苯酚的催化剂组合物,其特征在于,该载体选自SiO2、Al2O3及Zr2O3所组成组中的至少一个。
7.一种制备邻苯基苯酚的方法,包括:
在如权利要求1所述的催化剂组合物的存在下,使环己酮二聚物进行脱氢反应。
8.如权利要求7所述的制备邻苯基苯酚的方法,其特征在于,该脱氢反应中的环己酮二聚物的重时空速介于0.2至2.0。
9.如权利要求7所述的制备邻苯基苯酚的方法,其特征在于,该第二活性金属与载体的重量比介于0.0002至0.0015。
10.如权利要求7所述的制备邻苯基苯酚的方法,其特征在于,该第二活性金属选自铬、钌或镍。
11.如权利要求7所述的制备邻苯基苯酚的方法,其特征在于,该金属盐选自硫酸钾及碳酸钾所组成组中的至少一个。
12.如权利要求7所述的制备邻苯基苯酚的方法,其特征在于,该载体选自SiO2、Al2O3及Zr2O3所组成组中的至少一个。
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CN1490293A (zh) * | 2002-10-15 | 2004-04-21 | 徐州瑞赛科技实业有限公司 | 由环己酮缩合脱氢制备邻苯基苯酚 |
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FR1499878A (fr) * | 1965-12-08 | 1967-11-03 | Inst Francais Du Petrole | Procédé de fabrication de phénol par déshydrogénation catalytique de cyclohexanol, de cyclohexanone ou de leurs mélanges |
US3580970A (en) * | 1967-11-22 | 1971-05-25 | Gulf Research Development Co | Dehydrogenation of cycloaliphatic ketones and alcohols |
DE2314947C3 (de) | 1973-03-26 | 1978-04-27 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Hydroxydiphenyl |
US4060559A (en) * | 1975-05-12 | 1977-11-29 | Sugai Chemical Industry Co., Ltd. | Process for preparing O-phenylphenol |
CN1166604C (zh) | 2001-02-23 | 2004-09-15 | 南京理工大学 | 用环己酮合成邻苯基苯酚的方法 |
TW201226379A (en) * | 2010-12-28 | 2012-07-01 | China Petrochemical Dev Corp | Method of producing 2-(cyclohex-1'-enyl) cyclohexanone |
MX2014008252A (es) * | 2012-01-06 | 2014-08-08 | Celanese Int Corp | Catalizadores de hidrogenacion. |
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