CN105237317A - Combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid - Google Patents
Combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid Download PDFInfo
- Publication number
- CN105237317A CN105237317A CN201510712251.7A CN201510712251A CN105237317A CN 105237317 A CN105237317 A CN 105237317A CN 201510712251 A CN201510712251 A CN 201510712251A CN 105237317 A CN105237317 A CN 105237317A
- Authority
- CN
- China
- Prior art keywords
- substituted
- benzyl alcohol
- liquid
- toluene
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 152
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 150000003935 benzaldehydes Chemical class 0.000 title claims abstract description 64
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000005711 Benzoic acid Substances 0.000 title claims abstract description 62
- 235000010233 benzoic acid Nutrition 0.000 title claims abstract description 62
- 150000001558 benzoic acid derivatives Chemical class 0.000 title claims abstract description 61
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 187
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 151
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 150
- 230000003647 oxidation Effects 0.000 claims abstract description 148
- 230000007062 hydrolysis Effects 0.000 claims abstract description 138
- 239000007788 liquid Substances 0.000 claims abstract description 138
- 238000006243 chemical reaction Methods 0.000 claims abstract description 121
- 239000000047 product Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012071 phase Substances 0.000 claims abstract description 14
- 239000008346 aqueous phase Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 239000011541 reaction mixture Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 75
- 239000007791 liquid phase Substances 0.000 claims description 71
- 229960004217 benzyl alcohol Drugs 0.000 claims description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 42
- 229910052760 oxygen Inorganic materials 0.000 claims description 42
- 239000001301 oxygen Substances 0.000 claims description 42
- 239000000126 substance Substances 0.000 claims description 27
- -1 transition metal salt Chemical class 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 21
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical class O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 21
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical group CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 7
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 7
- 241001330002 Bambuseae Species 0.000 claims description 7
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 7
- 239000011425 bamboo Substances 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- BEARMXYKACECDH-UHFFFAOYSA-N methylsulfonylmethylbenzene Chemical compound CS(=O)(=O)CC1=CC=CC=C1 BEARMXYKACECDH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 5
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 claims description 5
- WJIFKOVZNJTSGO-UHFFFAOYSA-N 1-bromo-3-methylbenzene Chemical compound CC1=CC=CC(Br)=C1 WJIFKOVZNJTSGO-UHFFFAOYSA-N 0.000 claims description 5
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 claims description 5
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 claims description 5
- UALKQROXOHJHFG-UHFFFAOYSA-N 1-ethoxy-3-methylbenzene Chemical compound CCOC1=CC=CC(C)=C1 UALKQROXOHJHFG-UHFFFAOYSA-N 0.000 claims description 5
- WRWPPGUCZBJXKX-UHFFFAOYSA-N 1-fluoro-4-methylbenzene Chemical compound CC1=CC=C(F)C=C1 WRWPPGUCZBJXKX-UHFFFAOYSA-N 0.000 claims description 5
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- KGCNHWXDPDPSBV-UHFFFAOYSA-N p-nitrobenzyl chloride Chemical compound [O-][N+](=O)C1=CC=C(CCl)C=C1 KGCNHWXDPDPSBV-UHFFFAOYSA-N 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- UWNWYIUODRPXKH-UHFFFAOYSA-N toluene;hydrofluoride Chemical compound F.CC1=CC=CC=C1 UWNWYIUODRPXKH-UHFFFAOYSA-N 0.000 claims description 5
- BBUPBICWUURTNP-UHFFFAOYSA-N 2,4-dimethyl-1-nitrobenzene Chemical compound CC1=CC=C([N+]([O-])=O)C(C)=C1 BBUPBICWUURTNP-UHFFFAOYSA-N 0.000 claims description 4
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- MKACMVMZUIQKNY-UHFFFAOYSA-N 2-hydroxy-5-nitroisoindole-1,3-dione Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(=O)C2=C1 MKACMVMZUIQKNY-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- FVHAWXWFPBPFOS-UHFFFAOYSA-N 1,2-dimethyl-3-nitrobenzene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1C FVHAWXWFPBPFOS-UHFFFAOYSA-N 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 26
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000004821 distillation Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 150000003613 toluenes Chemical class 0.000 abstract 2
- 239000000463 material Substances 0.000 description 24
- 230000009466 transformation Effects 0.000 description 23
- 238000004458 analytical method Methods 0.000 description 22
- 238000012423 maintenance Methods 0.000 description 22
- 238000005070 sampling Methods 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 17
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical class C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 16
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 15
- 239000011572 manganese Substances 0.000 description 15
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 15
- 229960002903 benzyl benzoate Drugs 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- KLCQXXAKURQDOV-UHFFFAOYSA-N chlorobenzene methanol Chemical compound CO.CO.ClC1=CC=CC=C1 KLCQXXAKURQDOV-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 2
- ZWDVQMVZZYIAHO-UHFFFAOYSA-N 2-fluorobenzaldehyde Chemical group FC1=CC=CC=C1C=O ZWDVQMVZZYIAHO-UHFFFAOYSA-N 0.000 description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XHIXVZHYFBOAJT-UHFFFAOYSA-N (2-chloro-4-nitrophenyl)methanol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1Cl XHIXVZHYFBOAJT-UHFFFAOYSA-N 0.000 description 1
- QJANIQCEDPJNLO-UHFFFAOYSA-N (2-methyl-3-nitrophenyl)methanol Chemical compound CC1=C(CO)C=CC=C1[N+]([O-])=O QJANIQCEDPJNLO-UHFFFAOYSA-N 0.000 description 1
- IQWWTJDRVBWBEL-UHFFFAOYSA-N (3,5-dimethylphenyl)methanol Chemical compound CC1=CC(C)=CC(CO)=C1 IQWWTJDRVBWBEL-UHFFFAOYSA-N 0.000 description 1
- KOVQGYQQVNCUBR-UHFFFAOYSA-N (3-methyl-4-nitrophenyl)methanol Chemical compound CC1=CC(CO)=CC=C1[N+]([O-])=O KOVQGYQQVNCUBR-UHFFFAOYSA-N 0.000 description 1
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 description 1
- GVBXZIANHMNKAK-UHFFFAOYSA-N 2-chloro-4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C(Cl)=C1 GVBXZIANHMNKAK-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical group ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- NSTREUWFTAOOKS-UHFFFAOYSA-N 2-fluorobenzoic acid Chemical group OC(=O)C1=CC=CC=C1F NSTREUWFTAOOKS-UHFFFAOYSA-N 0.000 description 1
- QVTPWONEVZJCCS-UHFFFAOYSA-N 2-formylbenzonitrile Chemical compound O=CC1=CC=CC=C1C#N QVTPWONEVZJCCS-UHFFFAOYSA-N 0.000 description 1
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 1
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- NBEFMISJJNGCIZ-UHFFFAOYSA-N 3,5-dimethylbenzaldehyde Chemical class CC1=CC(C)=CC(C=O)=C1 NBEFMISJJNGCIZ-UHFFFAOYSA-N 0.000 description 1
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-UHFFFAOYSA-N 0.000 description 1
- VOIZNVUXCQLQHS-UHFFFAOYSA-N 3-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC(Br)=C1 VOIZNVUXCQLQHS-UHFFFAOYSA-N 0.000 description 1
- SRWILAKSARHZPR-UHFFFAOYSA-N 3-chlorobenzaldehyde Chemical compound ClC1=CC=CC(C=O)=C1 SRWILAKSARHZPR-UHFFFAOYSA-N 0.000 description 1
- MXNBDFWNYRNIBH-UHFFFAOYSA-N 3-fluorobenzoic acid Chemical compound OC(=O)C1=CC=CC(F)=C1 MXNBDFWNYRNIBH-UHFFFAOYSA-N 0.000 description 1
- WHJDQIWWIJARMK-UHFFFAOYSA-N 3-methyl-4-nitrobenzaldehyde Chemical compound CC1=CC(C=O)=CC=C1[N+]([O-])=O WHJDQIWWIJARMK-UHFFFAOYSA-N 0.000 description 1
- XDTTUTIFWDAMIX-UHFFFAOYSA-N 3-methyl-4-nitrobenzoic acid Chemical compound CC1=CC(C(O)=O)=CC=C1[N+]([O-])=O XDTTUTIFWDAMIX-UHFFFAOYSA-N 0.000 description 1
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- ADCUEPOHPCPMCE-UHFFFAOYSA-N 4-cyanobenzoic acid Chemical compound OC(=O)C1=CC=C(C#N)C=C1 ADCUEPOHPCPMCE-UHFFFAOYSA-N 0.000 description 1
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 1
- BBYDXOIZLAWGSL-UHFFFAOYSA-N 4-fluorobenzoic acid Chemical compound OC(=O)C1=CC=C(F)C=C1 BBYDXOIZLAWGSL-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 description 1
- QAYNSPOKTRVZRC-UHFFFAOYSA-N 99-60-5 Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1Cl QAYNSPOKTRVZRC-UHFFFAOYSA-N 0.000 description 1
- BEZGQCDETACFFH-UHFFFAOYSA-N COO.C1=CC=CC=C1 Chemical class COO.C1=CC=CC=C1 BEZGQCDETACFFH-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 235000014493 Crataegus Nutrition 0.000 description 1
- 241001092040 Crataegus Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- YNKMHABLMGIIFX-UHFFFAOYSA-N benzaldehyde;methane Chemical compound C.O=CC1=CC=CC=C1 YNKMHABLMGIIFX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QARVLSVVCXYDNA-IDEBNGHGSA-N bromobenzene Chemical group Br[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 QARVLSVVCXYDNA-IDEBNGHGSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical group O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZVKQEVIJSHOQBY-UHFFFAOYSA-N methylsulfonyl(phenyl)methanol Chemical compound CS(=O)(=O)C(O)C1=CC=CC=C1 ZVKQEVIJSHOQBY-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- OTVAEFIXJLOWRX-NXEZZACHSA-N thiamphenicol Chemical compound CS(=O)(=O)C1=CC=C([C@@H](O)[C@@H](CO)NC(=O)C(Cl)Cl)C=C1 OTVAEFIXJLOWRX-NXEZZACHSA-N 0.000 description 1
- 229960003053 thiamphenicol Drugs 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- 239000012808 vapor phase Substances 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid. The method comprises the following steps: (1) oxidation: a step of continuously introducing substituted toluene, a catalyst and oxygen-contained gas into an oxidation reactor and carrying out reaction so as to obtain oxidation reaction liquid; (2) hydrolyzation: a step of allowing the oxidation reaction liquid to continuously enter a hydrolysis reactor, and continuously adding water into the hydrolysis reactor and carrying out reaction so as to obtain a hydrolysis reaction mixture; (3) liquid-liquid layering: a step of layering the hydrolysis reaction mixture so as to obtain an oil phase and an aqueous phase; and (4) separation of products: a step of subjecting the oil phase to distillation so as to respectively obtain incompletely-reacted substituted toluene, substituted benzyl alcohol and substituted benzaldehyde, and subjecting the aqueous phase to cooling, crystallizing and filtering so as to obtain filtrate and substituted benzoic acid. The combined production method provided by the invention has the advantages of high raw material conversion rate, few by-products, good selectivity of target products, greenness and environmental protection.
Description
Technical field
The present invention relates to the preparation method of aromatic compound, particularly a kind of method of coproduction substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid.
Background technology
The phenylformic acid that phenyl ring is replaced by different substituents such as such as halogen, nitro, methyl, cyano group, methylsulfonyl, hydroxyl, methoxyl groups, phenylcarbinol and phenyl aldehyde are all important fine chemical products, be widely used in the industries such as medicine, agricultural chemicals, veterinary drug, food, dyestuff, organic synthesis, there are considerable market outlook.The method of current industrial production substituted benzyl alcohol, substituted benzaldehyde and substituted benzoic acid has four kinds:
(1) it is obtained through hydrolysis again after toluene halo will be replaced.The product selectivity that this method is produced is high, but the production stage of the method is many, processing condition more complicated, and the halogen of one of synthesis material is serious to equipment corrosion, produces a large amount of pollutents in hydrolytic process simultaneously.And cost of material is general costly, the economic benefit competitive power of technique is not strong.More seriously the aldehyde produced of this method and alcohol compound, due to containing halogenated compound, thus seriously constrains the application in the demand field in enormous quantities such as medicine, agriculture food of phenyl aldehyde, phenylcarbinol and phenylformic acid product that non-halogen replaces.
(2) toluene oxidation will be replaced when a large amount of Co/Mn/Br is catalyzer in a large amount of acetic acid.The cost of material of this method is cheaply easy to get, and production stage is relatively less, and economic competitiveness is strong.But use a large amount of acetic acid and make solvent, and key targets is generally corresponding substituted benzoic acid, the selectivity of intermediate product substituted benzyl alcohol and substituted benzaldehyde is general very low.And in actual production, the price of substituted benzyl alcohol and substituted benzaldehyde and economic benefit will be far superior to corresponding substituted benzoic acid.Therefore, the production process that it is key targets that this method is rarely used in substituted benzyl alcohol and substituted benzaldehyde.In addition, replace in the product of toluene oxidation oxidation, the raw material complete except unreacted replaces except toluene, primary product substituted benzoic acid, substituted benzaldehyde and substituted benzyl alcohol, also inevitably will produce a certain amount of substituted benzyl benzoate.The common aftertreatment technology of prior art is adopt rectifying that raw material complete for unreacted and product are carried out rectifying separation, not only consume a large amount of heat energy, and in rectifying substituted benzaldehyde be easily heated there is aldol reaction and loss, substituted benzyl alcohol is easily heated and the substituted benzoic acid generation esterification in system and loss, cause distillation tower stillage residue amount large, the yield of product is low, is generally no more than 90%.
(3) when a large amount of metal ions is catalyzer, nitric acid is will replace toluene oxidation in oxygenant.The cost of material of this method is cheaply easy to get, and production stage is relatively less.But oxygenant is nitric acid, produce a large amount of NOx and dust technology contaminate environment, key targets is also generally corresponding substituted benzoic acid, and the selectivity of intermediate product substituted benzyl alcohol and substituted benzaldehyde is general very low.
(4) obtained by the method for complicated organic synthesis.This method is generally for specific aldehyde or alcohol, and obtained by the method for the organic synthesis of complexity, production efficiency is generally lower, and can use a large amount of middle organism, and produce a large amount of three wastes, production cost is high, is not suitable for the production of mass-producing.
Replacement toluene oxidation product substituted benzaldehyde and substituted benzyl alcohol are the product of high added value, substituted benzoic acid relatively economical is worth lower, how while raising replaces toluene conversion, improve the overall selectivity of substituted benzoic acid, substituted benzyl alcohol and substituted benzaldehyde, the particularly target product substituted benzaldehyde of high added value and the selectivity of substituted benzyl alcohol and yield, reduce the generation of other by products, improving economy, is problem anxious to be resolved.
Summary of the invention
The invention solves the defect of prior art, provide that a kind of feed stock conversion is high, target product selectivity good, energy consumption is low, the method for the coproduction substituted benzaldehyde of environmental protection, substituted benzyl alcohol and substituted benzoic acid.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions: a kind of method of coproduction substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid, comprises the following steps:
(1) be oxidized: in oxidation reactor, pass into replacement toluene, catalyzer and oxygen-containing gas continuously react, tail oxygen concentration is controlled within 5% by the intake controlling oxygen-containing gas, the consumption of described catalyzer is the 1-10000ppm replacing toluene quality, temperature of reaction is 100 ~ 250 DEG C, reaction pressure 0.1 ~ 3MPa, be 0.4 ~ 6 hour in the mean residence time of the oxidation reactor of liquid phase substance, obtain oxidation liquid;
(2) be hydrolyzed: the oxidation liquid that step (1) obtains is entered in hydrolysis reactor continuously, and in hydrolysis reactor, add water continuously react, it is described that to add the water yield with the oxidation liquid volume ratio entering hydrolysis reactor be 0.05 ~ 1:1, temperature of reaction is 50 ~ 215 DEG C, reaction pressure is 0.1 ~ 2.0MPa, in hydrolysis reactor, the liquid phase residence time is 0.3 ~ 6 hour, obtains hydrolysis reaction mixture;
(3) liquid liquid layering: hydrolysis reaction mixture step (2) obtained is temperature 20 ~ 175 DEG C, pressure is the lower leaf of 0.1 ~ 2.0MPa condition, obtains containing replacing toluene and substituted benzyl alcohol, the oil phase of substituted benzaldehyde and the aqueous phase containing substituted benzyl alcohol, substituted benzaldehyde and substituted benzoic acid;
(4) separation of product: the oil phase that step (3) obtains is carried out rectifying and obtain unreacted respectively and replace toluene, substituted benzyl alcohol and substituted benzaldehyde product completely, aqueous phase crystallisation by cooling step (3) obtained filters, and obtains filtrate and substituted benzoyl acid product.
Replacement toluene of the present invention refers to that substituting group is in the compound on phenyl ring.Substituting group can be positioned at the ortho position of methyl, contraposition and a position.Substituting group can be one or more in halogen, nitro, methyl, cyano group, methylsulfonyl, hydroxyl, methoxyl group.Described replacement toluene be preferably parachlorotoluene, o-fluorotobuene, para-bromo toluene, para-nitrotoluene, to cyano group toluene, sym-trimethylbenzene, to methylsulfonyltoluene, to hydroxytoluene, p-Xylol, 2, the chloro-4-nitrotoluene of 3-dimethyl nitrobenzene, 2,4-dimethyl nitrobenzenes, 2-, ortho-chlorotolu'ene, a toluene fluoride, o-bromotoluene, Ortho Nitro Toluene, to the one in methoxy toluene, m-chlorotoluene, m-bromotoluene, o-Xylol, p-fluorotoluene, m-xylene.
In described oxygen-containing gas, the mass percentage of oxygen is preferably greater than or equal to 15%.
Described catalyzer is preferably the mixture of one or more in transition metal salt or oxide compound, HP and analogue thereof, the metalphthelein mountain valley with clumps of trees and bamboo, metalloporphyrin.
Described transition metal salt or oxide compound are preferably selected from the one in the salt of Co, Cu, Ni, Zn, Mn, Fe, Cr, Ce, Zr, Ru, Hf or oxide compound;
Described HP and analogue thereof are preferably selected from HP, N-hydroxyl-4-nitrophthalimide, N-hydroxyl-4-carboxyl phthalic imidine, N-hydroxy-4-methyl phthalic imidine, N-hydroxyl-3, 4, 5, 6-tetraphenyl phthalic imidine, N, N '-dihydroxyl phthalic imidine, the adjacent sulfonyl-benzoyl amine of N-hydroxyl, N-ethanoyl phthalic imidine, N, N ', N "-trihydroxy-tricarbimide, N-hydroxyl-3-picolyl phthalic imidine, N-glutarimide, one in N-hydroxysuccinimide.
Described metalloporphyrin preferably has the structure of general formula (I) or general formula (II) or general formula (III):
Atoms metal M in its formula of (I) is selected from Co, Cu, Ni, Zn, Ru, Mn, Fe; Atoms metal M in general formula (II) is selected from Fe, Mn, Cr, Co; Atoms metal M in general formula (III)
1, M
2be selected from Fe, Mn, Cr respectively; Dentate X in general formula (II) is acetate, methyl ethyl diketone root, halogen; Substituent R in general formula (I), (II) and (III)
1, R
2and R
3be respectively the one in hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, nitro.
The described metalphthelein mountain valley with clumps of trees and bamboo preferably has the structure of general formula (IV):
Wherein atoms metal M is selected from Co, Cu, Ni, Zn, Ru, Mn, Fe, substituent R
1and R
2be respectively hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, nitro.
As the preferred embodiment of the present invention, the unreacted that step (4) obtain can be replaced toluene completely and filtrate loops back in oxidation reactor and hydrolysis reactor respectively.
As the preferred embodiment of the present invention, in hydrolysis reactor, water is added continuously when reacting described in step (2), the oxygen-containing gas that oxygen mass percentage is more than or equal to 5% can be passed into continuously in hydrolysis reactor simultaneously, and control tail oxygen concentration within 5% by the intake controlling oxygen-containing gas.
As the preferred embodiment of the present invention, when passing into continuously in oxidation reactor described in step (1) replaces toluene, simultaneously can pass into solvent acetic acid in oxidation reactor, described in the acetic acid that passes into be 0.002 ~ 0.15:1 with the mass ratio replacing toluene.
During oxidizing reaction, catalyzer has important impact with the mass ratio replacing toluene to the yield of product substituted benzyl alcohol, substituted benzaldehyde and substituted benzoic acid and speed of response.Catalyzer is with when replacing the mass ratio height of toluene, and it is fiercer to react, and causes intermediate product substituted benzyl alcohol to be more easily further oxided into substituted benzoic acid with substituted benzaldehyde.Too high catalyst concn can cause catalyzer cost to increase simultaneously.Catalyzer is too little with the mass ratio replacing toluene, is not enough to initiation reaction, and cause speed of response slow, catalytic efficiency is low.Therefore in the present invention, the consumption of catalyzer is the 1-10000ppm replacing toluene quality.
The catalyzer that the present invention selects is the mixture of one or more in transition metal salt or oxide compound, HP and analogue thereof, the metalphthelein mountain valley with clumps of trees and bamboo, metalloporphyrin.Several mixture in preferred transition metal salt or oxide compound, HP and analogue thereof, the metalphthelein mountain valley with clumps of trees and bamboo, metalloporphyrin, the mixing of catalyzer can work in coordination with initiation reaction mutually, make under identical reaction conversion ratio, composite catalyst comparatively single catalyst consumption reduces, and the overall selectivity of substituted benzyl alcohol, substituted benzaldehyde and substituted benzoic acid also improves simultaneously.
During oxidation, temperature of reaction and pressure also have important impact to the yield of product substituted benzyl alcohol, substituted benzaldehyde and substituted benzoic acid and speed of response.The favourable raising speed of response of pyroreaction, increase production efficiency, is also conducive to substituted benzyl alcohol simultaneously and substituted benzaldehyde changes into substituted benzoic acid further.Meanwhile, too high temperature will make side reaction aggravate, and material loss increases, and also make facility investment increase simultaneously.The solubleness of reaction under high pressure favourable increase vapor-phase reactant oxygen-containing gas in reaction solution, improves speed of response.But too high pressure makes facility investment increase.After considering the catalyst system that above-mentioned pros and cons and the present invention specifically use, temperature of reaction suitable in the present invention is 90 ~ 250 DEG C, and reaction pressure is 0.1 ~ 3.0MPa.
The degree of depth of oxidation the reaction time major effect oxidizing reaction and the selectivity of target product substituted benzyl alcohol, substituted benzaldehyde and substituted benzoic acid, also affect substituted benzyl alcohol, substituted benzaldehyde and substituted benzoic acid proportional distribution in the product simultaneously.Reaction times is too short, and can cause replacing toluene conversion low, the total recovery of substituted benzyl alcohol, substituted benzaldehyde and substituted benzoic acid is lower; Reaction times is long, although the per pass conversion replacing toluene is high, the substituted benzaldehyde of high added value and substituted benzyl alcohol are more easily oxidized to substituted benzoic acid further, are even further oxidized to CO
2and water, cause selectivity to reduce.Considering above-mentioned factor, is 0.4 ~ 6 hour in the mean residence time of the oxidation reactor of liquid phase substance in the present invention.
On product separation is purified, the present invention has given up prior art and has adopted rectifying directly raw material complete for unreacted and each product to be carried out the operation be separated, but first adopt the hydrolysis reaction in water and liquid liquid hierarchical operations, completely avoid that prior art generally adopts by the significant deficiency of low boiling component rectifying separation from system, under the prerequisite ensureing actual production process safety, constantly greatly save energy consumption, and avoid the generation of side reaction in operating process as far as possible, the utilization ratio replacing toluene is improved, and economy significantly promotes.Also achieve following important result simultaneously:
(1) being separated of product substituted benzoic acid and other materials is achieved.Substituted benzoic acid is generally soluble in hot water, be insoluble in replacement toluene, therefore while hydrolysis reaction can to greatest extent by target product substituted benzoic acid from replacement toluene mutually be extracted in aqueous phase, realize and replace being separated of toluene, but important intermediate substituted benzyl alcohol and substituted benzaldehyde are due to molten with shipwreck, the overwhelming majority rests in organic phase, thus simple realization substituted benzoic acid and other materials are as replaced toluene, substituted benzyl alcohol is separated with substituted benzaldehyde, avoid the contact of substituted benzoic acid and substituted benzyl alcohol in traditional technology fractionation by distillation process, also reduce the generation probability of side reaction substituted benzoic acid Bian ester.
(2) make subsequent separation process safer.Replace in toluene oxidation process and have relatively large substituted benzene methyl hydroperoxide and replace benzoyl hydroperoxide.Traditional technique is direct rectifying, and superoxide easily causes larger potential safety hazard in the situation of being heated.The present invention continues reaction by being added by water in oxidation liquid, and the superoxide existed in system is decomposed completely, in acid condition fast for follow-up distillation procedure provides safety control.
(3) make the ester class product hydrolysis such as the substituted benzyl benzoate that generates in reaction process, improve the yield of substituted benzoic acid and substituted benzyl alcohol further.
In the present invention, after hydrolysis reaction terminates, hydrolysis reaction mixture is entered continuously liquid liquid quantizer, temperature 20 ~ 175 DEG C, pressure is the lower leaf of 0.1 ~ 2.0MPa condition, obtains containing replacing toluene and substituted benzyl alcohol, the oil phase of substituted benzaldehyde and the aqueous phase containing substituted benzyl alcohol, substituted benzaldehyde and substituted benzoic acid.To oil-phase product, due to without product substituted benzoic acid, in the sepn process replacing toluene, substituted benzyl alcohol and substituted benzaldehyde, adopt conventional rectifying, substituted benzyl alcohol and substituted benzoic acid can be avoided completely to be reacted into the reaction process of ester, the yield of important high added value product substituted benzyl alcohol can be significantly improved.To water-phase product, carry out conventional chilling crystallization filtration, substituted benzoyl acid product and the filtrate of purity more than 99.5% can be obtained.The main component of filtrate is water or acetic acid water, is mixed with a small amount of substituted benzyl alcohol, substituted benzaldehyde and substituted benzoic acid, can return continuation reaction in hydrolysis reactor by direct circulation.
According to the present invention, product such as the amount of substituted benzyl alcohol, substituted benzaldehyde, substituted benzoic acid, substituted benzyl benzoate of reacting in the amount of the replacement toluene in the reactor of front and back, system is analyzed quantitatively by liquid chromatography marker method (taking isopropyl benzene as internal standard substance).The replacement toluene conversion characterizing level of response is defined as:
Replace the amount of the fresh replacement toluene added in reactor of toluene conversion=(amount of the toluene in the substituted benzyl alcohol that the amount-step (4) of the replacement toluene continuously in the substituted benzoyl acid product that obtains of the fresh amount-step (4) adding the replacement toluene of reactor obtains and substituted benzaldehyde product)/continuously.Be expressed as a percentage in embodiment.
Characterize reaction product substituted benzyl alcohol selectivity to be defined as:
The mole number of the substituted benzyl alcohol of the selectivity=generation of substituted benzyl alcohol/(mole number of the substituted benzyl benzoate of the total mole number+generation of the substituted benzyl alcohol of generation, substituted benzaldehyde and substituted benzoic acid) (being expressed as a percentage).
Characterize reaction product substituted benzaldehyde selectivity to be defined as:
The mole number of the substituted benzaldehyde of the selectivity=generation of substituted benzaldehyde/(mole number of the substituted benzyl benzoate of the total mole number+generation of the substituted benzyl alcohol of generation, substituted benzaldehyde and substituted benzoic acid) (being expressed as a percentage).
Characterize reaction product substituted benzoic acid selectivity to be defined as:
The mole number of the substituted benzoic acid of the selectivity=generation of substituted benzoic acid/(mole number of the substituted benzyl benzoate of the total mole number+generation of the substituted benzyl alcohol of generation, substituted benzaldehyde and substituted benzoic acid) (being expressed as a percentage).
Compared with prior art, advantage of the present invention is:
1, reaction efficiency is high, product yield is high, selectivity is good, replace the transformation efficiency of toluene more than 95%, substituted benzyl alcohol, substituted benzaldehyde and substituted benzoic acid overall selectivity are 100%, and the target product substituted benzaldehyde of high added value and the selectivity sum of substituted benzyl alcohol are more than 85%;
2, low, the environmental protection of energy consumption, adopt hydrolysis operation, less energy-consumption achieve being separated of substituted benzoic acid and other product in system, avoid substituted benzoic acid simultaneously and contact the process generating by product substituted benzyl benzoate with substituted benzyl alcohol, sepn process energy consumption is reduced, significantly reduce the loss of various heat-sensitive substance due to distillation simultaneously, decomposed the by product substituted benzyl benzoate generated in oxidation reaction process, decreased the discharge of pollutent;
3, improve the security of operation, online has decomposed the superoxide existed in system, significantly reduces the risk of explosion that in traditional technology, distillation procedure exists.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Wherein, 1 is oxidation reactor, and 2 is hydrolysis reactor, and 3 is liquid liquid quantizer, and 4 is rectifying tower, and 5 is solid-liquid separation system
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but the present invention is not limited to described embodiment.
Metalloporphyrin in embodiment has the structure of general formula (I) or general formula (II) or general formula (III):
The metalphthelein mountain valley with clumps of trees and bamboo in embodiment has the structure of general formula (IV):
The tubular reactor of oxidation reactor 1 used in embodiment to be an internal diameter be 32mm, high 400mm, reactor outer wall belt chuck, moves heat by heat-eliminating medium to reaction.Hydrolysis reactor 2 used is integrated the stirring tank titanium material reactor amassed as 500mL, is with inner coil pipe to cool and the heating of still wall jacket steam.Liquid liquid quantizer 3 used is the 316L stainless steel cylinder of an internal diameter 32mm, high 400mm.Rectifying tower 4 internal diameter 100mm, high 5000mm, material is 316L.The volume that solid-liquid separation system 5 comprises three series connection is the 316L stirring tank with pressure of 1000L, the continuous filtration separation system of two interval filter-pressing device compositions.Each reactor and stirring tank are all with multi-stage gas-liquid condenser.
Concrete implementing procedure is: operation adopts operate continuously, after the mixture of catalyzer and fresh replacement toluene or catalyzer and fresh replacement toluene and solvent acetic acid configures in proportion, oxidation reactor 1 is entered continuously by charge pump, under the condition passing into oxygen-containing gas continuously, toluene one-step oxidation will be replaced, obtain oxidation liquid.The concentration of oxygen in oxidation reactor 1 gas phase tail gas is made to be no more than 5% by the amount controlling the oxygen-containing gas passed into.The oxidation liquid that oxidation reactor 1 obtains enters in hydrolysis reactor 2 continuously, in hydrolysis reactor 2, add water continuously carry out reacting or in hydrolysis reactor 2, adding water continuously simultaneously and pass into oxygen-containing gas continuously simultaneously reacting simultaneously, make the concentration of oxygen in hydrolysis reactor 2 gas phase tail gas be no more than 5% by the amount controlling the oxygen-containing gas passed into when passing into oxygen-containing gas, obtain hydrolysis reaction mixture.The tail gas of oxidation reactor 1 and hydrolysis reactor 2 all reclaims emptying after the replacement toluene evaporated by cooling.Hydrolysis reaction mixture enters layering in liquid liquid quantizer 3 continuously, obtains aqueous phase and oil phase.Oil phase mainly containing replacing toluene, substituted benzyl alcohol, substituted benzaldehyde, or contains replacement toluene, substituted benzyl alcohol, substituted benzaldehyde and partial solvent acetic acid; Aqueous phase mainly containing substituted benzoic acid, water, and has dissolved substituted benzyl alcohol and substituted benzaldehyde on a small quantity, or containing substituted benzoic acid and acetic acid, water, and dissolved substituted benzyl alcohol and substituted benzaldehyde on a small quantity.Oil phase enters rectifying in rectifying tower 4 continuously, tower top obtains the complete raw material of unreacted continuously and replaces toluene, or the complete raw material of unreacted replaces toluene and solvent acetic acid, raw material complete for unreacted is replaced toluene or the complete raw material of unreacted and replace toluene and solvent acetic acid direct circulation and return in oxidation reactor 1 and continue oxidation; Tower reactor obtains product substituted benzyl alcohol and substituted benzaldehyde.Aqueous phase is filtered through solid-liquid separation system 5 crystallisation by cooling and obtains product substituted benzoic acid and the filtrate containing a small amount of substituted benzyl alcohol, substituted benzaldehyde and substituted benzoic acid, filtrate continuous circulation is returned in hydrolysis reactor 2 and continue reaction.
Embodiment 1
Adding the catalyzer dissolved in the fresh material parachlorotoluene of system and acetic acid is HfO
2, the adjacent sulfonyl-benzoyl amine of N-hydroxyl, there is the metal phthalocyanine (R of general formula (IV) structure
1=H, R
2=F, M=Fe) and there is the metalloporphyrin (R of general formula (I) structure
1=R
3=OH, R
2=H, M=Ru) mixture, total concn is 600ppm, and the mass ratio of solvent and parachlorotoluene is 0.026.During device steady-state operation, the flow adding the fresh material in oxidation reactor is 6.2mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 2.4h, pressurization pure oxygen is passed in oxidation reactor continuously, maintenance system temperature of reaction is 165 DEG C, and reaction pressure is 1.4MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.33:1, and pass into the oxygen-denuded air that oxygen mass percentage is 10% continuously, the temperature of reaction maintained in hydrolysis reactor is 122 DEG C, reaction pressure is 0.9MPa, and now in hydrolysis reactor, the liquid phase residence time is 2.6h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 87.2 DEG C, and pressure is 0.8MPa.Through sampling analysis, the transformation efficiency of parachlorotoluene is 95.7%, and be respectively 72.1%, 23.2% and 4.7% to the selectivity of chlorobenzene methanol, 4-chloro-benzaldehyde and Chlorodracylic acid, other by product does not detect.
Embodiment 2
Add the catalyzer that dissolves in the fresh o-fluorotobuene in once oxidation reactor for having the metal phthalocyanine (R of general formula (IV) structure
1=H, R
2=CH
3cH
2, M=Co) and the mixture of manganese acetylacetonate, total concn is 450ppm.During device steady-state operation, the flow adding the fresh o-fluorotobuene in oxidation reactor is 10.9mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 2.2h, pressurization pure oxygen is passed in oxidation reactor continuously, maintenance system temperature of reaction is 185 DEG C, and reaction pressure is 1.7MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.90:1, and the temperature of reaction maintained in hydrolysis reactor is 144 DEG C, and reaction pressure is 1.2MPa, and now in hydrolysis reactor, the liquid phase residence time is 1.6h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 108 DEG C, and pressure is 1.1MPa.Through sampling analysis, the transformation efficiency of o-fluorotobuene is 97.0%, and the selectivity of adjacent fluorophenyl methanol, o fluorobenzaldehyde and o-fluorobenzoic acid is respectively 60.0%, 30.7% and 9.3%, and other by product does not detect.
Embodiment 3
Adding the catalyzer dissolved in fresh material para-bromo toluene in once oxidation reactor and acetic acid is Mn (Ac)
24H
2o, there is the metal phthalocyanine (R of general formula (IV) structure
1=NO
2, R
2=H, M=Co), there is the metalloporphyrin (R of general formula (I) structure
1=R
3=H, R
2=CH
3cH
2, M=Cu) mixture, total concn is 120ppm, and the mass ratio of acetic acid and para-bromo toluene is 0.056.During device steady-state operation, the flow adding the fresh material in oxidation reactor is 14.5mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 1.5h, pressurization pure oxygen is passed in oxidation reactor continuously, maintenance system temperature of reaction is 190 DEG C, and reaction pressure is 1.8MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.28:1, and pass into pressurization pure oxygen continuously, the temperature of reaction maintained in hydrolysis reactor is 149 DEG C, and reaction pressure is 1.2MPa, and now in hydrolysis reactor, the liquid phase residence time is 1.7h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 113 DEG C, and pressure is 1.1MPa.Through sampling analysis, the transformation efficiency that can obtain the para-bromo toluene in system is 99.9%, and be respectively 58.2%, 26.9% and 14.9% to the selectivity of bromobenzene methyl alcohol, p-bromobenzaldehyde and parabromobenzoic acid, other by product does not detect.
Embodiment 4
Add the catalyzer dissolved in fresh material para-nitrotoluene in once oxidation reactor and acetic acid to be N-hydroxyl-4-nitrophthalimide, there is the metal phthalocyanine (R of general formula (IV) structure
1=NH
2, R
2=H, M=Cu), cobalt naphthenate and there is the metalloporphyrin (R of general formula (III) structure
1=R
3=H, R
2=CH
3, M
1=M
2=Cr) mixture, total concn is 660ppm, and the mass ratio of acetic acid and para-nitrotoluene is 0.002.During device steady-state operation, the flow adding the fresh material in oxidation reactor is 5.3mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 4.5h, pressurization pure oxygen is passed in oxidation reactor continuously, maintenance system temperature of reaction is 105 DEG C, and reaction pressure is 0.2MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 1:1, and the temperature of reaction maintained in hydrolysis reactor is 56 DEG C, and reaction pressure is 0.2MPa, and now in hydrolysis reactor, the liquid phase residence time is 3.2h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 25.2 DEG C, and pressure is 0.1MPa.Through sampling analysis, the transformation efficiency that can obtain the para-nitrotoluene in system is 96.2%, and the selectivity of p nitrobenzyl alcohol, paranitrobenzaldehyde and p-nitrobenzoic acid is respectively 62.2%, 31.4% and 6.4%, and other by product does not detect.
Embodiment 5
The fresh catalyzer to dissolving in cyano group toluene adding once oxidation reactor is HP, cobalt naphthenate, have the metal phthalocyanine (R of general formula (IV) structure
1=H, R
2=H, M=Co) and there is the metalloporphyrin (R of general formula (III) structure
1=R
2=R
3=H, M
1=M
2=Mn) mixture, total concn is 800ppm.During device steady-state operation, the fresh flow to cyano group toluene added in oxidation reactor is 4.3mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 3.2h, pressurization pure oxygen is passed in oxidation reactor continuously, maintenance system temperature of reaction is 135 DEG C, and reaction pressure is 0.8MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.05:1, and the temperature of reaction maintained in hydrolysis reactor is 89 DEG C, and reaction pressure is 0.5MPa, and now in hydrolysis reactor, the liquid phase residence time is 4.3h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 56.2 DEG C, and pressure is 0.4MPa.Through sampling analysis, the transformation efficiency to cyano group toluene that can obtain in system is 97.0%, and to cyano group phenylcarbinol, be respectively 69.7%, 21.1% and 9.2% to the selectivity of cyanobenzaldehyde and paracyanobenzoic acid, other by product does not detect.
Embodiment 6
Adding the catalyzer dissolved in the fresh sym-trimethylbenzene in once oxidation reactor is N-hydroxyl-3,4,5,6-tetraphenyl phthalic imidine, acetylacetone cobalt and the metalloporphyrin (R with general formula (III) structure
1=R
3=H, R
2=NO
2, M
1=M
2=Mn) mixture, total concn is 40ppm.During device steady-state operation, the flow adding the fresh sym-trimethylbenzene in oxidation reactor is 13.6mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 0.6h, pressurization pure oxygen is passed in oxidation reactor continuously, maintenance system temperature of reaction is 250 DEG C, and reaction pressure is 3.0MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.21:1, and the temperature of reaction maintained in hydrolysis reactor is 215 DEG C, and reaction pressure is 2.0MPa, and now in hydrolysis reactor, the liquid phase residence time is 0.7h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 175 DEG C, and pressure is 1.9MPa.Through sampling analysis, the transformation efficiency that can obtain the sym-trimethylbenzene in system is 96.6%, 3,5-dimethylphenylcarbinol, the selectivity of 3,5-dimethylbenzaldehydes and 3,5-mesitylenic acid is respectively 76.0%, 16.0% and 8.0%, and other by product does not detect.
Embodiment 7
The fresh material added in once oxidation reactor is MnO to the catalyzer dissolved in methylsulfonyltoluene and acetic acid
2with Co (Ac)
24H
2the mixture of O, total concn is 150ppm, acetic acid be 0.15 to the mass ratio of methylsulfonyltoluene.During device steady-state operation, the fresh flow to methylsulfonyltoluene added in oxidation reactor is 9.4mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 3.5h, pressurization pure oxygen is passed in oxidation reactor continuously, maintenance system temperature of reaction is 150 DEG C, and reaction pressure is 1.1MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.42:1, and the temperature of reaction maintained in hydrolysis reactor is 105 DEG C, and reaction pressure is 0.7MPa, and now in hydrolysis reactor, the liquid phase residence time is 3.5h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 136 DEG C, and pressure is 0.6MPa.Through sampling analysis, the transformation efficiency to methylsulfonyltoluene that can obtain in system is 97.0%, and to methylsulfonyl phenylcarbinol, be respectively 51.5%, 39.2% and 9.3% to methylsulfonyl phenyl aldehyde with to the selectivity of thiamphenicol benzoic acid, other by product does not detect.
Embodiment 8
Add fresh material in once oxidation reactor to be HP to the catalyzer dissolved in hydroxytoluene and acetic acid, cobalt iso-octoate, to there is the metal phthalocyanine (R of general formula (IV) structure
1=OH, R
2=H, M=Ru) and there is the metalloporphyrin (R of general formula (III) structure
1=R
3=H, R
2=OH, M
1=M
2=Mn) mixture, total concn is 10000ppm, acetic acid be 0.10 to the mass ratio of hydroxytoluene.During device steady-state operation, the flow adding the fresh material in oxidation reactor is 11.6mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 0.4h, pressurization pure oxygen is passed in oxidation reactor continuously, maintenance system temperature of reaction is 155 DEG C, and reaction pressure is 1.2MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.70:1, and the temperature of reaction maintained in hydrolysis reactor is 111 DEG C, and reaction pressure is 0.8MPa, and now in hydrolysis reactor, the liquid phase residence time is 0.3h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 98 DEG C, and pressure is 0.7MPa.Through sampling analysis, the transformation efficiency to hydroxytoluene that can obtain in system is 98.5%, and the selectivity of p-Hydroxybenzylalcohol, p-Hydroxybenzaldehyde and P-hydroxybenzoic acid is respectively 73.4%, 11.7% and 14.9%, and other by product does not detect.
Embodiment 9
Adding the catalyzer dissolved in the fresh p-Xylol in once oxidation reactor is CuCl
2, there is the metal phthalocyanine (R of general formula (IV) structure
1=F, R
2=H, M=Fe) and there is the metalloporphyrin (R of general formula (II) structure
1=R
2=R
3=F, M=Co, X=Br) mixture, total concn is 30ppm.During device steady-state operation, the flow adding the fresh p-Xylol in oxidation reactor is 16.6mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 0.8h, pressurization pure oxygen is passed in oxidation reactor continuously, maintenance system temperature of reaction is 205 DEG C, and reaction pressure is 2.1MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.45:1, and pass into the oxygen-denuded air that oxygen mass percentage is 5% continuously, the temperature of reaction maintained in hydrolysis reactor is 166 DEG C, reaction pressure is 1.4MPa, and now in hydrolysis reactor, the liquid phase residence time is 0.8h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 129 DEG C, and pressure is 1.3MPa.Through sampling analysis, the transformation efficiency that can obtain the p-Xylol in system is 95.2%, and be respectively 75.0%, 22.1% and 2.9% to the selectivity of methylbenzyl alcohol, p-tolyl aldehyde and p-methylbenzoic acid, other by product does not detect.
Embodiment 10
Adding the catalyzer dissolved in fresh 2, the 3-dimethyl nitrobenzenes in once oxidation reactor is N-hydroxy-4-methyl phthalic imidine, cobalt iso-octoate and the metalloporphyrin (R with general formula (III) structure
1=R
3=H, R
2=NH
2, M
1=Mn, M
2=Cr) mixture, total concn is 550ppm.During device steady-state operation, add fresh 2 in oxidation reactor, the flow of 3-dimethyl nitrobenzene is 11.7mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 6h, pressurization pure oxygen is passed in oxidation reactor continuously, maintenance system temperature of reaction is 100 DEG C, and reaction pressure is 0.1MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.40:1, and the temperature of reaction maintained in hydrolysis reactor is 50 DEG C, and reaction pressure is 0.1MPa, and now in hydrolysis reactor, the liquid phase residence time is 6.0h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 20 DEG C, and pressure is 0.1MPa.Through sampling analysis, 2 in system can be obtained, the transformation efficiency of 3-dimethyl nitrobenzene is 96.2%, 2-methyl-3-nitro phenylcarbinol, 2-methyl-3-nitro phenyl aldehyde and the benzoic selectivity of 2-methyl-3-nitro are respectively 16.7%, 76.8% and 6.5%, and other by product does not detect.
Embodiment 11
Adding the catalyzer dissolved in fresh material 2,4-dimethyl nitrobenzene in once oxidation reactor and acetic acid is CeO
2, cobalt naphthenate and there is the metal phthalocyanine (R of general formula (IV) structure
1=H, R
2=CH
3cH
2, M=Mn) mixture, total concn is 450ppm, and the mass ratio of acetic acid and 2,4-dimethyl nitrobenzene is 0.08.During device steady-state operation, the flow adding the fresh material in oxidation reactor is 6.0mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 5.0h, by oxygen mass percentage be 80% oxygen-rich air pass into continuously in oxidation reactor, maintenance system temperature of reaction is 125 DEG C, and reaction pressure is 0.6MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.43:1, and pass into the oxygen-rich air that oxygen mass percentage is 80% continuously, the temperature of reaction maintained in hydrolysis reactor is 78 DEG C, reaction pressure is 0.4MPa, and now in hydrolysis reactor, the liquid phase residence time is 5.0h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 45.8 DEG C, and pressure is 0.3MPa.Through sampling analysis, 2 in system can be obtained, the transformation efficiency of 4-dimethyl nitrobenzene is 97.0%, 3-methyl-4-nitrobenzyl alcohol, the selectivity of 3-methyl-4-nitrobenzaldehyde and 3-methyl-4-nitrobenzoic acid is respectively 54.2%, 36.5% and 9.3%, and other by product does not detect.
Embodiment 12
Adding the catalyzer dissolved in the chloro-4-nitrotoluene of fresh material 2-in once oxidation reactor and acetic acid is Co (Ac)
24H
2o, there is the metal phthalocyanine (R of general formula (IV) structure
1=CH
3cH
2, R
2=H, M=Mn), there is the metalloporphyrin (R of general formula (I) structure
1=R
2=H, R
3=CH
3, M=Cu) mixture, total concn is 225ppm, and the mass ratio of acetic acid and the chloro-4-nitrotoluene of 2-is 0.04.During device steady-state operation, the flow adding the fresh material in oxidation reactor is 4.3mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 4.0h, by oxygen mass percentage be 60% oxygen-rich air pass into continuously in oxidation reactor, maintenance system temperature of reaction is 130 DEG C, and reaction pressure is 0.7MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.57:1, and pass into the oxygen-rich air that oxygen mass percentage is 60% continuously, the temperature of reaction maintained in hydrolysis reactor is 83 DEG C, reaction pressure is 0.5MPa, and now in hydrolysis reactor, the liquid phase residence time is 3.6h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 51 DEG C, and pressure is 0.4MPa.Through sampling analysis, the transformation efficiency that can obtain the chloro-4-nitrotoluene of 2-in system is 97.2%, the selectivity of 2-chloro-4-nitrobenzyl alcohol, 2-chloro-4-nitrobenzaldehyde and the chloro-4-nitrobenzoic acid of 2-is respectively 65.6%, 24.2% and 10.2%, and other by product does not detect.
Embodiment 13
Adding the catalyzer dissolved in the fresh ortho-chlorotolu'ene in once oxidation reactor is RuCl
2, N-hydroxyl-3-picolyl phthalic imidine and there is the metalloporphyrin (R of general formula (III) structure
1=R
3=H, R
2=Cl, M
1=M
2=Fe) mixture, total concn is 300ppm.During device steady-state operation, the flow adding the fresh ortho-chlorotolu'ene in oxidation reactor is 23.4mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 2.2h, forced air is passed in oxidation reactor continuously, maintenance system temperature of reaction is 160 DEG C, and reaction pressure is 1.3MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.52:1, and pass into forced air continuously, the temperature of reaction maintained in hydrolysis reactor is 116 DEG C, and reaction pressure is 0.9MPa, and now in hydrolysis reactor, the liquid phase residence time is 2.1h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 82 DEG C, and pressure is 0.8MPa.Through sampling analysis, the transformation efficiency that can obtain the ortho-chlorotolu'ene in system is 95.6%, and the selectivity of adjacent chlorobenzene methanol, o-chlorobenzaldehyde and 0-chloro-benzoic acid is respectively 36.1%, 59.6% and 4.3%, and other by product does not detect.
Embodiment 14
Adding the catalyzer dissolved in fresh toluene fluoride in once oxidation reactor is Co (Ac)
24H
2o, there is the metal phthalocyanine (R of general formula (IV) structure
1=CH
3cH
2, R2=H, M=Mn), there is the metalloporphyrin (R of general formula (I) structure
1=R
2=H, R
3=CH
3, M=Cu) mixture, total concn is 380ppm.During device steady-state operation, the flow adding fresh toluene fluoride in oxidation reactor is 15.7mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 2.8h, forced air is passed in oxidation reactor continuously, maintenance system temperature of reaction is 186 DEG C, and reaction pressure is 1.8MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.24:1, and pass into forced air continuously, the temperature of reaction maintained in hydrolysis reactor is 145 DEG C, and reaction pressure is 1.2MPa, and now in hydrolysis reactor, the liquid phase residence time is 3.2h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 109 DEG C, and pressure is 1.1MPa.Through sampling analysis, between can obtaining in system, the transformation efficiency of toluene fluoride is 95.8%, and the selectivity of a fluorophenyl methanol, a fluorobenzaldehyde and m-fluorobenzoic acid is respectively 43.1%, 51.8% and 5.1%, and other by product does not detect.
Embodiment 15
Adding the catalyzer dissolved in the fresh o-bromotoluene in once oxidation reactor is Co (NO
3)
4, N-ethanoyl phthalic imidine, there is the metal phthalocyanine (R of general formula (IV) structure
1=OCH
3, R
2=H, M=Ni) and there is the metalloporphyrin (R of general formula (I) structure
1=R
3=OCH
3, R
2=H, M=Fe) mixture, total concn is 7800ppm.During device steady-state operation, the flow adding the fresh o-bromotoluene in oxidation reactor is 6.5mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 2.0h, pressurization pure oxygen is passed in oxidation reactor continuously, maintenance system temperature of reaction is 182 DEG C, and reaction pressure is 1.7MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.19:1, and pass into pressurization pure oxygen continuously, the temperature of reaction maintained in hydrolysis reactor is 140 DEG C, and reaction pressure is 1.1MPa, and now in hydrolysis reactor, the liquid phase residence time is 2.4h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 105 DEG C, and pressure is 1.0MPa.Through sampling analysis, the transformation efficiency that can obtain the o-bromotoluene in system is 97.7%, and the selectivity of adjacent bromobenzene methyl alcohol, o-bromobenzaldehye and o-bromobenzoic acid is respectively 68.1%, 19.8% and 12.1%, and other by product does not detect.
Embodiment 16
Adding the catalyzer dissolved in the fresh Ortho Nitro Toluene in once oxidation reactor is N-hydroxyl-3,4,5,6-tetraphenyl phthalic imidine and Co (Ac)
2, total concn is 8000ppm.During device steady-state operation, the flow adding the fresh adjacent nitro in oxidation reactor is 4.7mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 4.2h, by oxygen mass percentage be 40% pressurization oxygen enrichment pass into continuously in oxidation reactor, maintenance system temperature of reaction is 110 DEG C, and reaction pressure is 0.3MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.37:1, and pass into the pressurization oxygen enrichment that oxygen mass percentage is 40% continuously, the temperature of reaction maintained in hydrolysis reactor is 61 DEG C, reaction pressure is 0.2MPa, and now in hydrolysis reactor, the liquid phase residence time is 4.4h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 30.3 DEG C, and pressure is 0.1MPa.Through sampling analysis, the transformation efficiency that can obtain the Ortho Nitro Toluene in system is 97.5%, and the selectivity of nitro alcohol, Ortho Nitro Benzaldehyde and o-Carboxynitrobenzene is respectively 62.5%, 26.2% and 11.3%, and other by product does not detect.
Embodiment 17
The fresh catalyzer to dissolving in methoxy toluene added in once oxidation reactor is MnO
2, there is the metal phthalocyanine (R of general formula (IV) structure
1=H, R
2=OH, M=Ru) and there is the metalloporphyrin (R of general formula (II) structure
1=R
3=NH
2, R
2=H, M=Cr, X=acetate) mixture, total concn is 360ppm.During device steady-state operation, the fresh flow to methoxy toluene added in oxidation reactor is 30.8mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 1.0h, forced air is passed in oxidation reactor continuously, maintenance system temperature of reaction is 168 DEG C, and reaction pressure is 1.4MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.30:1, and the temperature of reaction maintained in hydrolysis reactor is 125 DEG C, and reaction pressure is 1.0MPa, and now in hydrolysis reactor, the liquid phase residence time is 1.1h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 90.3 DEG C, and pressure is 0.9MPa.Through sampling analysis, the transformation efficiency to methoxy toluene that can obtain in system is 96.1%, and the selectivity of p-methoxybenzyl alcohol, aubepine and anisic acid is respectively 55.4%, 38.4% and 6.2%, and other by product does not detect.
Embodiment 18
Adding the catalyzer dissolved in the fresh m-chlorotoluene in once oxidation reactor is ZrO
2, N, N '-dihydroxyl phthalic imidine, there is the metal phthalocyanine (R of general formula (IV) structure
1=H, R
2=NO
2, M=Co), manganese naphthenate and there is the metalloporphyrin (R of general formula (I) structure
1=R
3=Cl, R
2=H, M=Zn) mixture, total concn is 100ppm.During device steady-state operation, the flow adding the fresh m-chlorotoluene in oxidation reactor is 8.8mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 1.2h, forced air is passed in oxidation reactor continuously, maintenance system temperature of reaction is 175 DEG C, and reaction pressure is 1.5MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.43:1, and pass into forced air continuously, the temperature of reaction maintained in hydrolysis reactor is 127 DEG C, and reaction pressure is 1.0MPa, and now in hydrolysis reactor, the liquid phase residence time is 1.2h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 92.3 DEG C, and pressure is 0.9MPa.Through sampling analysis, the transformation efficiency that can obtain the m-chlorotoluene in system is 96.2%, and the selectivity of a chlorobenzene methanol, m chlorobenzaldehyde and m-chlorobenzoic acid is respectively 74.9%, 18.6% and 6.5%, and other by product does not detect.
Embodiment 19
Add the catalyzer dissolved in fresh material m-bromotoluene in once oxidation reactor and acetic acid to be N-hydroxyl-4-carboxyl phthalic imidine, there is the metal phthalocyanine (R of general formula (IV) structure
1=Cl, R
2=H, M=Zn), acetylacetone cobalt and there is the metalloporphyrin (R of general formula (III) structure
1=R
3=H, R
2=OCH
3, M
1=Fe, M
2=Mn) mixture, total concn is 1200ppm, and the mass ratio of solvent and m-bromotoluene is 0.084.During device steady-state operation, the flow adding the fresh material in oxidation reactor is 10.9mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 3.2h, pressurization pure oxygen is passed in oxidation reactor continuously, maintenance system temperature of reaction is 202 DEG C, and reaction pressure is 2.1MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.24:1, and pass into pressurization pure oxygen continuously, the temperature of reaction maintained in hydrolysis reactor is 162 DEG C, and reaction pressure is 1.4MPa, and now in hydrolysis reactor, the liquid phase residence time is 3.7h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 125 DEG C, and pressure is 1.3MPa.Through sampling analysis, the transformation efficiency that can obtain the m-bromotoluene in system is 96.5%, and the selectivity of bromobenzene methyl alcohol, 3-bromobenzaldehyde and m-bromobenzoic acid is respectively 50.8%, 41.6% and 7.6%, and other by product does not detect.
Embodiment 20
Add the catalyzer that dissolves in the fresh o-Xylol in once oxidation reactor for having the metalloporphyrin (R of general formula (I) structure
1=R
2=R
3=H, M=Co) be catalyzer, total concn is 10ppm.During device steady-state operation, the flow adding the fresh o-Xylol in oxidation reactor is 26.7mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 1.5h, forced air is passed in oxidation reactor continuously, maintenance system temperature of reaction is 198 DEG C, and reaction pressure is 1.9MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.21:1, and pass into forced air continuously, the temperature of reaction maintained in hydrolysis reactor is 155 DEG C, and reaction pressure is 1.3MPa, and now in hydrolysis reactor, the liquid phase residence time is 1.8h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 118 DEG C, and pressure is 1.2MPa.Through sampling analysis, the transformation efficiency that can obtain the o-Xylol in system is 95.6%, and the selectivity of o-methyl-benzene methyl alcohol, o-tolualdehyde and o-toluic acid is respectively 46.8%, 47.8% and 5.4%, and other by product does not detect.
Embodiment 21
Adding the catalyzer dissolved in the fresh p-fluorotoluene in once oxidation reactor is FeCl
2, N-glutarimide and there is the metal phthalocyanine (R of general formula (IV) structure
1=H, R
2=OCH
3, M=Ni) and there is the metalloporphyrin (R of general formula (I) structure
1=R
3=CH
3, R
2=H, M=Mn) mixture, total concn is 1000ppm.During device steady-state operation, the flow adding the fresh p-fluorotoluene in oxidation reactor is 6.4mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 2.4h, by oxygen mass percentage be 15% oxygen-denuded air pass into continuously in oxidation reactor, maintenance system temperature of reaction is 222 DEG C, and reaction pressure is 2.5MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.51:1, and pass into the oxygen-denuded air that oxygen mass percentage is 15% continuously, the temperature of reaction maintained in hydrolysis reactor is 184 DEG C, reaction pressure is 1.6MPa, and now in hydrolysis reactor, the liquid phase residence time is 2.3h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 146 DEG C, and pressure is 1.5MPa.Through sampling analysis, the transformation efficiency that can obtain the p-fluorotoluene in system is 95.0%, and be respectively 73.4%, 24.4% and 2.2% to the selectivity of fluorophenyl methanol, p-Fluorobenzenecarboxaldehyde and parafluorobenzoic acid, other by product does not detect.
Embodiment 22
Add the catalyzer that dissolves in the fresh m-xylene in once oxidation reactor for having the metalloporphyrin (R of general formula (III) structure
1=R
3=Cl, R
2=H, M=Mn) mixture, concentration is 1ppm.During device steady-state operation, the flow adding the fresh m-xylene in oxidation reactor is 3.0mL/h, now in the mean residence time of the oxidation reactor of liquid phase substance for 4h, forced air is passed in oxidation reactor continuously, maintenance system temperature of reaction is 220 DEG C, and reaction pressure is 2.4MPa.The water yield adding hydrolysis reactor and the oxidation liquid volume ratio entering hydrolysis reactor are 0.95:1, and pass into forced air continuously, the temperature of reaction maintained in hydrolysis reactor is 182 DEG C, and reaction pressure is 1.6MPa, and now in hydrolysis reactor, the liquid phase residence time is 2.9h.Hydrolysis reactor outlet liquid phase enters liquid liquid quantizer continuously, and liquid liquid quantizer temperature is 144 DEG C, and pressure is 1.5MPa.Through sampling analysis, the transformation efficiency that can obtain the m-xylene in system is 98.5%, and the selectivity of a methylbenzyl alcohol, a tolyl aldehyde and m-methyl benzoic acid is respectively 67.0%, 18.1% and 14.9%, and other by product does not detect.
Claims (10)
1. a method for coproduction substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid, is characterized in that comprising the following steps:
(1) be oxidized: in oxidation reactor, pass into replacement toluene, catalyzer and oxygen-containing gas continuously react, tail oxygen concentration is controlled within 5% by the intake controlling oxygen-containing gas, the consumption of described catalyzer is the 1-10000ppm replacing toluene quality, temperature of reaction is 100 ~ 250 DEG C, reaction pressure 0.1 ~ 3MPa, be 0.4 ~ 6 hour in the mean residence time of the oxidation reactor of liquid phase substance, obtain oxidation liquid;
(2) be hydrolyzed: the oxidation liquid that step (1) obtains is entered in hydrolysis reactor continuously, and in hydrolysis reactor, add water continuously react, it is described that to add the water yield with the oxidation liquid volume ratio entering hydrolysis reactor be 0.05 ~ 1:1, temperature of reaction is 50 ~ 215 DEG C, reaction pressure is 0.1 ~ 2.0MPa, in hydrolysis reactor, the liquid phase residence time is 0.3 ~ 6 hour, obtains hydrolysis reaction mixture;
(3) liquid liquid layering: hydrolysis reaction mixture step (2) obtained is 20 ~ 175 DEG C in temperature, pressure is the lower leaf of 0.1 ~ 2.0MPa condition, obtains containing replacing toluene and substituted benzyl alcohol, the oil phase of substituted benzaldehyde and the aqueous phase containing substituted benzyl alcohol, substituted benzaldehyde and substituted benzoic acid;
(4) separation of product: the oil phase that step (3) obtains is carried out rectifying and obtain unreacted respectively and replace toluene, substituted benzyl alcohol and substituted benzaldehyde product completely, aqueous phase crystallisation by cooling step (3) obtained filters, and obtains filtrate and substituted benzoyl acid product.
2. coproduction substituted benzaldehyde according to claim 1, the method of substituted benzyl alcohol and substituted benzoic acid, it is characterized in that described replacement toluene is parachlorotoluene, o-fluorotobuene, para-bromo toluene, para-nitrotoluene, to cyano group toluene, sym-trimethylbenzene, to methylsulfonyltoluene, to hydroxytoluene, p-Xylol, 2, 3-dimethyl nitrobenzene, 2, 4-dimethyl nitrobenzene, the chloro-4-nitrotoluene of 2-, ortho-chlorotolu'ene, between toluene fluoride, o-bromotoluene, Ortho Nitro Toluene, to methoxy toluene, m-chlorotoluene, m-bromotoluene, o-Xylol, p-fluorotoluene, one in m-xylene.
3. the method for coproduction substituted benzaldehyde according to claim 1, substituted benzyl alcohol and substituted benzoic acid, is characterized in that the mass percentage of oxygen in described oxygen-containing gas is more than or equal to 15%.
4. the method for coproduction substituted benzaldehyde according to claim 1, substituted benzyl alcohol and substituted benzoic acid, is characterized in that described catalyzer is the mixture of one or more in transition metal salt or oxide compound, HP and analogue thereof, the metalphthelein mountain valley with clumps of trees and bamboo, metalloporphyrin.
5. the method for coproduction substituted benzaldehyde according to claim 4, substituted benzyl alcohol and substituted benzoic acid, is characterized in that described transition metal salt or oxide compound are selected from the one in the salt of Co, Cu, Ni, Zn, Mn, Fe, Cr, Ce, Zr, Ru, Hf or oxide compound, described HP and analogue thereof are selected from HP, N-hydroxyl-4-nitrophthalimide, N-hydroxyl-4-carboxyl phthalic imidine, N-hydroxy-4-methyl phthalic imidine, N-hydroxyl-3, 4, 5, 6-tetraphenyl phthalic imidine, N, N '-dihydroxyl phthalic imidine, the adjacent sulfonyl-benzoyl amine of N-hydroxyl, N-ethanoyl phthalic imidine, N, N ', N "-trihydroxy-tricarbimide, N-hydroxyl-3-picolyl phthalic imidine, N-glutarimide, one in N-hydroxysuccinimide.
6. the method for coproduction substituted benzaldehyde according to claim 4, substituted benzyl alcohol and substituted benzoic acid, is characterized in that described metalloporphyrin has the structure of general formula (I) or general formula (II) or general formula (III):
Atoms metal M in its formula of (I) is selected from Co, Cu, Ni, Zn, Ru, Mn, Fe; Atoms metal M in general formula (II) is selected from Fe, Mn, Cr, Co; Atoms metal M in general formula (III)
1, M
2be selected from Fe, Mn, Cr respectively; Dentate X in general formula (II) is acetate, methyl ethyl diketone root, halogen; Substituent R in general formula (I), (II) and (III)
1, R
2and R
3be respectively the one in hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, nitro.
7. the method for coproduction substituted benzaldehyde according to claim 4, substituted benzyl alcohol and substituted benzoic acid, is characterized in that the described metalphthelein mountain valley with clumps of trees and bamboo has the structure of general formula (IV):
Wherein atoms metal M is selected from Co, Cu, Ni, Zn, Ru, Mn, Fe, substituent R
1and R
2be respectively hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, nitro.
8. the method for coproduction substituted benzaldehyde according to claim 1, substituted benzyl alcohol and substituted benzoic acid, is characterized in that the unreacted that step (4) obtains to replace toluene completely and filtrate loops back in oxidation reactor and hydrolysis reactor respectively.
9. the method for coproduction substituted benzaldehyde according to claim 1, substituted benzyl alcohol and substituted benzoic acid, it is characterized in that in hydrolysis reactor, adding water continuously when reacting described in step (2), in hydrolysis reactor, pass into the oxygen-containing gas that oxygen mass percentage is more than or equal to 5% continuously simultaneously, and control tail oxygen concentration within 5% by the intake controlling oxygen-containing gas.
10. the method for coproduction substituted benzaldehyde according to claim 1, substituted benzyl alcohol and substituted benzoic acid, when it is characterized in that passing into continuously in oxidation reactor described in step (1) replaces toluene, simultaneously in oxidation reactor, pass into solvent acetic acid, described in the acetic acid that passes into be 0.002 ~ 0.15:1 with the mass ratio replacing toluene.
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