CN106831392B - Method for co-producing benzoic acid, p-methylbenzoic acid and m-methylbenzoic acid - Google Patents
Method for co-producing benzoic acid, p-methylbenzoic acid and m-methylbenzoic acid Download PDFInfo
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- CN106831392B CN106831392B CN201611100762.4A CN201611100762A CN106831392B CN 106831392 B CN106831392 B CN 106831392B CN 201611100762 A CN201611100762 A CN 201611100762A CN 106831392 B CN106831392 B CN 106831392B
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- xylene
- benzoic acid
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 150
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 title claims abstract description 138
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000005711 Benzoic acid Substances 0.000 title claims abstract description 75
- 235000010233 benzoic acid Nutrition 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 49
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 188
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 141
- 238000006243 chemical reaction Methods 0.000 claims abstract description 123
- 239000008096 xylene Substances 0.000 claims abstract description 107
- 230000003647 oxidation Effects 0.000 claims abstract description 73
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 238000009835 boiling Methods 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 6
- 239000012071 phase Substances 0.000 claims abstract description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 110
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 102
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 94
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 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 claims description 18
- 239000000543 intermediate Substances 0.000 claims description 16
- -1 transition metal salt Chemical class 0.000 claims description 12
- 229940078552 o-xylene Drugs 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- CNRMRKSNOUGQLV-UHFFFAOYSA-N 2-hydroxy-4,5,6,7-tetraphenylisoindole-1,3-dione Chemical compound O=C1N(O)C(=O)C(C(=C(C=2C=CC=CC=2)C=2C=3C=CC=CC=3)C=3C=CC=CC=3)=C1C=2C1=CC=CC=C1 CNRMRKSNOUGQLV-UHFFFAOYSA-N 0.000 claims description 4
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical class C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-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
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- NBIJDQIBCRZHFK-UHFFFAOYSA-N 1,3,5-trihydroxy-1,3,5-triazinane-2,4,6-trione Chemical compound ON1C(=O)N(O)C(=O)N(O)C1=O NBIJDQIBCRZHFK-UHFFFAOYSA-N 0.000 claims description 3
- GTFDJMHTJNPQFS-UHFFFAOYSA-N 1-hydroxypiperidine-2,6-dione Chemical compound ON1C(=O)CCCC1=O GTFDJMHTJNPQFS-UHFFFAOYSA-N 0.000 claims description 3
- INZUQGFQRYAKQQ-UHFFFAOYSA-N 2-acetylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(C(=O)C)C(=O)C2=C1 INZUQGFQRYAKQQ-UHFFFAOYSA-N 0.000 claims description 3
- HFZILYOGBNDBNK-UHFFFAOYSA-N 2-hydroxy-5-methylisoindole-1,3-dione Chemical compound CC1=CC=C2C(=O)N(O)C(=O)C2=C1 HFZILYOGBNDBNK-UHFFFAOYSA-N 0.000 claims description 3
- 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
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- VBBUVIWLZBAEEF-UHFFFAOYSA-N 2,6-dihydroxypyrrolo[3,4-f]isoindole-1,3,5,7-tetrone Chemical compound C1=C2C(=O)N(O)C(=O)C2=CC2=C1C(=O)N(O)C2=O VBBUVIWLZBAEEF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- XXYNZSATHOXXBJ-UHFFFAOYSA-N 4-hydroxyisoindole-1,3-dione Chemical class OC1=CC=CC2=C1C(=O)NC2=O XXYNZSATHOXXBJ-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 68
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 41
- 230000000694 effects Effects 0.000 description 32
- 230000035484 reaction time Effects 0.000 description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 18
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 15
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 13
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 9
- 150000003738 xylenes Chemical class 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 5
- JJCKHVUTVOPLBV-UHFFFAOYSA-N 3-Methylbenzyl alcohol Chemical compound CC1=CC=CC(CO)=C1 JJCKHVUTVOPLBV-UHFFFAOYSA-N 0.000 description 4
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 3
- 229960003424 phenylacetic acid Drugs 0.000 description 3
- 239000003279 phenylacetic acid Substances 0.000 description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-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
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ILJTZGSGCNDILQ-UHFFFAOYSA-N 2-hydroxy-1,3-dioxoisoindole-5-carboxylic acid Chemical compound C1=C(C(O)=O)C=C2C(=O)N(O)C(=O)C2=C1 ILJTZGSGCNDILQ-UHFFFAOYSA-N 0.000 description 1
- VTURQLGQZRYNSS-UHFFFAOYSA-N 2-hydroxy-4-(pyridin-3-ylmethyl)isoindole-1,3-dione Chemical compound ON1C(C=2C(C1=O)=C(C=CC=2)CC=1C=NC=CC=1)=O VTURQLGQZRYNSS-UHFFFAOYSA-N 0.000 description 1
- IRWZGODUFFQVBQ-UHFFFAOYSA-N C=1(C(=CC=CC1)C(=O)O)C.C(C1=CC=C(C(=O)O)C=C1)(=O)O Chemical compound C=1(C(=CC=CC1)C(=O)O)C.C(C1=CC=C(C(=O)O)C=C1)(=O)O IRWZGODUFFQVBQ-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NHAOZLUXPKUBGM-UHFFFAOYSA-N [N+](=O)(O)[O-].CC1=C(C=CC=C1)C Chemical compound [N+](=O)(O)[O-].CC1=C(C=CC=C1)C NHAOZLUXPKUBGM-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229960002903 benzyl benzoate Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 210000001136 chorion Anatomy 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical group Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920003240 metallophthalocyanine polymer Polymers 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for coproducing benzoic acid, p-methyl benzoic acid and m-methyl benzoic acid, which comprises the following steps: (1) and (3) oxidation: adding a xylene mixture, a catalyst and oxygen-containing gas with the oxygen content of not less than 15 percent by mass into an oxidation reactor for reaction; (2) gas-liquid separation and purification: and (3) feeding the oxidation reaction liquid into a gas-liquid separator, condensing and separating a gas phase part, circulating a condensate to the oxidation reaction liquid for continuous oxidation, treating non-condensable gas and emptying, performing conventional rectification on a liquid phase part, obtaining a low-boiling-point component with a boiling point lower than that of benzoic acid at the tower top, circulating the low-boiling-point component back to the oxidation reactor for continuous oxidation, and further performing conventional rectification on a tower bottom component to sequentially obtain benzoic acid, m-methylbenzoic acid and p-methylbenzoic acid products. The method has the advantages of simple process, low raw material cost, less equipment investment, high yield, good selectivity and good economic benefit.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a method for co-producing benzoic acid, p-toluic acid and m-toluic acid.
Technical Field
Benzoic acid is an important bulk organic chemical raw material, is used for producing chemical products such as benzyl benzoate, methyl benzoate, ethyl benzoate and the like in the chemical industry, is used for producing medicaments such as chorion and the like in medicine, is used for producing alkyd resin, polyamide resin and the like in the synthetic resin industry, and is widely used as a preservative in the food industry. The preparation method is mainly a toluene air oxidation method.
Methyl benzoic acid is also an important bulk organic chemical raw material which can be used as an intermediate of medicines, pesticides, organic pigments, whitening agents and the like, and the preparation method of the methyl benzoic acid mainly comprises a dimethylbenzene nitric acid oxidation method, a dimethylbenzene air oxidation method, a methylbenzene carbonylation-oxidation method and the like, and the most economical and effective method is the dimethylbenzene air oxidation method. The methyl benzoic acid can be further oxidized into phthalic acid, which is an important raw material in the polyester industry and a large amount of chemical raw materials related to the countryside, but the price of the phthalic acid is far lower than that of the methyl benzoic acid. Therefore, the target product of xylene oxidation should be methylbenzoic acid as much as possible and phthalic acid production should be avoided as much as possible from the viewpoint of economic added value.
In the process of preparing methylbenzoic acid by air oxidation of xylene, methyl on the xylene is the most inert substance in the reaction system, and the activation of the methyl on the xylene is the most difficult step in the whole reaction, so that the required reaction conditions are the most severe. Once the methyl reaction on the benzene ring is initiated, the subsequent reactions are relatively easy to occur. In order to activate the methyl group on the benzene ring, strict reaction conditions are generally adopted, and the strict reaction conditions can simultaneously lead the target product methyl benzoic acid generated in the system to be further deeply oxidized, so that the selectivity of the high value-added target product methyl benzoic acid is reduced, and the selectivity of a byproduct (namely, a product obtained by oxidizing a second methyl group on the benzene ring) is improved. This is also the reason why the selectivity of the product is not high and the final by-products are more when the xylene is selectively oxidized to prepare methyl benzoic acid in the industry at present.
Furthermore, in the production process of the methyl benzoic acid, the cost of the raw material dimethylbenzene accounts for more than 75% of the production cost of the whole methyl benzoic acid. The existing p-xylene and m-xylene are both separated from mixed xylene. Because the boiling points of p-xylene and m-xylene are very similar, the separation is very difficult in industry, and the conversion and the cost are very high, so that the prices of the p-xylene and the m-xylene which are used as raw materials are far higher than the price of mixed xylene. In particular, m-xylene has a large price fluctuation due to limited market demand, concentration of manufacturers, and a large amount of price fluctuation. Therefore, the research on the m-methyl benzoic acid and p-methyl benzoic acid technology which has wide raw material source, low price, diversified product structure and high risk of resisting market situation change is the research target of the technicians in the field. The mixed xylene is from naphtha or coal, the annual domestic productivity has broken through 3000 ten thousand tons, the market price is strict and the petroleum price is hooked, the fluctuation range is obviously small, the source is wide, and the price is low. The mixed dimethylbenzene is used for co-catalytic oxidation to produce m-methyl benzoic acid and p-methyl benzoic acid, which is a process method capable of obtaining better expected effects.
From the literature published at present, the target products of oxidation of mixed xylenes are mostly concentrated on phthalic acid. Representative publications include: the method for preparing phthalic acid by a catalyst system for mixed xylene co-oxidation (CN102924266A), the production method of mixed aromatic dicarboxylic acid (CN103183607A, CN102584572A), the method for producing benzenedicarboxylic acid by mixed xylene co-oxidation (CN1962598A), and the research on the mixed oxidation process of p-xylene and m-xylene (Liujian, Liuyang. synthetic fiber industry, 2016,39(3): 38-40.). The common point of the methods is that the mixture of m-xylene and p-xylene is used as raw material, corrosive acetic acid is used as solvent, the raw material is oxidized into final products of isophthalic acid and terephthalic acid under harsh reaction conditions, and then refining and purification are carried out. However, the raw material source of the method still has the defects of high cost and not wide source. This is because the raw material of the method still needs to be separated from the mixed xylene, and the method needs to firstly rectify and separate the o-xylene (boiling point 144.4 ℃) with high boiling point which is easy to separate, and then separate the ethylbenzene (boiling point 136.2 ℃) with boiling point which is very close to that of the m-xylene (boiling point 139.0 ℃) and the p-xylene (boiling point 138.4 ℃) by a high energy consumption method. The separation energy consumption is high, which leads to high cost price of raw materials.
CN10318890A and CN101508638A disclose a method for preparing mixed phthalic acid and phenylacetic acid by directly oxidizing mixed xylene without further treatment. Wherein the mixed xylene is a mixture of ethylbenzene, o-xylene, m-xylene and p-xylene. The method adopts a traditional MC oxidation system, namely a Co/Mn/Br/acetic acid system, is consistent with the common knowledge of the technical personnel in the field, and the products are phthalic acid and phenylacetic acid.
Article "selective oxidation of mixed xylenes catalyzed by cobalt hydroxylamine acid complex (Chenjun, Zhang, Hujiayuan, Lixianhu. chemical research and application, 2002, 14(2),178-N-benzoyl-NThe activity of liquid phase catalytic oxidation of different mixed dimethylbenzenes is evaluated under the pressure of 0.5MPa by taking a complex of phenylhydroxylamine and cobalt salt as a catalyst and pure oxygen as an oxygen source, and the catalyst is proved to have good activity, wherein the order of the reaction activity of the three dimethylbenzenes is as follows: para-xylene>Ortho-xylene>Meta-xylene. When the reaction temperature is 125 ℃ under the condition of the 1:1 ratio of the isomeric dimethylbenzene for 2 hours, the oxidation speed of p-xylene is 7 times faster than that of m-xylene, and the oxidation speed of o-xylene is 4 times faster than that of m-xylene. The method has the obvious defects that in addition to being the same as the method for producing the mixed aromatic dicarboxylic acid by adopting the mixture of the p-xylene and the m-xylene as the raw material, under the catalytic system, the oxidation rate difference of the m-xylene and the p-xylene is large, the m-xylene and the p-xylene can not be completely oxidized at the same time, and the defects of high raw material cost and wide source still exist.
Disclosure of Invention
The invention aims to provide a method for coproducing benzoic acid, p-toluic acid and m-toluic acid, and solves the problems of low sources of raw materials required for production, high production cost and large difference of oxidation rates of mixed dimethylbenzene in the prior art.
The technical scheme adopted for realizing the purpose comprises the following steps:
(1) and (3) oxidation: adding a xylene mixture, a catalyst and oxygen-containing gas with the oxygen content of not less than 15 mass percent into an oxidation reactor for reaction, wherein the xylene mixture comprises ethylbenzene, p-xylene and m-xylene, impurities in the xylene mixture are o-xylene, the mass percent of the ethylbenzene in the xylene mixture is not less than 10 percent, and the mass percent of the o-xylene impurity is not more than 0.5 percentPercent, the catalyst is transition metal salt or oxide,NOne or a mixture of more of a hydroxyphthalimide compound, metal phthalocyanine and metalloporphyrin, wherein the dosage of the catalyst is 10-10000ppm of the mass of the xylene mixture, the reaction temperature is 115-190 ℃, the reaction pressure is 0.2-3 MPa, and the average residence time of the oxidation reactor calculated by liquid phase substances is 0.3-5 hours, so that oxidation reaction liquid containing raw materials, various oxygen-containing intermediates with the boiling point lower than that of benzoic acid and products of benzoic acid, p-toluic acid and m-toluic acid is obtained;
(2) gas-liquid separation and purification: and (3) feeding the oxidation reaction liquid into a gas-liquid separator, condensing and separating a gas phase part, circulating a condensate to the oxidation reaction liquid for continuous oxidation, treating non-condensable gas and emptying, performing conventional rectification on a liquid phase part, obtaining a low-boiling-point component with a boiling point lower than that of benzoic acid at the tower top, circulating the low-boiling-point component back to the oxidation reactor for continuous oxidation, and further performing conventional rectification on a tower bottom component to sequentially obtain benzoic acid, m-methylbenzoic acid and p-methylbenzoic acid products.
Advantageous effects
Compared with the prior art, the invention has the following advantages.
1. The raw materials are wide in source and low in price, the product structure is diversified, and the risk of resisting market situation change is high;
2. the reaction condition is mild, the conversion rate is high, and the selectivity is good;
3. the process is simple, and the equipment investment is low;
4. the economic benefit is good.
Detailed Description
A method for coproducing benzoic acid, p-methylbenzoic acid and m-methylbenzoic acid comprises the following steps:
(1) and (3) oxidation: adding a xylene mixture, a catalyst and oxygen-containing gas with the oxygen content of not less than 15 mass percent into an oxidation reactor for reaction, wherein the xylene mixture comprises ethylbenzene, p-xylene and m-xylene, impurities in the xylene mixture are o-xylene, the mass percent of the ethylbenzene in the xylene mixture is not less than 10 percent, the mass percent of the o-xylene impurity is not more than 0.5 percent, and the mixed product is prepared by the steps ofThe catalyst is transition metal salt or oxide,NOne or a mixture of more of a hydroxyphthalimide compound, metal phthalocyanine and metalloporphyrin, wherein the dosage of the catalyst is 10-10000ppm of the mass of the xylene mixture, the reaction temperature is 115-190 ℃, the reaction pressure is 0.2-3 MPa, and the average residence time of the oxidation reactor calculated by liquid phase substances is 0.3-5 hours, so that oxidation reaction liquid containing raw materials, various oxygen-containing intermediates with the boiling point lower than that of benzoic acid and products of benzoic acid, p-toluic acid and m-toluic acid is obtained;
(2) gas-liquid separation and purification: and (3) feeding the oxidation reaction liquid into a gas-liquid separator, condensing and separating a gas phase part, circulating a condensate to the oxidation reaction liquid for continuous oxidation, treating non-condensable gas and emptying, performing conventional rectification on a liquid phase part, obtaining a low-boiling-point component with a boiling point lower than that of benzoic acid at the tower top, circulating the low-boiling-point component back to the oxidation reactor for continuous oxidation, and further performing conventional rectification on a tower bottom component to sequentially obtain benzoic acid, m-methylbenzoic acid and p-methylbenzoic acid products.
The transition metal salt or oxide is selected from one of the salts or oxides of Co, Cu, Ni, Zn, Mn, Fe, Cr, Ce, Zr, Ru and Hf.
The above-mentionedN-hydroxyphthalimide compounds selected fromN-hydroxyphthalimides,N-hydroxy-4-nitrophthalimide,N-hydroxy-4-carboxyphthalimide,N-hydroxy-4-methylphthalimide,N-hydroxy-3, 4,5, 6-tetraphenylphthalimide,N,N’-dihydroxypyromellitic diimide,N-hydroxy-o-sulfonylbenzoylimines,N-acetylphthalimide, a salt thereof,N,N’,N’’-trihydroxyisocyanuric acid,N-hydroxy-3-pyridylmethyl-phthalimide,N-hydroxyglutarimide,N-one of hydroxysuccinimide.
The metalloporphyrin has a structure of general formula (I) or general formula (II) or general formula (III):
| general formula (I): | general formula (II): |
 |
 |
general formula (III):
wherein the metal atom M in the general formula (I) is selected from Co, Cu, Ru, Mn and Fe; the metal atom M in the general formula (II) is selected from Fe, Mn and Co; a metal atom M in the formula (III)1，M2Are respectively selected from Fe, Mn and Cr; the ligand X in the general formula (II) is acetate, acetylacetone and halogen; the substituents R in the general formulae (I), (II) and (III)1、R2And R3Respectively one of hydrogen, alkyl, alkoxy, hydroxyl, halogen, amido and nitryl.
The metal phthalocyanine has a structure of formula (IV):
general formula (IV):
wherein the metal atom M is selected from Co, Cu, Ni, Zn, Ru, Mn, Fe, and substituent R1And R2Are respectively hydrogen, alkyl, alkoxy, hydroxyl, halogen and aminoAnd a nitro group.
The invention has the advantages of wide raw material source, low price, diversified product structure and strong risk of resisting market situation change; the reaction condition is mild, the conversion rate is high, and the selectivity is good; the process is simple, and the equipment investment is low; good economic benefit and the like.
1. The raw materials have wide sources and low price, the product has diversified structures, and the risk of resisting the change of market situation is strong. From the product structure, the existing benzoic acid, p-toluic acid and m-toluic acid, particularly p-toluic acid and m-toluic acid, have limited market capacity, and the price of a single product is greatly influenced by the fluctuation of short-term supply and demand relations, so that the existing p-toluic acid and m-toluic acid production enterprises have weak risk capability of resisting market situation changes. From the raw material source, the concentration of m-xylene in the production industry is very high, the first 3-4 enterprises in the world account for more than 80% of the total production energy, the price fluctuation of m-xylene is large, the latest price fluctuation is that m-xylene rises from about 7500 yuan/ton at the end of 2015 to about 12500 yuan/ton in 5 months in 2016, and the risk capability of m-toluic acid production enterprises depending on a single raw material source for resisting market situation changes is weak. The present invention resists this market risk from both raw materials and products. The following table gives the price quotes given by the domestic mainstream supplier in 2016 and 9 months:
TABLE 1 xylene quotes given by the domestic mainstream supplier in 2016 month 9
| Raw materials | Mixed xylenes | Toluene | Para-xylene | Meta-xylene |
| Price (Yuan/ton) | 4700~4800 | 5500~5600 | 6200~6500 | 9800~10500 |
Therefore, the invention adopts mixed dimethylbenzene to oxidize and coproduce benzoic acid, p-methyl benzoic acid and m-methyl benzoic acid, and the raw material price is lower than that of a single benzoic acid product, particularly far lower than that of a m-methyl benzoic acid product. The method has the advantages of obvious low raw material price, wide sources and low price, the mixed xylene is derived from naphtha or coal, the annual domestic productivity has broken through 3000 ten thousand tons, the market price is strictly hooked with the petroleum price, the price fluctuation is far smaller than the fluctuation range of single xylene or toluene.
2. Mild reaction condition, high conversion rate and good selectivity. The invention adopts an oxygen-containing intermediate compound and a catalyst to co-catalyze ethylbenzene to initiate reaction, then catalyzes and oxidizes p-xylene and m-xylene to generate p-methyl benzoic acid and m-methyl benzoic acid, and ethylbenzene is oxidized and degraded into benzoic acid. After the process is adopted, the yield of the reaction is greatly improved, and the selectivity of benzoic acid, p-toluic acid and m-toluic acid in the final oxidation product is over 99 percent, which is obviously higher than the product selectivity of the industry in a single oxidation process, in particular to the product selectivity of the industries of the p-toluic acid and the m-toluic acid. The conversion rate of the mixed dimethylbenzene is more than 99.9 percent, and after rectification separation, the yield of the benzoic acid is more than 96 percent, the yield of the p-toluic acid is more than 94 percent, and the yield of the m-toluic acid is more than 90 percent.
In the process of preparing p-methyl benzoic acid and m-methyl benzoic acid by oxidizing p-xylene or m-xylene, the first methyl on a benzene ring is an inert substance in the reaction system, and the activation of the first methyl is the most difficult step in the whole reaction. And once the first methyl group on the benzene ring is initiated, the subsequent reaction of intermediate methylbenzyl alcohol and methylbenzaldehyde occurs relatively easily. In order to activate the first methyl group on the benzene ring, strict reaction conditions are generally adopted, and the strict reaction conditions simultaneously lead to further deep oxidation of the methyl group on the target product methyl benzoic acid generated in the system, thereby leading to the reduction of the selectivity of the target product methyl benzoic acid, and various intermediate products are mixed in the product. One desirable reaction mode is to simultaneously realize the activation of the first methyl group and the further deep oxidation of the intermediate methyl benzyl alcohol and methyl benzaldehyde into the target methyl benzoic acid under mild reaction conditions.
The key to initiating the p-xylene or m-xylene reaction is the presence in the system of free radicals capable of activating the methyl hydride on the benzene ring of p-xylene. The inventor of the present invention further found that under the condition of existence of the co-oxidant, the co-oxidant can be firstly oxidized to generate free radicals under mild conditions, and then the free radicals attack hydrogen on methyl on a benzene ring which is difficult to be oxidized to generate benzyl free radicals, so as to initiate the reaction, and finally the methyl benzoic acid and deep oxidation products thereof are generated through one-step oxidation.
The inventors of the present invention have found that, deviating from the general knowledge of the skilled person, ethylbenzene is an excellent co-oxidant in the catalytic system according to the present invention. The molecular structure of ethylbenzene has a methylene group connected with a benzene ring, and the activity of the ethylbenzene is far stronger than that of methyl. Under the condition which is much milder than methyl initiation, the free radical can be firstly oxidized to generate a free radical, then the free radical attacks hydrogen on a methyl on a benzene ring of xylene which is difficult to oxidize to generate a benzyl free radical, so that the reaction is initiated, and finally methyl benzoic acid and deep oxidation products thereof are generated through one-step oxidation. Ethylbenzene itself is also oxidized sequentially to 1-phenylethyl alcohol, acetophenone, benzaldehyde and the final product benzoic acid as intermediates rather than the phenylacetic acid product as conventionally understood by those skilled in the art (as described in CN10318890A and CN 101508638A).
The inventors of the present invention further found that oxidation intermediates such as methyl benzyl alcohol, methyl benzaldehyde, and ethylbenzene generated in the oxidation process of methyl benzyl alcohol, methyl benzaldehyde, and ethylbenzene, which are present in the reaction system for preparing methyl benzoic acid by oxidizing xylene, are also superior co-oxidants mainly due to the following reasons:
(a) they are intermediate products generated in the reaction system, and after the intermediate products are added into the reaction system in the initiation stage, new impurities cannot be brought to the system.
(b) Under the catalytic system of the present invention, these oxidation intermediates can be oxidized under relatively much milder conditions to generate free radicals which can rapidly initiate the reaction of the methyl group on the benzene ring of xylene. The oxidation intermediates act as a co-catalytic oxidation of xylene.
(c) Methyl benzyl alcohol, methyl benzaldehyde, acetophenone, 1-phenethyl alcohol and benzaldehyde are also self-generated substances in the reaction system, can be conveniently generated by reaction and recycled, no additional addition is needed, and the production cost is greatly reduced. The method realizes the online in-situ generation and addition of the methyl benzyl alcohol, the methyl benzaldehyde, the acetophenone, the 1-phenethyl alcohol and the benzaldehyde by directly recycling the low-boiling-point components obtained in the operation of the step (1) to the reaction step (1).
The inventors of the present invention have also found that: the oxidation intermediate of ethylbenzene is 1-phenethyl alcohol, acetophenone and benzaldehyde, and one molecule of CO is released in the reaction process2. CO is reported according to the common general knowledge and extensive literature of those skilled in the art2Is advantageous for promoting the oxidation of aromatic hydrocarbons. The invention achieves an unexpected technical effect that: in-situ generated oxidation promoter CO in intermediate products of acetophenone and benzaldehyde2Under the combined action of the two catalysts, the difference between the oxidation speed of p-xylene and the oxidation speed of m-xylene reported in documents (Chenjun such as Zhang, Hujiayuan, Lixianshu. cobalt hydroxylamine acid complex for catalyzing selective oxidation of mixed xylene, chemical research and application, 2002, 14(2),178-181) is greatly shortened, so that the two catalysts can be simultaneously oxidized.
To achieve the effect of the present invention, the mass percentage of ethylbenzene in xylene should not be less than 10%. Preferred is 3 ℃ premium xylene as specified in GB 3407-90. The low content of ethylbenzene causes the difference of the oxidation speed of p-xylene and m-xylene to be large, and simultaneously causes the oxidation reaction conditions to become relatively harsh, and simultaneously the selectivity of the products p-methyl benzoic acid and m-methyl benzoic acid is reduced.
To achieve the effect of the present invention, the content of the isomer o-xylene in xylene is not higher than 0.5% by mass. The high o-xylene content leads to high o-methylbenzoic acid content of impurities in m-methylbenzoic acid and poor product quality.
3. Simple process and less equipment investment. The atmospheric boiling points of the various primary intermediates and feedstocks, products produced during the xylene oxidation process described in this invention are given in the following table:
TABLE 2 atmospheric boiling points of various major intermediates and feedstocks, products formed during xylene oxidation
| Compound (I) | Para-xylene | P-methyl benzyl alcohol | Para-methyl benzaldehyde | Para methyl benzoic acid | Terephthalic acid (TPA) |
| Boiling point (. degree.C.) | 138.4 | 217 | 204.5 | 274.5 | 392.4 |
| Compound (I) | Meta-xylene | M-methyl benzyl alcohol | Meta-methyl benzaldehyde | M-methyl benzoic acid | Isophthalic acid |
| Boiling point (. degree.C.) | 139.0 | 218.4 | 199 | 263.0 | 412.3 |
| Compound (I) | Ethylbenzene production | 1-Phenylethanolic acid | Acetophenone | Benzaldehyde | Benzoic acid |
| Boiling point (. degree.C.) | 136.2 | 203.6 | 202.0 | 179 | 249.0 |
In the industry, mixed xylene is used as a starting material, and three procedures of mixed xylene separation, single xylene oxidation and rectification separation of benzoic acid or methylbenzoic acid are required. As can be seen from Table 2, for the separation of mixed xylenes, conventional methods are difficult to separate due to the similar boiling points of ethylbenzene, para-xylene and meta-xylene in the composition. The separation process is also a process recognized by those skilled in the art to be particularly complex, high in equipment investment and particularly high in energy consumption. The invention creatively abandons the separation process, adopts commercial mixed dimethylbenzene to directly oxidize in air, and coproduces benzoic acid, p-toluic acid and m-toluic acid. As can be seen from table 2: on one hand, the boiling points of benzoic acid, m-methylbenzoic acid and p-methylbenzoic acid are 249.0, 263.0 and 274.5 ℃ in sequence, the boiling point difference is large, and the obvious boiling point differences of the benzoic acid, the m-methylbenzoic acid and the p-methylbenzoic acid are conveniently utilized to separate products by adopting a conventional rectification process; on the other hand: the boiling points of the raw materials and all intermediate oxidation products (such as 1-phenethyl alcohol, acetophenone, benzaldehyde, m/p-methylbenzyl alcohol and m/p-methylbenzyl alcohol) are obviously lower than that of the target product benzoic acid with the lowest boiling point, so that the intermediate oxidation products can be separated from the benzoic acid, the m-methylbenzoic acid and the p-methylbenzoic acid by simple conventional rectification operation. In another aspect: the boiling points of the terephthalic acid and the isophthalic acid which are byproducts are far higher than the boiling point of the p-toluic acid which is the target product with the highest boiling point, so that the byproducts of the deep oxidation can be separated from the benzoic acid, the m-toluic acid and the p-toluic acid by simple and conventional rectification operation. The special product structure and the boiling point difference ensure that the process of the invention is simple and the equipment investment is greatly reduced.
4. The economic benefit is good. The following table gives the price quotes for the product of the invention given by the domestic mainstream supplier in 2016 and 9 months:
TABLE 3 quoted quotes for benzoic acid and methylbenzoic acid from the mainstream domestic supplier in 2016 and 9 months
| Product(s) | Benzoic acid | Para methyl benzoic acid | M-methyl benzoic acid |
| Price (Yuan/ton) | 8500 | 19800 | 21800 |
According to the published data, the consumption indexes of the prior art are as follows: 850kg of toluene is consumed by 1 ton of benzoic acid, 6kg of medium-pressure steam is consumed, and the cost of direct raw materials (the price is calculated according to the price given in the table 1, the same below) and energy consumption (the price is calculated according to 160 yuan of steam per ton, the same below) is 5677.5 yuan/ton; 1150kg of m-xylene is consumed by 1 ton of m-methylbenzoic acid, 8kg of medium-pressure steam is consumed, and the direct raw material and energy consumption cost is 14703.4 yuan/ton; 1100kg of p-xylene is consumed by 1 ton of p-methylbenzoic acid, 9kg of medium-pressure steam is consumed, and the direct raw material and energy consumption cost is 8425 yuan/ton. The invention adopts mixed xylene as raw material, and takes 3 ℃ top grade xylene specified in GB3407-90 as an example, ethylbenzene: m-xylene: p-xylene =3:4:3 (mass ratio). According to the implementation effect of the invention, each ton of xylene contains 300kg of ethylbenzene, and can be rectified to obtain 331.5kg of benzoic acid with the value of 2817.8 yuan; contains 400kg of m-xylene, and can be rectified to obtain 455.1kg of m-toluic acid with the value of 9921.2 yuan; contains 300kg of p-xylene, and can be rectified to obtain 356.5kg of p-toluic acid with the value of 7058.5 yuan. The consumption of medium-pressure steam is 14kg per ton of mixed xylene oxidized, which is equivalent to 2240 yuan. From this, it can be estimated that the direct feed and energy costs are 6990 yuan per ton of mixed xylenes oxidized. According to the calculation, the direct raw material and energy consumption cost of the prior art for generating the benzoic acid, the m-toluic acid and the p-toluic acid with corresponding values are as follows: 5677.5 × 0.3315 +14703.4 × 0.4551+8425 × 0.356= 11572.9-membered. The cost of the prior art is about 65.6 percent higher than that of the direct raw material and energy consumption of the method of the invention. The method has good economic benefit and obvious advantages.
According to the invention, the main products of the oxidation reaction are benzoic acid, p-toluic acid and m-toluic acid. The amount was determined by analysis using a liquid chromatography internal standard method (using cumene as an internal standard). The xylene conversion, which characterizes the extent of reaction, is defined as:
xylene conversion = (number of moles of xylene freshly charged to oxidation reactor-number of moles of xylene remaining in system after initial distillation)/number of moles of xylene freshly charged to oxidation reactor. Expressed as a percentage in the examples.
The definition characterizing the selectivity and yield of the reaction product benzoic acid is:
benzoic acid selectivity = the number of moles of benzoic acid in the oxidation reaction liquid obtained in step (1)/the number of moles of (acetophenone + 1-phenethyl alcohol + benzaldehyde + benzoic acid) in the oxidation reaction liquid obtained in step (1), expressed as a percentage.
Benzoic acid yield = moles of benzoic acid obtained in step (2) per mole of ethylbenzene in the xylenes fed fresh to the oxidation reactor, expressed as a percentage.
The definition characterizing the selectivity and yield of the reaction product p-toluic acid is:
p-toluic acid selectivity = the number of moles of p-toluic acid in the oxidation reaction liquid obtained in step (1)/the number of moles of (p-methylbenzyl alcohol + p-tolualdehyde + p-toluic acid + terephthalic acid) in the oxidation reaction liquid obtained in step (1), expressed as a percentage.
Yield of p-toluic acid = moles of p-toluic acid obtained in step (2)/moles of p-xylene in the xylenes freshly fed to the oxidation reactor, expressed as a percentage.
The definition characterizing the selectivity and yield of the reaction product m-toluic acid is:
the m-toluic acid selectivity = the number of moles of m-toluic acid in the oxidation reaction liquid obtained in step (1)/the number of moles of (m-methylbenzyl alcohol + m-tolualdehyde + m-toluic acid + m-phthalic acid) in the oxidation reaction liquid obtained in step (1), expressed as a percentage.
The m-toluic acid yield = the number of moles of m-toluic acid obtained in step (2)/the number of moles of m-xylene in the xylene freshly fed into the oxidation reactor, expressed as a percentage.
The primary oxidation reactor and the gas-liquid separator in the embodiment of the invention are both a 1L titanium kettle, the interior of the primary oxidation reactor and the gas-liquid separator is provided with a cooling coil pipe, the outer wall of the primary oxidation reactor is provided with a jacket, heat can be supplied to the reaction by heating the jacket or heat can be transferred to the reaction by introducing a cooling medium into the coil pipe, and the purification system is a 316L small rectifying tower made of materials with the inner diameter of 100mm and the height of 5000 mm.
Example 1
The amount of fresh xylene added to the system was 91.4g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =45:50:5, dissolved catalyst isN-hydroxyphthalimides, metal phthalocyanines (R) having the general formula (IV)1=OH，R2= H, M = Ru), metalloporphyrin (R) having a structure of general formula (III)1=R3=H，R2=OH，M1=M2= Mn) and cobalt naphthenate, the total concentration being 10000 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 488.6 g. Continuously introducing pressurized pure oxygen into an oxidation reaction kettle, maintaining the reaction temperature of the system at 130 ℃, the reaction pressure at 0.2MPa and the reaction time at 3.2And (4) hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 97.8 percent, the yield of the m-methylbenzoic acid is 90.2 percent, and the yield of the p-methylbenzoic acid is 96.2 percent.
Example 2
The amount of fresh xylene added to the system was 66.9g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =25:25:50, dissolved catalyst ni (ac)2、N,N’,N’’Trihydroxyisocyanuric acid, a metal phthalocyanine (R) having the structure of the general formula (IV)1= H，R2= Cl, M = Zn) and a metalloporphyrin (R) having a structure of the general formula (II)1=R2=CH3CH2，R3Mixture of = H, M = Fe, X = Br), in a total concentration of 420 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 513.1 g. Continuously introducing pressurized pure oxygen into the oxidation reaction kettle, maintaining the reaction temperature of the system at 125 ℃, the reaction pressure at 0.6MPa and the reaction time at 1.5 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 98.1 percent, the yield of the m-methylbenzoic acid is 93.4 percent, and the yield of the p-methylbenzoic acid is 95.1 percent.
Example 3
The amount of fresh xylene added to the system was 169.2g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =20:30:50, dissolved catalyst mn (ac)2·4H2O, a metal phthalocyanine (R) having a structure of the general formula (IV)1=NO2，R2= H, M = Co), metalloporphyrin (R) having the structure of general formula (I)1=R3=H，R2=CH3CH2M = Cu), total concentration of 120 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 410.8 g. Continuously introducing pressurized pure oxygen into the oxidation reaction kettle, maintaining the reaction temperature of the system at 175 ℃, the reaction pressure at 0.7MPa and the reaction time at 1.5 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 96.5 percent, the yield of the m-methylbenzoic acid is 93.0 percent,The yield of p-toluic acid was 94.4%.
Example 4
The amount of fresh xylene added to the system was 61.4g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =25:25:50, dissolved catalyst is Cr (NO)3)4、N-acetylphthalimide, a metal phthalocyanine (R) having the general formula (IV)1=OCH3，R2= H, M = Ni), metalloporphyrin (R) having the structure of general formula (I)1=R3=OCH3，R2= H, M = Fe) and cobalt naphthenate, in a total concentration of 7800 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 518.6 g. Continuously introducing pressurized pure oxygen into the oxidation reaction kettle, maintaining the reaction temperature of the system at 115 ℃, the reaction pressure at 0.2MPa and the reaction time at 4.8 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 98.0 percent, the yield of the m-methyl benzoic acid is 91.8 percent, and the yield of the p-methyl benzoic acid is 94.2 percent.
Example 5
The amount of fresh xylene added to the system was 64.8g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =30:30:40, dissolved catalyst is HfO2、N-hydroxy o-sulfonylbenzoylimine, a metal phthalocyanine (R) having the structure of formula (IV)1=H，R2= F, M = Fe) and a metalloporphyrin (R) having the structure of formula (I)1=R3=OH，R2= H, M = Ru) in a total concentration of 600 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 512.5 g. Continuously introducing pressurized pure oxygen into the oxidation reaction kettle, maintaining the reaction temperature of the system at 179 ℃, the reaction pressure at 0.8MPa, and the reaction time at 1.6 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 97.0 percent, the yield of the m-methyl benzoic acid is 92.3 percent, and the yield of the p-methyl benzoic acid is 95.8 percent.
Example 6
Fresh xylene added to the system was 75.1g, the quality of the xyleneThe quantitative composition is ethylbenzene: p-xylene: meta-xylene =25:25:50, dissolved catalyst co (ac)2·4H2O, a metal phthalocyanine (R) having a structure of the general formula (IV)1=CH3CH2，R2= H, M = Mn), metalloporphyrin (R) having the structure of general formula (I)1=R2=H，R3=CH3M = Cu), total concentration of 225 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 504.9 g. Continuously introducing pressurized oxygen-enriched air with oxygen mass concentration of 60% into an oxidation reaction kettle, maintaining the reaction temperature of the system at 125 ℃, the reaction pressure at 0.6MPa and the reaction time at 2.5 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 96.6 percent, the yield of the m-methyl benzoic acid is 94.2 percent, and the yield of the p-methyl benzoic acid is 94.8 percent.
Example 7
The amount of fresh xylene added to the system was 67.2g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =10:10:80, dissolved catalyst isN-hydroxy-4-nitrophthalimide, a metal phthalocyanine (R) having the structure of formula (IV)1=NH2，R2= H, M = Cu) and metalloporphyrin (R) having the structure of formula (III)1=R3=H，R2=CH3，M1=M2= Cr), total concentration 660 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 512.8 g. Continuously introducing pressurized pure oxygen into the oxidation reaction kettle, maintaining the reaction temperature of the system at 145 ℃, the reaction pressure at 1.6MPa and the reaction time at 1.4 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 96.0 percent, the yield of the m-methyl benzoic acid is 95.0 percent, and the yield of the p-methyl benzoic acid is 94.4 percent.
Example 8
The amount of fresh xylene added to the system was 118.0g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =25:25:50, dissolved catalyst being CeO2And a metal phthalocyanine (R) having a structure of the general formula (IV)1=H，R2=CH3CH2M = Mn) in a total concentration of 450 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 462.0 g. And continuously introducing pressurized oxygen-enriched air with oxygen mass concentration of 80% into the oxidation reaction kettle, maintaining the reaction temperature of the system at 160 ℃, the reaction pressure at 1.6MPa and the reaction time at 1.2 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 96.8 percent, the yield of the m-methyl benzoic acid is 93.0 percent, and the yield of the p-methyl benzoic acid is 95.8 percent.
Example 9
The amount of fresh xylene added to the system was 94.2g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =25:25:50, dissolved catalyst is RuCl2、N-hydroxy-3-pyridylmethyl phthalimide and metalloporphyrin (R) having the structure of general formula (III)1=R3=H，R2=Cl，M1=M2= Fe) in a total concentration of 300 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 485.8 g. And continuously introducing pressurized air into the oxidation reaction kettle, and maintaining the reaction temperature of the system at 185 ℃, the reaction pressure at 1.4MPa and the reaction time at 0.6 hour. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 97.8 percent, the yield of the m-methylbenzoic acid is 92.2 percent, and the yield of the p-methylbenzoic acid is 95.1 percent.
Example 10
The amount of fresh xylene added to the system was 94.2g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =30:25:45, dissolved catalyst isN-hydroxy-4-methylphthalimide and metalloporphyrin (R) having the structure of formula (III)1=R3=H，R2=NH2，M1=Mn，M2= Cr), total concentration 550 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 485.8 g. Continuously introducing pressurized pure oxygen into an oxidation reaction kettle, maintaining the reaction temperature of the system at 155 ℃, the reaction pressure at 0.9MPa and the reaction timeIt was 2.0 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 97.0 percent, the yield of the m-methyl benzoic acid is 92.7 percent, and the yield of the p-methyl benzoic acid is 95.6 percent.
Example 11
The amount of fresh xylene added to the system was 62.3g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =60:30:10, dissolved catalyst is CuCl2Metal phthalocyanine (R) having a structure of the general formula (IV)1=F，R2= H, M = Fe) and a metalloporphyrin (R) having the structure of the general formula (II)1=R2=R3Mixture of = F, M = Co, X = Br) in a total concentration of 30 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 517.7 g. Continuously introducing pressurized pure oxygen into the oxidation reaction kettle, maintaining the reaction temperature of the system at 190 ℃, the reaction pressure at 2.9MPa and the reaction time at 0.3 hour. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 98.5 percent, the yield of the m-methyl benzoic acid is 90.3 percent, and the yield of the p-methyl benzoic acid is 95.8 percent.
Example 12
The amount of fresh xylene added to the system was 56.0g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =25:25:50, dissolved catalyst is Zn (Ac)2、N-hydroxysuccinimide, a metal phthalocyanine (R) having the structure of formula (IV)1= H，R2=NH2M = Cu) and metalloporphyrin (R) having a structure of general formula (II)1=R3=NO2，R2= H, M = Mn, X = acetylacetonate) in a total concentration of 3000 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 524.0 g. Continuously introducing pressurized oxygen-enriched air with oxygen mass concentration of 30% into an oxidation reaction kettle, maintaining the reaction temperature of the system at 124 ℃, the reaction pressure at 0.4MPa and the reaction time at 1.5 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 97.1 percent, the yield of the m-methylbenzoic acid is 92.5 percent, and the yield of the p-methylbenzoic acid isThe content was found to be 96.2%.
Example 13
The amount of fresh xylene added to the system was 139.2g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =25:10:65, dissolved catalyst isN-hydroxy-3, 4,5, 6-tetraphenylphthalimide and metalloporphyrin (R) having the structure of formula (III)1=R3=H，R2=NO2，M1= M2= Mn), total concentration 40 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 440.8 g. Continuously introducing pressurized pure oxygen into the oxidation reaction kettle, maintaining the reaction temperature of the system at 186 ℃, the reaction pressure at 1.1MPa and the reaction time at 1.8 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 96.8 percent, the yield of the m-methyl benzoic acid is 94.0 percent, and the yield of the p-methyl benzoic acid is 94.0 percent.
Example 14
The amount of fresh xylene added to the system was 79.8g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =25:25:50, dissolved catalyst is ZrO2、N,N’-dihydroxyorthophthalic acid tetracarboxydiimide, metal phthalocyanine (R) with general formula (IV) structure1=H，R2=NO2M = Co) and metalloporphyrin (R) having the structure of formula (I)1=R3=Cl，R2H, M = Zn), total concentration 100 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 500.2 g. And continuously introducing pressurized air into the oxidation reaction kettle, maintaining the reaction temperature of the system at 170 ℃, the reaction pressure at 1.8MPa and the reaction time at 1.5 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 97.4 percent, the yield of the m-methylbenzoic acid is 93.6 percent, and the yield of the p-methylbenzoic acid is 96.8 percent.
Example 15
The amount of fresh xylene added to the system was 101.0g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =25:25:50, dissolved catalyst co (ac)2·4H2O, a metal phthalocyanine (R) having a structure of the general formula (IV)1=CH3CH2，R2= H, M = Mn), metalloporphyrin (R) having the structure of general formula (I)1=R2=H，R3=CH3M = Cu), total concentration 75 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 479.0 g. And continuously introducing pressurized air into the oxidation reaction kettle, and maintaining the reaction temperature of the system at 180 ℃, the reaction pressure at 2.0MPa and the reaction time at 1.0 hour. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 97.4 percent, the yield of the m-methyl benzoic acid is 92.9 percent, and the yield of the p-methyl benzoic acid is 93.9 percent.
Example 16
The amount of fresh xylene added to the system was 128.3g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =25:25:50, dissolved catalyst being FeCl2、N-hydroxyglutarimide and a metal phthalocyanine (R) having the structure of the general formula (IV)1=H，R2=OCH3M = Ni) and metalloporphyrin (R) having the structure of formula (I)1=R3=CH3，R2= H, M = Mn), total concentration 1000 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 451.7 g. And continuously introducing pressurized lean oxygen with the oxygen mass concentration of 15% into an oxidation reaction kettle, maintaining the reaction temperature of the system at 188 ℃, the reaction pressure at 2.8MPa, and the reaction time at 2.8 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 97.8 percent, the yield of the m-methylbenzoic acid is 93.2 percent, and the yield of the p-methylbenzoic acid is 94.8 percent.
Example 17
The amount of fresh xylene added to the system was 62.4g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =25:25:50, dissolved catalyst isNHydroxy-3, 4,5, 6-tetraphenylphthalimide and cobalt isooctanoate in a total concentration of 8000 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 517.6 g. The mass concentration of oxygen is 40 percentThe pressurized oxygen-enriched air is continuously introduced into the oxidation reaction kettle, the reaction temperature of the system is maintained at 138 ℃, the reaction pressure is 0.4MPa, and the reaction time is 1.5 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 96.2 percent, the yield of the m-methylbenzoic acid is 92.9 percent, and the yield of the p-methylbenzoic acid is 94.6 percent.
Example 18
The amount of fresh xylene fed to the system was 148.8g, the mass composition of xylene being ethylbenzene: p-xylene: m-xylene =25:25:50, dissolved catalyst is MnO2Metal phthalocyanine (R) having a structure of the general formula (IV)1= H，R2= OH, M = Ru) and metalloporphyrin (R) having a structure of the general formula (II)1=R3=NH2，R2= H, M = Cr, X = acetate), in a total concentration of 360 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 431.2 g. And continuously introducing pressurized air into the oxidation reaction kettle, maintaining the reaction temperature of the system at 195 ℃, the reaction pressure at 1.9MPa and the reaction time at 0.6 hour. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 96.2 percent, the yield of the m-methylbenzoic acid is 92.1 percent, and the yield of the p-methylbenzoic acid is 96.3 percent.
Example 19
The amount of fresh xylene added to the system was 71.0g, the mass composition of xylene being ethylbenzene: p-xylene: m-xylene =35:5:60, dissolved catalyst is MnO2And cobalt isooctanoate in a total concentration of 150 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 509.0 g. Continuously introducing pressurized pure oxygen into the oxidation reaction kettle, maintaining the reaction temperature of the system at 156 ℃, the reaction pressure at 1.0MPa and the reaction time at 1.0 hour. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 97.3 percent, the yield of the m-methylbenzoic acid is 93.7 percent, and the yield of the p-methylbenzoic acid is 98.0 percent.
Example 20
Fresh xylene added to the system is103.0g, the mass composition of xylene is ethylbenzene: p-xylene: meta-xylene =25:25:50, dissolved catalyst isN-hydroxy-4-carboxyphthalimide, a metal phthalocyanine (R) having the general formula (IV)1=Cl，R2= H, M = Zn) and a metalloporphyrin (R) having a structure of the general formula (III)1=R3=H，R2=OCH3，M1=Fe，M2= Mn), total concentration 140 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 477.0 g. Continuously introducing pressurized pure oxygen into the oxidation reaction kettle, maintaining the reaction temperature of the system at 168 ℃, the reaction pressure at 0.8MPa and the reaction time at 1.2 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 96.4 percent, the yield of the m-methylbenzoic acid is 93.4 percent, and the yield of the p-methylbenzoic acid is 95.5 percent.
Example 21
The amount of fresh xylene added to the system was 107.1g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =25:25:50, the dissolved catalyst being a metalloporphyrin (R) having the structure of formula (I)1=R2= R3= H, M = Co) as catalyst, total concentration 10 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 472.9 g. And continuously introducing pressurized air into the oxidation reaction kettle, and maintaining the reaction temperature of the system at 190 ℃, the reaction pressure at 2.8MPa and the reaction time at 0.5 hour. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 97.8 percent, the yield of the m-methyl benzoic acid is 92.0 percent, and the yield of the p-methyl benzoic acid is 94.8 percent.
Example 22
The amount of fresh xylene added to the system was 85.3g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =15:10:75, dissolved catalyst isN-hydroxyphthalimides, metal phthalocyanines (R) having the general formula (IV)1=H，R2= H, M = Co) and metalloporphyrin (R) having the structure of formula (III)1=R2=R3=H，M1=M2= Mn), total concentration 800 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 494.7 g. Continuously introducing pressurized pure oxygen into the oxidation reaction kettle, maintaining the reaction temperature of the system at 135 ℃, the reaction pressure at 0.5MPa and the reaction time at 3.0 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 96.3 percent, the yield of the m-methyl benzoic acid is 94.7 percent, and the yield of the p-methyl benzoic acid is 94.4 percent.
Example 23
The amount of fresh xylene fed to the system was 208.8g, the mass composition of xylene being ethylbenzene: p-xylene: meta-xylene =50:25:25, the dissolved catalyst being a metallophthalocyanine (R) having the structure of formula (IV)1=H，R2=CH3CH2M = Co), total concentration 45 ppm. After the system was circulated and stabilized, the mass of the oxidation reaction liquid circulated and charged was 371.2 g. Continuously introducing pressurized pure oxygen into the oxidation reaction kettle, maintaining the reaction temperature of the system at 185 ℃, the reaction pressure at 2.2MPa and the reaction time at 3.5 hours. The implementation effect is that the conversion rate of the dimethylbenzene is more than 99.9 percent, the selectivity of each target product is more than 99 percent, the yield of the benzoic acid is 98.0 percent, the yield of the m-methyl benzoic acid is 91.3 percent, and the yield of the p-methyl benzoic acid is 96.2 percent.
Claims (5)
1. A method for coproducing benzoic acid, p-methyl benzoic acid and m-methyl benzoic acid is characterized by comprising the following steps:
(1) and (3) oxidation: adding a xylene mixture, a catalyst and oxygen-containing gas with the oxygen content of not less than 15 mass percent into an oxidation reactor for reaction, wherein the xylene mixture comprises ethylbenzene, p-xylene and m-xylene, the impurity in the xylene mixture is o-xylene, the mass percent of the ethylbenzene in the xylene mixture is not less than 10 percent, the mass percent of the impurity o-xylene is not more than 0.5 percent, the catalyst is transition metal salt or oxide,N-one or a mixture of a plurality of hydroxyphthalimide compounds, metal phthalocyanines and metalloporphyrins, wherein the dosage of the catalyst is 10-1000 of the mass of the xylene mixture0ppm, the reaction temperature is 115-190 ℃, the reaction pressure is 0.2-3 MPa, and the average residence time of the oxidation reactor calculated by liquid phase substances is 0.3-5 hours, so that the oxidation reaction liquid containing the raw materials, various oxygen-containing intermediates with boiling points lower than that of benzoic acid, and products of benzoic acid, p-toluic acid and m-toluic acid is obtained;
(2) gas-liquid separation and purification: and (3) feeding the oxidation reaction liquid into a gas-liquid separator, condensing and separating a gas phase part, circulating a condensate to the oxidation reaction liquid for continuous oxidation, treating non-condensable gas and emptying, performing conventional rectification on a liquid phase part, obtaining a low-boiling-point component with a boiling point lower than that of benzoic acid at the tower top, circulating the low-boiling-point component back to the oxidation reactor for continuous oxidation, and further performing conventional rectification on a tower bottom component to sequentially obtain benzoic acid, m-methylbenzoic acid and p-methylbenzoic acid products.
2. A process for Co-producing benzoic acid, p-toluic acid and m-toluic acid as claimed in claim 1, wherein said transition metal salt or oxide is selected from one of Co, Cu, Ni, Zn, Mn, Fe, Cr, Ce, Zr, Ru, Hf salts or oxides.
3. The method for coproducing benzoic acid, p-methyl benzoic acid and m-methyl benzoic acid as claimed in claim 1, wherein the method is characterized in thatN-hydroxyphthalimide compounds selected fromN-hydroxyphthalimides,N-hydroxy-4-nitrophthalimide,N-hydroxy-4-carboxyphthalimide,N-hydroxy-4-methylphthalimide,N-hydroxy-3, 4,5, 6-tetraphenylphthalimide,N,N’-dihydroxypyromellitic diimide,N-hydroxy-o-sulfonylbenzoylimines,N-acetylphthalimide, a salt thereof,N,N’,N’’-trihydroxyisocyanuric acid,N-hydroxy-3-pyridylmethyl-phthalimide,N-hydroxyglutarimide,N-one of hydroxysuccinimide.
4. The method for coproducing benzoic acid, p-methylbenzoic acid and m-methylbenzoic acid as claimed in claim 1, wherein the metalloporphyrin has a structure of the general formula (I) or (II) or (III):
general formula (III):
wherein the metal atom M in the general formula (I) is selected from Co, Cu, Ru, Mn and Fe; the metal atom M in the general formula (II) is selected from Fe, Mn and Co; a metal atom M in the formula (III)1，M2Are respectively selected from Fe, Mn and Cr; the ligand X in the general formula (II) is acetate, acetylacetone and halogen; the substituents R in the general formulae (I), (II) and (III)1、R2And R3Respectively one of hydrogen, alkyl, alkoxy, hydroxyl, halogen, amido and nitryl.
5. The process for co-producing benzoic acid, p-toluic acid and m-toluic acid according to claim 1, characterized in that said metal phthalocyanine has the general formula (IV):
general formula (IV):
wherein the metal atom M is selected from Co, Cu, Ni, Zn, Ru, Mn, Fe, and substituent R1And R2Respectively hydrogen, alkyl, alkoxy, hydroxyl, halogen, amido and nitryl.
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