CN1453259A - Method of catalyzing oxidation of aromatic methyl benzene with air to prepare aromatic carboxylic acid - Google Patents
Method of catalyzing oxidation of aromatic methyl benzene with air to prepare aromatic carboxylic acid Download PDFInfo
- Publication number
- CN1453259A CN1453259A CN 03124410 CN03124410A CN1453259A CN 1453259 A CN1453259 A CN 1453259A CN 03124410 CN03124410 CN 03124410 CN 03124410 A CN03124410 A CN 03124410A CN 1453259 A CN1453259 A CN 1453259A
- Authority
- CN
- China
- Prior art keywords
- carboxylic acid
- aromatic carboxylic
- catalyst
- general formula
- metal
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 48
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 title abstract 4
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 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 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 10
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 239000003426 co-catalyst Substances 0.000 claims description 5
- 239000003205 fragrance Substances 0.000 claims description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 150000005172 methylbenzenes Chemical class 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- -1 transition metal salt Chemical class 0.000 claims description 3
- 229920002101 Chitin Polymers 0.000 claims description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000003147 glycosyl group Chemical group 0.000 claims 2
- 239000001913 cellulose Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 description 10
- 238000007796 conventional method Methods 0.000 description 10
- 238000000746 purification Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- UALKQROXOHJHFG-UHFFFAOYSA-N 1-ethoxy-3-methylbenzene Chemical compound CCOC1=CC=CC(C)=C1 UALKQROXOHJHFG-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
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012453 solvate Substances 0.000 description 2
- KZNRNQGTVRTDPN-UHFFFAOYSA-N 2-chloro-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(Cl)=C1 KZNRNQGTVRTDPN-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
- 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
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-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
- 239000002253 acid Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses the technological process of catalyzing oxidation of aromatic methyl benzene with air containing some or no CO2 to prepare aromatic carboxylic acid. Under the condition of 1-20 atm air pressure and reaction temperature 50-250 deg.c and under the catalysis of single catalyst of mu-bimetallic porphyrin or single-metal porphyrin or composite catalyst comprising the single catalyst and the salt or oxide of transition metal in a concentration of 1-100 ppm, aromatic methyl benzene is oxidized to produce corresponding aromatic carboxylic acid. The catalytic reaction may be homogeneous one or heterogeneous. The present invention has aromatic methyl benzene converting rate of 50-90 % and aromatic carboxylic acid selectivity of 50-90 % depending on the catalyst composition and reaction temperature.
Description
Technical field
The present invention relates to a kind of fragrant methylbenzene by the method for air or the corresponding aromatic carboxylic acid of carbonated air direct oxidation becoming.
Background technology
Aromatic carboxylic acid is important industrial raw material.The industrial oxidation of fragrance methylbenzene needs high-temperature and high-pressure conditions, and under these conditions, the poor stability of aromatic carboxylic acid, decarboxylation easily, reaction conversion ratio and selectivity are undesirable in the production process.The industrial production of aromatic carboxylic acid is general at present earlier is transformed into the corresponding carboxylic acid ester with fragrant methylbenzene, and then is hydrolyzed into carboxylic acid.The technology of above-mentioned fragrant methylbenzene oxidation had both existed reaction conversion ratio and the low problem of selectivity of product, also had the serious environmental pollution problem simultaneously.The science and technology circle is being devoted to fragrant methylbenzene is become corresponding aromatic carboxylic acid by the air direct oxidation novel process research always.US 5,763,648 disclose in acetate solvate and to use Cobaltous diacetate or manganese and Potassium Bromide to make catalyzer, directly become method of terephthalic acid with the atmospheric oxidation p-Xylol, US 6,175,038 discloses in acetic acid-water mixed solvent and to use composite metal salt and Potassium Bromide to make catalyzer, become method of terephthalic acid by the oxygen-rich air oxidation of p-xylene, US 6,194,607 disclose in acetate solvate and to use metal-salt and basic metal or alkaline-earth metal to make compound catalyzer, become method of terephthalic acid by carbonic acid gas with Air mixing gas oxidation of p-xylene.But above-mentioned patent all exists metal-salt fouling in the commercial run and productive rate is lower, selectivity is not high problem.
Summary of the invention
The object of the present invention is to provide a kind of productive rate height, selectivity height, catalyst consumption is little, cost is low, catalytic efficiency height, a kind of method that is prepared aromatic carboxylic acid by fragrant methylbenzene that speed of response is accelerated, temperature of reaction is lower.
The object of the present invention is achieved like this: under the air conditions that feeds 1-20atm carbonated 0-15% (volume), controlled temperature 50-250 ℃, select for use by general formula (I) or μ (II)-oxygen bimetallic porphyrin or monometallic porphyrin or their immobilized thing and make the composite catalyst that catalyzer or they and filtering metal salt or oxide compound constitute separately, catalyst concn is 1-100PPM, and metalloporphyrin can be efficient as biological enzyme under biological concentration, the fragrant methylbenzene of high-selectivity oxidation becomes the corresponding aroma carboxylic acid.
Preferred pressure scope of the present invention is 6-10atm, and preferred temperature range is 140-170 ℃, and preferred catalyst concn is 2-8PPM, and carbon dioxide content is 2-5% in the preferred oxic gas.
Described composite catalyst be by general formula (I) or (II) metalloporphyrin or their immobilized thing as Primary Catalysts, with transition metal salt or oxide compound as co-catalyst, Primary Catalysts concentration is 1-100PPM, and the mol ratio of Primary Catalysts and co-catalyst is 1: 1-40.
Atoms metal M in the above-mentioned metal porphyrins structure, M
1, M
2Can be transition metal atoms or lanthanide series metal atom; Substituent R on the phenyl ring
1, R
2, R
3Can be hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, amino, the candy base replaces candy base and cyclodextrin.Dentate X can be an acetate, methyl ethyl diketone, halogen.
The carrier that constitutes the supported metalloporphyrin catalyzer with above-mentioned metalloporphyrin has: silica gel, molecular sieve, aluminum oxide, zeolite, sepiolite, porous ceramics, polyvinyl chloride, polyvinyl chloride, polystyrene etc.
Described transition metal salt or oxide compound as co-catalyst has: Cu, Zn, Fe, Co, Mn, Cr, the salt of metals such as Ni or oxide compound.These metal-salts or oxide compound can obviously improve the catalytic performance of metalloporphyrin to air or carbonated oxidation fragrance methylbenzene.
Employed fragrant series inlet methyl benzene compounds can be toluene, o-Xylol, m-xylene, p-Xylol, hemimellitol, sym-trimethylbenzene, unsym-trimethyl benzene among the present invention.Also can be the substituted aroma methylbenzene, substituting group be nitro, halogen, hydroxyl, the alkoxyl group that is positioned at the phenyl ring different positions.Can also be the xylene mixture or the trimethylbenzene mixture of different ratios.
The composite catalyst that is made of metalloporphyrin or they and transition metal or oxide compound shows through on probation, and the reaction that atmospheric oxidation fragrance series inlet methyl benzene compounds or their mixture is generated corresponding carboxylic acid has good catalytic performance.With the variation of catalysis of metalloporphyrin agent composition and temperature of reaction, the transformation efficiency of fragrant methylbenzene is between 50-90%, and the selectivity of corresponding carboxylic acid is between 50-95%.The consumption of catalyst system therefor is little, catalytic efficiency is high, and speed of response quickening, temperature of reaction and reaction pressure are lower, product purity is high, separate easily.
Embodiment
Embodiment 1:
3mg had the metalloporphyrin of general formula (I), R
1=R
2=R
3=CH
3, M=Co adds in the 400ml p-Xylol, feeds the 8atm air.In 180 ℃ of following reaction stirred 3 hours, separation and purification according to a conventional method, the dimethylbenzene transformation efficiency is 85%, terephthalic acid yield 70% in the reaction product.
Embodiment 2:
5mg had the metalloporphyrin of general formula (II), R
1=R
2=R
3=Cl, M=Cu adds in the 400ml sym-trimethylbenzene, feeds the air of 7atm carbonated 4%.In 210 ℃ of following reaction stirred 4 hours, separation and purification according to a conventional method, the sym-trimethylbenzene transformation efficiency is 65%, trimesic acid yield 53% in the reaction product.
Embodiment 3:
3mg had the metalloporphyrin of general formula (I), R
1=R
2=R
3=H, M=Mn adds in the 400ml toluene, feeds the air of 8atm carbonated 2%.In 145 ℃ of following reaction stirred 4 hours, separation and purification according to a conventional method, toluene conversion is 90%, phenylformic acid yield 80% in the reaction product.
Embodiment 4:
5mg had the metalloporphyrin of general formula (II), R
1=R
2=R
3=Br, M
1=M
2=Fe adds in the 400ml para-nitrotoluene, feeds the 3atm air.In 160 ℃ of following reaction stirred 3 hours, separation and purification according to a conventional method, the para-nitrotoluene transformation efficiency is 65%, p-nitrobenzoic acid yield 83% in the reaction product.
Embodiment 5:
8mg had the metalloporphyrin of general formula (I), R
1=R
2=R
3=F, M=Fe and 15mg CoCl
2Add in the 500ml parachlorotoluene, feed the 10atm air.In 100 ℃ of following reaction stirred 5 hours, separation and purification according to a conventional method, the parachlorotoluene transformation efficiency is 82%, Chlorodracylic acid yield 83% in the reaction product.
Embodiment 6:
4mg had the chitin supported metalloporphyrin of general formula (II), R
1=R
2=R
3=Cl, M=Fe adds in the 500ml m-xylene, feeds the 15atm air.In 100 ℃ of following reaction stirred 8 hours, separation and purification according to a conventional method, the m-xylene transformation efficiency is 58%, dibenzoic acid yield 90% in the middle of the reaction product.
Embodiment 7:
10mg had the metalloporphyrin of general formula (II), R
1=R
2=R
3=OCH
3, M=Fe and 20mg neutralized verdigris add 500ml p-Xylol and m-xylene and respectively account in 50% the mixture, feed the 17atm air.80 ℃ of following reaction stirred 2 hours, separation and purification according to a conventional method, benzene mixed diacid yield 85% in the reaction product.
Embodiment 8:
2mg had the metalloporphyrin of general formula (I), R
1=R
2=R
3=N (CH
3)
2, M=Cu adds 500ml 2-chloro-1, in the 4-dimethylbenzene, feeds the 12atm air.In 180 ℃ of following reaction stirred 3 hours, separation and purification according to a conventional method, 2-chloro-1,4-dimethylbenzene transformation efficiency is 81%, 2-chloro-1 in the reaction product, 4-phthalic acid yield 79%.
Embodiment 9:
5mg had the metalloporphyrin of general formula (I), R
1=R
2=R
3=Cl, M=Co adds 500ml and contains in the mixture of p-Xylol 40% and 60% m-xylene, feeds the 13atm air.220 ℃ of following reaction stirred 1 hour, separation and purification according to a conventional method, benzene mixed diacid yield 87% in the reaction product.
Embodiment 10:
4mg had the metalloporphyrin of general formula (I), R
1=R
2=R
3=Cl, M=Mn adds 500ml in the methoxy toluene, feeds the air of 8atm carbonated 12%.150 ℃ of following reaction stirred 4 hours, separation and purification according to a conventional method was 75% to the methoxy toluene transformation efficiency, anisic acid yield 80% in the reaction product.
Claims (10)
1, a kind of catalytic air oxidation fragrance methylbenzene prepares the method for aromatic carboxylic acid, it is characterized in that, under the air conditions that feeds 1-20atm carbonated 0-15% (volume), controlled temperature 50-250 ℃, select for use by general formula (I) or μ (II)-oxygen bimetallic porphyrin or monometallic porphyrin or their immobilized thing and make the composite catalyst that catalyzer or they and filtering metal salt or oxide compound constitute separately, catalyst concn is 1-100PPM
General formula (I)
General formula (II)
Atoms metal M in the said structure, M
1, M
2Can be whole transition metal atoms or lanthanide series metal atom; Substituent R on the phenyl ring
1, R
2, R
3Can be hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, amino, glycosyl replaces glycosyl and cyclodextrin; Dentate X can be an acetate, methyl ethyl diketone, halogen.
2, according to the described method for preparing aromatic carboxylic acid of claim 1, it is characterized in that described composite catalyst is as Primary Catalysts by general formula (I) or metalloporphyrin (II) or their immobilized thing, with transition metal salt or oxide compound as co-catalyst, Primary Catalysts concentration is 1-100PPM, and the mol ratio of Primary Catalysts and co-catalyst is 1: 1-40.
3,, it is characterized in that the preferred pressure scope is 6-10atm according to the described method for preparing aromatic carboxylic acid of claim 1.
4. according to the described method for preparing aromatic carboxylic acid of claim 1, it is characterized in that preferred temperature range is 140-170 ℃.
5. according to the described method for preparing aromatic carboxylic acid of claim 1, it is characterized in that preferred catalyst concn scope is 2-8PPM.
6,, it is characterized in that carbon dioxide content is 2-5% in the preferred oxic gas according to the described method for preparing aromatic carboxylic acid of claim 1.
7. according to the described method for preparing aromatic carboxylic acid of claim 1, it is characterized in that described fragrant series inlet methyl benzene compounds is toluene, o-Xylol, m-xylene, p-Xylol, hemimellitol, sym-trimethylbenzene, unsym-trimethyl benzene, substituted aroma methylbenzene, xylene mixture, trimethylbenzene mixture.
8. method according to claim 7, the substituting group that it is characterized in that described substituted aroma methylbenzene are nitro, halogen, hydroxyl, the alkoxyl group that is positioned at the phenyl ring different positions.
9. according to claim 1 or 2 described methods, it is characterized in that described supported metalloporphyrin is that metalloporphyrin and following carrier constitute: silica gel, molecular sieve, aluminum oxide, zeolite, sepiolite, porous ceramics, polyvinyl chloride, polyvinyl chloride, polystyrene, chitin, Mierocrystalline cellulose.
10,, it is characterized in that described metal-salt or oxide compound can be the salt or the oxide compound of following metal: Cu, Zn, Fe, Co, Mn, Cr, Ni according to claim 1 or 2 described methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031244106A CN1310865C (en) | 2003-05-26 | 2003-05-26 | Method of catalyzing oxidation of aromatic methyl benzene with air to prepare aromatic carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031244106A CN1310865C (en) | 2003-05-26 | 2003-05-26 | Method of catalyzing oxidation of aromatic methyl benzene with air to prepare aromatic carboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1453259A true CN1453259A (en) | 2003-11-05 |
| CN1310865C CN1310865C (en) | 2007-04-18 |
Family
ID=29260309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031244106A Expired - Fee Related CN1310865C (en) | 2003-05-26 | 2003-05-26 | Method of catalyzing oxidation of aromatic methyl benzene with air to prepare aromatic carboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1310865C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010040251A1 (en) * | 2008-10-08 | 2010-04-15 | 湖南大学 | Process and apparatus for preparing terephthalic acid by air oxidation of para-xylene |
| CN103193631A (en) * | 2013-03-15 | 2013-07-10 | 北京工业大学 | Method for preparing ortho-hydroxybenzoic acid by catalyzing and oxidizing ortho-cresol with metalloporphyrin and metal salt compound as catalyst |
| CN105218344A (en) * | 2015-09-15 | 2016-01-06 | 沅江华龙催化科技有限公司 | Atmospheric oxidation is utilized to replace the method for toluene production substituted-phenyl formic acid based on Reaction Separation synchronous reaction device |
| CN105348067A (en) * | 2015-09-29 | 2016-02-24 | 衢州群颖化学科技有限公司 | Co-production method for methyl benzoic acid and phthalic acid |
| CN106866403A (en) * | 2017-02-15 | 2017-06-20 | 中山大学惠州研究院 | A kind of preparation method of benzoic acid |
| CN106883117A (en) * | 2017-02-15 | 2017-06-23 | 中山大学惠州研究院 | A kind of method of coproduction benzoic acid and cyclonene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156421C (en) * | 2001-07-18 | 2004-07-07 | 湖南大学 | Process for preparing methyl benzaldehyde, methyl methanol and methyl benzoic acid by selectiveoxidizing dimethylbenzene |
-
2003
- 2003-05-26 CN CNB031244106A patent/CN1310865C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010040251A1 (en) * | 2008-10-08 | 2010-04-15 | 湖南大学 | Process and apparatus for preparing terephthalic acid by air oxidation of para-xylene |
| CN103193631A (en) * | 2013-03-15 | 2013-07-10 | 北京工业大学 | Method for preparing ortho-hydroxybenzoic acid by catalyzing and oxidizing ortho-cresol with metalloporphyrin and metal salt compound as catalyst |
| CN105218344A (en) * | 2015-09-15 | 2016-01-06 | 沅江华龙催化科技有限公司 | Atmospheric oxidation is utilized to replace the method for toluene production substituted-phenyl formic acid based on Reaction Separation synchronous reaction device |
| CN105218344B (en) * | 2015-09-15 | 2020-09-04 | 沅江华龙催化科技有限公司 | Method for producing substituted phenylformic acid by using air oxidation substituted toluene based on reaction separation synchronous reactor |
| CN105348067A (en) * | 2015-09-29 | 2016-02-24 | 衢州群颖化学科技有限公司 | Co-production method for methyl benzoic acid and phthalic acid |
| CN106866403A (en) * | 2017-02-15 | 2017-06-20 | 中山大学惠州研究院 | A kind of preparation method of benzoic acid |
| CN106883117A (en) * | 2017-02-15 | 2017-06-23 | 中山大学惠州研究院 | A kind of method of coproduction benzoic acid and cyclonene |
| CN106883117B (en) * | 2017-02-15 | 2019-09-20 | 中山大学惠州研究院 | A kind of method of coproduction benzoic acid and cyclonene |
| CN106866403B (en) * | 2017-02-15 | 2019-09-20 | 中山大学惠州研究院 | A kind of preparation method of benzoic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1310865C (en) | 2007-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8410315B2 (en) | Method for producing olefinically unsaturated carbonyl compounds by oxidative dehydrogenation of alcohols | |
| CN102070382B (en) | Method for preparing benzaldehyde or substituted benzaldehyde by catalytically oxidizing methylbenzene or substituted methylbenzene | |
| US7351867B2 (en) | Catalyst system for aerobic oxidation of primary and secondary alcohols | |
| Rispens et al. | Catalytic enantioselective allylic oxidation | |
| CN101613269B (en) | Method for preparing phenylformic acid through liquid phase oxidation of methylbenzene | |
| CN1191218C (en) | Method for atmospheric catalytic oxidation of cyclohexane by metalloporphyrin | |
| CN1310865C (en) | Method of catalyzing oxidation of aromatic methyl benzene with air to prepare aromatic carboxylic acid | |
| CN1218922C (en) | Method of preparing adipic acid by air-oxidating hexacarbocyclic compound | |
| CN1865210A (en) | Process for preparing ketoisophorone | |
| CN100402477C (en) | Method for catalytic conversion of alkyl cyclohexanol and alkyl cyclohexanone from air oxidized alkyl cyclohexane | |
| CN1156421C (en) | Process for preparing methyl benzaldehyde, methyl methanol and methyl benzoic acid by selectiveoxidizing dimethylbenzene | |
| US7153806B2 (en) | Encapsulated oxo-bridged organometallic cluster catalyst and a process for the preparation thereof | |
| CN1116258C (en) | Catalytic oxidation process of alkane and naphthene hydrocarbon | |
| CN1521153A (en) | Process for preparing aldehyde and alcohol by selective catalysis air oxidation of toluene and substituted toluene | |
| CN1544404A (en) | Method of catalyzed oxidation of olefin to produce enol, ketenes and epoxy compound | |
| CN1629120A (en) | Process for preparing aldehyde ketone and acid by oxidation of olefin | |
| CN108144612B (en) | Cobalt-based catalyst for synthesizing carboxylic ester by one-pot method and preparation and application thereof | |
| CN1740129A (en) | Prepn process of hydroquinone and phenol | |
| CN1300094C (en) | Method for preparing methyl formate through selected oxidizing dimethyl ether | |
| US6565754B1 (en) | Process for the production and purification of aromatic acids | |
| JPH09278675A (en) | Oxidation of conjugated compound | |
| CN1271031C (en) | Method for preparing 3,5,5-trimethyl-hexamethylene-2-olefin-1,4 diketone | |
| CN1923783A (en) | Method of preparing 3,5,5-trimethyl-cyclohex-2-en-1,4-dione by heterophase oxidation | |
| CN1491930A (en) | Synthetic process for p-methoxy benzaldehyde | |
| CN1775725A (en) | Method for preparing terephthalic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: HUNAN UNIVERSITY Free format text: FORMER OWNER: GUO CANCHENG Effective date: 20040430 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20040430 Address after: 410082 , Changsha, Hunan, Hunan University Applicant after: Hunan University Address before: 410082 School of chemistry and chemical engineering, Hunan University, Changsha, Hunan, Applicant before: Guo Cancheng |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070418 Termination date: 20120526 |