CN1310865C - 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
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- CN1310865C CN1310865C CNB031244106A CN03124410A CN1310865C CN 1310865 C CN1310865 C CN 1310865C CN B031244106 A CNB031244106 A CN B031244106A CN 03124410 A CN03124410 A CN 03124410A CN 1310865 C CN1310865 C CN 1310865C
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- carboxylic acid
- catalyst
- air
- aromatic carboxylic
- porphyrin
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Abstract
The present invention discloses a process for directly oxidizing aromatic methyl benzene into corresponding aromatic carboxylic acid by air or air containing CO2. Under the air condition of 1 to 20 atm, reaction temperature is 50 to 250 DEG C, mu-bimetallic porphyrin or single-metal porphyrin or solid carrier thereof is singly used as catalyst, or mu-bimetallic porphyrin or single-metal porphyrin and filtration metal salt or oxides can form composite catalyst. Catalyst concentration is 1 to 100PPM, the metalloporphyrin can catalyze the air or the air containing CO2 like biologic enzyme in biologic concentration with high efficiency and high selectivity, and aromatic methyl benzene can be oxidized into the corresponding aromatic carboxylic acid. The catalytic reaction can be homogeneous catalysis or heterogeneous catalysis after immobilization. Along with the variation of the composition and the reaction temperature of the metalloporphyrin catalyst, the transformation rate of the aromatic methyl benzene is 50 to 90%, and the selectivity of the corresponding carboxylic acid is 50 to 95%. The catalyst has the advantages of little dosage, high catalysis efficiency, low reaction temperature and low reaction pressure.
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 transition metal salt or oxide compound constitute separately, the catalysis of metalloporphyrin agent concentration 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.
Reaction can be carried out under condition of no solvent, also can carry out in acetic acid-aqueous solution of 80%-100%.
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.
Metalloporphyrin or their immobilized thing are as Primary Catalysts by general formula (I) or (II) for described composite catalyst, and as co-catalyst, Primary Catalysts concentration is 1-100PPM with transition metal salt or oxide compound, and the mol ratio of Primary Catalysts and co-catalyst is 1: 1-40.
Atoms metal M in the above-mentioned metalloporphyrin thing 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=(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 (9)
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 volume ratio 0-15%, controlled temperature 50-250 ℃, select for use by general formula (I) or monometallic porphyrin (II) or μ-oxygen bimetallic porphyrin or their immobilized thing and make the composite catalyst that catalyzer or they and transition metal salt or oxide compound constitute separately, wherein when μ-oxygen bimetallic porphyrin or monometallic porphyrin or their immobilized thing are made catalyzer separately, catalyst concn is 1-100ppm, when they and transition metal salt or oxide compound constitute composite catalyst, by general formula (I) or metalloporphyrin (II) 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;
General formula (I)
General formula (II)
Atoms metal M, M in the said structure
1, M
2Be transition metal atoms; Substituent R on the phenyl ring
1, R
2, R
3Be hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, amino, glycosyl, replacement glycosyl or cyclodextrin; Dentate X is acetate, methyl ethyl diketone or halogen.
2,, it is characterized in that pressure range is 6-10atm according to the described method for preparing aromatic carboxylic acid of claim 1.
3. according to the described method for preparing aromatic carboxylic acid of claim 1, it is characterized in that temperature range is 140-170 ℃.
4. according to the described method for preparing aromatic carboxylic acid of claim 1, it is characterized in that the catalyst concn scope is 2-8ppm.
5,, it is characterized in that Carbon Dioxide in Air content is 2-5% according to the described method for preparing aromatic carboxylic acid of claim 1.
6. 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.
7. method according to claim 6, the substituting group that it is characterized in that described substituted aroma methylbenzene are nitro, halogen, hydroxyl or the alkoxyl group that is positioned at the phenyl ring different positions.
8. according to claim 1 or 2 described methods, it is characterized in that described immobilized thing is μ-oxygen bimetallic porphyrin or monometallic porphyrin and following carrier formation: silica gel, molecular sieve, aluminum oxide, zeolite, sepiolite, porous ceramics, polyvinyl chloride, polyvinyl chloride, polystyrene, chitin or Mierocrystalline cellulose.
9,, it is characterized in that described metal-salt or oxide compound are the salt or the oxide compound of following metal: Cu, Zn, Fe, Co, Mn, Cr or Ni according to the described method of claim 1.
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 |
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|---|---|---|---|
| CNB031244106A CN1310865C (en) | 2003-05-26 | 2003-05-26 | Method of catalyzing oxidation of aromatic methyl benzene with air to prepare aromatic carboxylic acid |
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|---|---|
| CN1453259A CN1453259A (en) | 2003-11-05 |
| CN1310865C true CN1310865C (en) | 2007-04-18 |
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| 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 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362687B (en) * | 2008-10-08 | 2012-04-11 | 湖南大学 | Method and equipment for preparing terephthalic acid by air oxidation of p-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 |
| 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 |
| CN105348067B (en) * | 2015-09-29 | 2017-12-12 | 江西科苑生物药业有限公司 | A kind of method of coproducing methyl benzoic acid and phthalic acid |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333200A (en) * | 2001-07-18 | 2002-01-30 | 湖南大学 | Process for preparing methyl benzaldehyde, methyl methanol and methyl benzoic acid by selectiveoxidizing dimethylbenzene |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333200A (en) * | 2001-07-18 | 2002-01-30 | 湖南大学 | Process for preparing methyl benzaldehyde, methyl methanol and methyl benzoic acid by selectiveoxidizing dimethylbenzene |
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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 |
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