CN1333200A - Process for preparing methyl benzaldehyde, methyl methanol and methyl benzoic acid by selectiveoxidizing dimethylbenzene - Google Patents
Process for preparing methyl benzaldehyde, methyl methanol and methyl benzoic acid by selectiveoxidizing dimethylbenzene Download PDFInfo
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- CN1333200A CN1333200A CN 01114593 CN01114593A CN1333200A CN 1333200 A CN1333200 A CN 1333200A CN 01114593 CN01114593 CN 01114593 CN 01114593 A CN01114593 A CN 01114593A CN 1333200 A CN1333200 A CN 1333200A
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- methyl
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- dimethylbenzene
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Abstract
The present invention discloses a method for synthesizing toluyl aldehyde, methyl benzyl alcohol and methyl benzoic acid by means of catalytic atmospheric oxidation of xylene. In said invention the monometalloporphyrin or micro-oxobimetalloporpyrin or their solid carrier which is similar to biological enzyme in structure is selected and used as catalyst. It can independently or under the cocatalysis of metal salt high-effectively and high selectively catatyze air as biological enzyme to selectively oxidate xylene at 50-160 deg.c and 4-10 atm, and its reaction time is 8-12 hr. It can effectively prevent formation of deep oxide product, and its catalyst dose is small and its catalystic effect is good. When its raw material is p-xylene, it can utilize selection of catalyst to control oxidation main products and make them be p-methyl benzaldehyde, p-methyl benzyl alcohol and p-methyl benzoic acid.
Description
(1) technical field: the present invention relates to the method that metalloporphyrin selectivity catalytic air oxidation dimethylbenzene becomes tolyl aldehyde, methylbenzyl alcohol and tolyl acid.
(2) background technology: the dimethylbenzene oxidation generally need be carried out poor selectivity under high temperature, condition of high voltage.And because two methyl can step-by-step oxidation on the phenyl ring, side reaction is many, and product is difficult to be separated.So up to the present, can only obtain the Industrial products phthalic acid by the air complete oxidation at industrial dimethylbenzene.Clear 51-33101 discloses with the method for the catalyzer that contains palladium, rubidium or caesium by the synthetic p-tolyl aldehyde of air gaseous oxidation p-Xylol, it is catalyzer that clear 54-157534 discloses with the solubility cobalt salt, lower fatty acid is a solvent, the method of in the presence of Sodium Bromide, synthesizing p-tolyl aldehyde by air liquid-phase oxidation p-Xylol, but these methods all do not make the air selective oxidation industrialization of dimethylbenzene obtain to break through.
(3) summary of the invention: the purpose of this invention is to provide the novel process that a kind of highly selective catalytic air oxidation dimethylbenzene becomes tolyl aldehyde, methylbenzyl alcohol and tolyl acid.
Technical scheme is: in the reaction ax that raw material dimethylbenzene is housed, add with the biological enzyme similar by the μ-oxygen bimetallic porphyrin of the monometallic porphyrin of general formula (I) or general formula (II) or their immobilized thing as Primary Catalysts, the Primary Catalysts consumption is less than 40ppm, make co-catalyst with transition metal or its oxide compound, the mol ratio of Primary Catalysts and co-catalyst is 1: 3-5, at temperature 50-160 ℃, pressure 4-10atm, and under agitation condition, reacted 8-12 hour.
Method of the present invention also can at temperature 50-160 ℃, pressure 4-10atm, and under agitation condition, be reacted 8-12 hour by general formula (I) or metalloporphyrin (II) or its immobilized thing separately as catalyzer.
General formula (I)
General formula (II)
Atoms metal M in the said structure, M
1, M
2It can be transition metal atoms; Substituent R on the phenyl ring
1, R
2, R
3Can be hydrogen, alkyl, alcoxyl (hydroxyl) base, halogen, amine (ammonia) base, glycosyl replaces glycosyl and cyclodextrin.Dentate X can be an acetate, methyl ethyl diketone, halogen and other acid radical anions.
Catalyzer of the present invention can be one or more of above-mentioned metalloporphyrin.
The carrier that constitutes the supported metalloporphyrin catalyzer with above-mentioned metalloporphyrin has: silica gel, molecular sieve, aluminum oxide, zeolite, sepiolite, porous ceramics, chitosan, Mierocrystalline cellulose, polyvinyl chloride, polyvinyl chloride, polystyrene etc.
Transition metal salt or oxide compound can be Cu, Zn, Fe, Co, Mn, Cr, Ni etc.These metal-salts or oxide compound can obviously improve the catalytic performance of metalloporphyrin to atmospheric oxidation dimethylbenzene.Composite catalyst and heterocatalysis better effects if.
In the dimethylbenzene catalytic oxidation process, metalloporphyrin and μ-oxygen bimetallic porphyrin can be efficient as biological enzyme under biological concentration, the selective oxidation of highly selective catalytic air p-Xylol.Because the catalyst efficiency height, temperature of reaction and reaction pressure are lower, and therefore, the oxidizing reaction degree of depth is easy to control.By selecting catalyst structure and suitable adjusting process parameter, can selectivity obtain the oxidation products of different dimethylbenzene.The product purity height, separate easily.The composite catalyst that metalloporphyrin or they and transition metal salt and oxide compound constitute shows through on probation, becomes the reaction of tolyl aldehyde, methylbenzyl alcohol and tolyl acid to have good catalytic performance to atmospheric oxidation dimethylbenzene.When raw material was p-Xylol, product was p-tolyl aldehyde, to methylbenzyl alcohol and p-methylbenzoic acid.Because temperature of reaction is lower than 160 ℃, effectively controlled the deep oxidation of p-Xylol, the p-Xylol transformation efficiency between 5-20%, p-tolyl aldehyde, to methylbenzyl alcohol and p-methylbenzoic acid yield greater than 95%.
(4) specific embodiment:
Embodiment 1:
With the metalloporphyrin that 20mg has general formula (I) structure, R1=R
2=R
3=CH
3, M=Mn and 30mg Cu2Cl
2Add in the 500ml paraxylene, pass into the 5atm air. 125 ℃ of lower reaction stirred 10 hours, The paraxylene conversion ratio is 10.5%, p-tolyl aldehyde in the product, to methylbenzyl alcohol with to the methylbenzene first Acid yield 95%, wherein p-tolyl aldehyde and to methylbenzyl alcohol greater than 70%.
Embodiment 2:
With the metalloporphyrin that 15mg has general formula (II) structure, R1=R
2=R
3=Cl,M
1=M
2=Fe and 50mg Cu2O adds in the 500ml paraxylene, passes into the 8atm air. 145 ℃ of lower reaction stirred 8 hours, right The dimethylbenzene conversion ratio is 12.4%, p-tolyl aldehyde in the product, to methylbenzyl alcohol and p-methylbenzoic acid Yield 95%, wherein p-tolyl aldehyde and to methylbenzyl alcohol greater than 75%.
Embodiment 3:
With the metalloporphyrin that 20mg has general formula (I) structure, R1=R
2=R
3=Cl, M=Fe, and 30mgCoCl2Add in the 500ml ortho-xylene, pass into the 6atm air. 125 ℃ of lower reaction stirred 10 hours, adjacent two Toluene conversion is 9.5%, and o-tolualdehyde, o-methyl-benzene methyl alcohol and o-toluic acid are received in the product Rate 98%.
Embodiment 4:
With the metalloporphyrin that 20mg has general formula (I) structure, R1=R
2=R
3=Cl, M=Fe, and 30mgCu2Cl
2Add in the 500ml meta-xylene, pass into the 8atm air. 140 ℃ of lower reaction stirred 10 hours, two Toluene conversion is 15%, tolyl aldehyde, a methylbenzyl alcohol and m-methyl benzoic acid yield in the middle of the product 95%.
Embodiment 5:
With the metalloporphyrin that 10mg has general formula (II) structure, R1=R
2=H,R
3Be 2,3,4,6-tetrem acyl glucosyl group, M1=M
2=Fe, and 30mgCoCl2Add the 500ml paraxylene, pass into the 8atm air. 140 ℃ lower reaction stirred 10 hours, reaction effect is with embodiment 4.
Embodiment 6:
With the metalloporphyrin that 15mg has general formula (II) structure, R1=R
2=R
3=H,M=Mn,30mgCu
2Cl
2Add in the 500ml meta-xylene, pass into the 8atm air. 150 ℃ of lower reaction stirred 6 hours, the reaction effect Fruit is with embodiment 4.
Embodiment 7:
With the metalloporphyrin that 15mg has general formula (I) structure, R1=R
2=R
3=Cl, M=Fe is with 3 gram celluloses After immobilized, add in the 500ml paraxylene, pass into the 8atm air. 140 ℃ of lower reaction stirred 8 hours, The paraxylene conversion ratio is 8.5%, p-tolyl aldehyde in the product, to methylbenzyl alcohol with to the methylbenzene first Acid yield 95%. Solid-carried catalyst is reclaimed, repeat above-mentioned experiment, come to the same thing.
Embodiment 8:
With the metalloporphyrin that 18mg has general formula (II) structure, R1=R
2=H,R
3Be 2,3,4,6 tetrem acyl glucosyl groups, M1=M
2=Fe adds in the 500ml paraxylene, passes into the 8atm air. 130 ℃ of reactions 10 hours, the paraxylene conversion ratio was 8%, p-tolyl aldehyde yield 75%. To methylbenzyl alcohol with to methyl Benzoic acid yield 20%.
Claims (6)
1, selectivity catalytic air oxidation dimethylbenzene becomes tolyl aldehyde, the method of methylbenzyl alcohol and tolyl acid, it is characterized in that in the reaction ax that raw material dimethylbenzene is housed adding with the biological enzyme similar by the μ-oxygen bimetallic porphyrin of the monometallic porphyrin of general formula (I) or general formula (II) or their immobilized thing as Primary Catalysts, the Primary Catalysts consumption is less than 40ppm, make co-catalyst with transition metal or its oxide compound, the mol ratio of Primary Catalysts and co-catalyst is 1: 3-5, at temperature 50-160 ℃, pressure 4-10atm, and under agitation condition, reacted 8-12 hour.
General formula (I) general formula (II)
Atoms metal M in the said structure, M
1, M
2It can be transition metal atoms; Substituent R on the phenyl ring
1, R
2, R
3Can be hydrogen, alkyl, alcoxyl (hydroxyl) base, halogen, amine (ammonia) base, glycosyl replaces glycosyl and cyclodextrin.Dentate X can be an acetate, methyl ethyl diketone, halogen and other acid radical anions.
2. selectivity catalytic air oxidation dimethylbenzene becomes the method for tolyl aldehyde, methylbenzyl alcohol and tolyl acid, it is characterized in that by general formula (I) or metalloporphyrin (II) or its immobilized thing separately as catalyzer, at temperature 50-160 ℃, pressure 4-10atm, and under agitation condition, reacted 8-12 hour.
3, method according to claim 1 and 2 is characterized in that catalyzer can be one or more of above-mentioned metalloporphyrin.
4. according to claim 1 or 2 or 3 described methods, when it is characterized in that raw material is p-Xylol, product is p-tolyl aldehyde, to methylbenzyl alcohol and p-methylbenzoic acid.
5. according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that described immobilized thing is that metalloporphyrin and following carrier constitute by physics or chemical process: silica gel, molecular sieve, aluminum oxide, zeolite, sepiolite, porous ceramics, chitosan, Mierocrystalline cellulose, polyvinyl chloride, polyvinyl chloride, polystyrene etc.
6,, it is characterized in that transition metal salt or oxide compound can be Cu, Zn, Fe, Co, Mn, Cr, Ni etc. according to claim 1 or 2 or 3 or 4 described methods.
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1310865C (en) * | 2003-05-26 | 2007-04-18 | 湖南大学 | Method of catalyzing oxidation of aromatic methyl benzene with air to prepare aromatic carboxylic acid |
CN100490976C (en) * | 2006-02-15 | 2009-05-27 | 中国科学院大连化学物理研究所 | Bionic composite catalyst system for selective oxidation of arene |
CN104519466A (en) * | 2013-09-29 | 2015-04-15 | 普天信息技术有限公司 | SPS (Semi-persistent scheduling) method of point-to-multipoint centrex service |
CN105152906A (en) * | 2015-09-29 | 2015-12-16 | 衢州群颖化学科技有限公司 | Method for co-producing 3,5-dimethylbenzoic acid and trimesic acid |
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 |
CN105237344A (en) * | 2015-09-29 | 2016-01-13 | 衢州群颖化学科技有限公司 | Coproduction method of methyl benzoic acid, methyl benzaldehyde, and methyl benzyl alcohol |
CN105601473A (en) * | 2015-10-28 | 2016-05-25 | 衢州群颖化学科技有限公司 | Method for combined production of benzyl alcohol, benzaldehyde and benzoic acid through oxidizing toluene |
CN108503518A (en) * | 2017-02-28 | 2018-09-07 | 湖南师范大学 | A kind of preparation and its application of compound sepiolite base catalyst |
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CN105237343B (en) * | 2015-09-29 | 2017-05-31 | 江西科苑生物药业有限公司 | A kind of method of coproducing methyl phenmethylol, tolyl aldehyde and methyl benzoic acid |
CN105237345A (en) * | 2015-10-28 | 2016-01-13 | 衢州群颖化学科技有限公司 | Method for preparing cyclooctanol and cyclooctanone through cyclooctane oxidation |
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2001
- 2001-07-18 CN CNB011145935A patent/CN1156421C/en not_active Expired - Fee Related
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1310865C (en) * | 2003-05-26 | 2007-04-18 | 湖南大学 | Method of catalyzing oxidation of aromatic methyl benzene with air to prepare aromatic carboxylic acid |
CN100490976C (en) * | 2006-02-15 | 2009-05-27 | 中国科学院大连化学物理研究所 | Bionic composite catalyst system for selective oxidation of arene |
CN104519466A (en) * | 2013-09-29 | 2015-04-15 | 普天信息技术有限公司 | SPS (Semi-persistent scheduling) method of point-to-multipoint centrex service |
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 |
CN105152906A (en) * | 2015-09-29 | 2015-12-16 | 衢州群颖化学科技有限公司 | Method for co-producing 3,5-dimethylbenzoic acid and trimesic acid |
CN105237344A (en) * | 2015-09-29 | 2016-01-13 | 衢州群颖化学科技有限公司 | Coproduction method of methyl benzoic acid, methyl benzaldehyde, and methyl benzyl alcohol |
CN105601473A (en) * | 2015-10-28 | 2016-05-25 | 衢州群颖化学科技有限公司 | Method for combined production of benzyl alcohol, benzaldehyde and benzoic acid through oxidizing toluene |
CN108503518A (en) * | 2017-02-28 | 2018-09-07 | 湖南师范大学 | A kind of preparation and its application of compound sepiolite base catalyst |
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