CN100379715C - Process for preparation of carboxylic acid esters - Google Patents
Process for preparation of carboxylic acid esters Download PDFInfo
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- CN100379715C CN100379715C CNB2006100314818A CN200610031481A CN100379715C CN 100379715 C CN100379715 C CN 100379715C CN B2006100314818 A CNB2006100314818 A CN B2006100314818A CN 200610031481 A CN200610031481 A CN 200610031481A CN 100379715 C CN100379715 C CN 100379715C
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- carboxylic acid
- general formula
- metalloporphyrin
- oxygen
- porphyrin
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Abstract
The present invention discloses a carboxylate synthesis method. In a neutral environment, paraffin, cyclanes, olefin, aromatic hydrocarbon or other low-carbon hydrocarbon mixtures are used as raw materials, molecular oxygen is used as an oxidant. One or more kinds of monometallic porphyrin of a general formula (I) or mu-oxidant bimetallic porphyrin of a general formula (II), or solid carriers thereof are used as catalysts, or the monometallic porphyrin, the bimetallic porphyrin, the solid carriers and transition metal salt or oxides can form composite catalysts, and metal porphyrin concentration in the catalyst is from 1 to 100 ppm. The reaction temperature is controlled at 80 to 200 DEG C, the reaction pressure is from 0.1 to 2MPa, and the reaction time is from 1 to 10 hours. Molecular oxygen firstly oxidizes hydrocarbon into carboxylic acid and alcohols, and the carboxylic acid and the alcohols are further oxidized to produce ester. The method can simultaneously complete hydrocarbon oxidation and esterification reaction, can produce various types of carboxylate, and has the advantages of no corrosion to metal devices, simple process, wide raw material sources, no need of intermediate product separation, and high product purity.
Description
Technical field
The present invention relates to a kind of synthetic method of carboxylicesters.
Background technology
Carboxylicesters is important meticulous organic chemical industry's product, mainly as solvent, additive, medicine, essence and flavoring agent etc.Present industrial production carboxylic acid ester compound mainly obtains by the esterification or the transesterification reaction of carboxylic acid with alcohol.These production methods need soda acid to make catalyzer, seriously corroded to equipment, CN03108171.1 disclose a kind of with sulfuric acid as acid catalyst, with heteropolyacid (salt) as inhibiter, though can reduce some etching problems, can not solve fully, and the synthesis material that uses still is carboxylic acid and alcohol hardware, because the kind of alcohol and source are very limited, can not produce various types of carboxylicesterss.
Summary of the invention
The object of the present invention is to provide does not a kind ofly have corrosion to hardware, and technology is easy, and raw material sources are extensive, the product purity height, and separate easily can be finished OXIDATION OF HYDROCARBONS and esterification simultaneously, can produce the synthetic method of all kinds carboxylicesters.
Technical scheme of the present invention is: in neutral environment, with alkane, naphthenic hydrocarbon, alkene, aromatic hydrocarbons is raw material, with the molecular oxygen is oxygenant, select for use by the immobilized thing of one or more or they of the μ-oxygen bimetallic porphyrin of the monometallic porphyrin of general formula (I) or general formula (II) and make the composite catalyst that catalyzer or they and transition metal salt or oxide compound constitute separately, metalloporphyrin concentration is 1-100ppm in the catalyzer; Control reaction temperature is 80-200 ℃, and reaction pressure is 0.1-2MPa., reacts 1-10 hour, and molecular oxygen becomes carboxylic acid and alcohol with oxidizing hydrocarbon earlier, and the further oxidation of carboxylic acid and alcohol generates ester then.
General formula I
General formula I I
For synthesizing of asymmetric carboxylicesters, then should add carboxylic acid therein is solvent, is catalyzer with above-mentioned metalloporphyrin equally also, with molecular oxygen oxidizing hydrocarbon is become alcohol, and the further oxidation of carboxylic acid and alcohol generates ester then.Described carboxylic acid solvent can be C
1-C
6Carboxylic acid, vegetable oil acid or aromatic carboxylic acid.
Atoms metal M in general formula (I) and the general formula (II) is transition metal atoms: Fe, Mn, Cr, Co, Cu, Zn, Ni or Ru; M
1, M
2Be Fe, Mn or Cr atom; Substituent R
1, R
2, R
3Be hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, amino or nitro;
X is hydroxyl, acetate, methyl ethyl diketone or halogen in the general formula (I).
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, chitosan or chitin.
Described molecular oxygen can be air, oxygen or oxygen enrichment or oxygen-denuded air.
Described catalyzer can be that above-mentioned metalloporphyrin or their immobilized thing are made catalyzer separately, also can be the salt of they and other metal or the composite catalyst that oxide compound constitutes.
Described composite catalyst be by one or more of the salt of metalloporphyrin or supported metalloporphyrin and following metal or oxide compound with 1: 3-5 constitutes: Cu, Zn, Fe, Co, Mn, Cr, Ni etc.
Our experiments show that this composite catalyst can obviously improve molecular oxygen hydrocarbon compound is oxidized to the ability of carboxylicesters, with the variation of hydrocarbon structure and catalysis of metalloporphyrin agent composition and temperature of reaction, the selectivity of carboxylicesters changes between 50-80%.
Advantage of the present invention: OXIDATION OF HYDROCARBONS and esterification can be finished simultaneously, to hardware do not have that burn into technology is easy, raw material sources extensively, not isolation of intermediate products, product purity height, can produce all kinds carboxylicesters.
Embodiment
Embodiment 1:
In the 500ml hexanaphthene, add the metalloporphyrin with Fig. 1 structure, R
1=H, R
2=R
3=CH
3, M=Mn, to metalloporphyrin concentration be 3ppm.Feed the 0.8MPa air, 160 ℃ of following reaction stirred 4 hours, cyclohexane conversion was 20%, and reaction product is pentanedioic acid cyclohexyl and hexanodioic acid cyclohexyl, monoesters and dibasic acid esters selectivity 78%.
Embodiment 2:
Add the metalloporphyrin with Fig. 2 structure in 100ml acetate and 300ml Trimethylmethane, metalloporphyrin concentration is 10ppm, R in the formula
1=R
2=OCH
3, R
3=Cl, M
1=M
2=Fe adds Cu
2O to 20ppm feeds the air that 1.8MPa contains oxygen 15%.120 ℃ of following reaction stirred 6 hours, the Trimethylmethane transformation efficiency was 8%, reaction product tert.-butyl acetate selectivity 67%.
Embodiment 3:
Contain C at 150ml propionic acid and 300ml
2-C
4In the mixed alkanes, add metalloporphyrin, R in the formula with Fig. 1 structure
1=R
2=C
2H
5, R
3=Br, M=Fe, to metalloporphyrin concentration be 20ppm, add CoCl
2To 30ppm.Feed the 0.4MPa air, 85 ℃ of following reaction stirred 10 hours, alkane conversion is 20%, mixes propionic ester selectivity 55% in the reaction product.
Embodiment 4:
In 50ml caproic acid and 350ml butane, add the metalloporphyrin with Fig. 2 structure, R in the formula
1=R
2=CH
3, R
3=OH, M
1=M
2=Mn, to metalloporphyrin concentration be 5ppm.Feeding 1MPa contains the air of oxygen 18%.150 ℃ of following reaction stirred 5 hours, butanes conversion was 12%, reaction product isobutyl hexanoate selectivity 73%.
Embodiment 5:
In 80ml ricinolic acid and 320ml butene-2, add metalloporphyrin, R with Fig. 1 structure
1=R
2=R
3=Cl, M=Co, to metalloporphyrin concentration be 30ppm.Feeding 0.6MPa contains the air of oxygen 26%.110 ℃ of following reaction stirred 8 hours, the butene-2 transformation efficiency was 80%, ricinolic acid butene esters selectivity 62% in the reaction product.
Embodiment 6:
In 100ml propionic acid and 320ml tetrahydrobenzene, add metalloporphyrin, R with Fig. 1 structure
1=OC
2H
5, R
2=R
3=H,, M=Cu, to metalloporphyrin concentration be 80ppm, add FeCl
3To 15ppm.Feeding 0.3MPa contains the air of oxygen 30%.140 ℃ of following reaction stirred 10 hours, the tetrahydrobenzene transformation efficiency was 85%, propionic acid tetrahydrobenzene ester selectivity 68% in the reaction product.
Embodiment 7:
In the 350ml pentamethylene, add metalloporphyrin R with Fig. 2 structure
1=R
2=C
3H
7, R
3=NO
2, M
1=M
2=CrR
1=R
2=C
3H
7, R
3=NO
2, M
1=M
2=Cr to metalloporphyrin concentration be 10ppm.Feed the 0.9MPa air.120 ℃ of following reaction stirred 4 hours, the pentamethylene transformation efficiency was 14%, reaction product pentanedioic acid ring pentyl ester selectivity 53%.
Embodiment 8:
In 100ml acetate and 350ml toluene, add metalloporphyrin, R with Fig. 1 structure
1=NH
2,
R
2=R
3=CH
3, M=Ni, M=Ni, to metalloporphyrin concentration be 40ppm.Feed the 1.5MPa air.180 ℃ of following reaction stirred 3 hours, toluene conversion was 20%, jasmal selectivity 78% in the reaction product.
Embodiment 9:
At 350ml C
2-C
4The metalloporphyrin that adds the immobilized 12ppm Fig. 1 of chitin structure in the mixed alkanes,, R
1=R
2=OH, R
3=N (NH
3)
2, M=Ru feeds the 1.2MPa air.Reacted 2 hours down at 160 ℃, the mixed alkanes transformation efficiency is 10%, and low-carbon ester 76% in the reaction product.
Embodiment 10:
The metalloporphyrin that in 300ml propylene and 100ml acetate, adds the immobilized 6ppm Fig. 1 of molecular sieve structure, R
1=R
2=H, R
3=C
4H
9, M=Pt feeds the 0.8MPa air.Reacted 1 hour down at 190 ℃, propylene conversion is 90%, reaction product propylene acetate 68%.
Claims (6)
1. the synthetic method of a carboxylicesters, it is characterized in that in neutral environment, with alkane, naphthenic hydrocarbon, alkene or aromatic hydrocarbons is raw material, with the molecular oxygen is oxygenant, select for use by the immobilized thing of one or more or they of the μ-oxygen bimetallic porphyrin of the monometallic porphyrin of general formula (I) or general formula (II) and make the composite catalyst that catalyzer or they and transition metal salt or oxide compound constitute separately, metalloporphyrin concentration is 1-100ppm in the catalyzer; Control reaction temperature is 80-200 ℃, and reaction pressure is 0.1-2MPa., reacts 1-10 hour, and molecular oxygen becomes carboxylic acid and alcohol with oxidizing hydrocarbon earlier, and carboxylic acid and alcohol further oxidation generate ester;
General formula I
General formula I I
Atoms metal M in general formula (I) and the general formula (II) is transition metal atoms: Fe, Mn, Cr, Co, Cu, Zn, Ni or Ru; M
1, M
2Be Fe, Mn or Cr atom; Substituent R
1, R
2, R
3Be hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, amino or nitro;
X is hydroxyl, acetate, methyl ethyl diketone or halogen in the general formula (I).
2. according to the synthetic method of the described carboxylicesters of claim 1, it is characterized in that synthetic for asymmetric carboxylicesters, then adding carboxylic acid therein is solvent.
3. according to the synthetic method of claim 1 or 2 described carboxylicesterss, it is characterized in that the carrier that constitutes the supported metalloporphyrin catalyzer with above-mentioned metalloporphyrin has: silica gel, molecular sieve, aluminum oxide, sepiolite, porous ceramics, polyvinyl chloride, polyvinyl chloride, polystyrene, chitosan or chitin.
4. according to the synthetic method of claim 1 or 2 described carboxylicesterss, it is characterized in that described molecular oxygen is air, oxygen, oxygen-rich air or oxygen-denuded air.
5. according to the synthetic method of claim 1 or 2 described carboxylicesterss, it is characterized in that described composite catalyst be by one or more of the salt of metalloporphyrin or supported metalloporphyrin and Cu, Zn, Fe, Co, Mn, Cr or Ni metal or oxide compound with 1: the compound formation of 3-5.
6. according to the synthetic method of the described carboxylicesters of claim 2, it is characterized in that described carboxylic acid solvent is C1-C6 carboxylic acid, senior vegetable oil acid or aromatic carboxylic acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100314818A CN100379715C (en) | 2006-04-11 | 2006-04-11 | Process for preparation of carboxylic acid esters |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100314818A CN100379715C (en) | 2006-04-11 | 2006-04-11 | Process for preparation of carboxylic acid esters |
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|---|---|
| CN1844075A CN1844075A (en) | 2006-10-11 |
| CN100379715C true CN100379715C (en) | 2008-04-09 |
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|---|---|---|---|
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014056850A1 (en) * | 2012-10-08 | 2014-04-17 | Dsm Ip Assets B.V. | Flavor and fragrance formulation (v) |
| CN105367422B (en) * | 2014-08-27 | 2017-08-01 | 湖南中创化工股份有限公司 | A kind of method for preparing tert-butyl acetate with acetic acid and iso-butane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1269343A (en) * | 2000-01-17 | 2000-10-11 | 郭灿城 | Catalytic oxidation process of alkane and naphthene hydrocarbon |
| CN1629120A (en) * | 2004-09-02 | 2005-06-22 | 湖南大学 | Process for preparing aldehyde ketone and acid by oxidation of olefin |
-
2006
- 2006-04-11 CN CNB2006100314818A patent/CN100379715C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1269343A (en) * | 2000-01-17 | 2000-10-11 | 郭灿城 | Catalytic oxidation process of alkane and naphthene hydrocarbon |
| CN1629120A (en) * | 2004-09-02 | 2005-06-22 | 湖南大学 | Process for preparing aldehyde ketone and acid by oxidation of olefin |
Non-Patent Citations (1)
| Title |
|---|
| 金属卟啉化合物及其对烷烃的仿生催化氧化. 阳卫军，郭灿城.应用化学，第21卷第6期. 2004 * |
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Granted publication date: 20080409 Termination date: 20110411 |