CN101723817B - Method for preparing 2, 3-butanedione - Google Patents
Method for preparing 2, 3-butanedione Download PDFInfo
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- CN101723817B CN101723817B CN 200910310246 CN200910310246A CN101723817B CN 101723817 B CN101723817 B CN 101723817B CN 200910310246 CN200910310246 CN 200910310246 CN 200910310246 A CN200910310246 A CN 200910310246A CN 101723817 B CN101723817 B CN 101723817B
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- acetaldehyde
- reaction
- dimethyl diketone
- acetoin
- butanedione
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Abstract
The invention discloses a method for preparing 2, 3-butanedione, which takes acetaldehyde as raw material, substituted 5-ethoxy thiazole salt as catalyst of acetaldehyde coupling condensation reaction and one or more in MnO2, Bi2O3, CuSO4 or Fe2(SO4)3 as catalyst for preparing the 2, 3-butanedione by acetylmethylcarbinol oxidative dehydrogenation; and the method adopts a 'one pot' method to realize the new technique for preparing the 2, 3-butanedione by carrying out coupling condensation reaction and oxidative dehydrogenation reaction on dimolecular acetaldehyde. The thiazole salt catalyst of the method is simple in preparation and low in cost, the dosage of the catalyst in the oxidative dehydrogenation reaction is less, and the technique process flow for preparing the 2, 3-butanedione is simplified by the 'one pot' method. The acetaldehyde has the conversion rate of 80-91%, and the 2, 3-butanedione has the selectively of 80-90%. Therefore, the process route provides a new method for the industrial production of the 2, 3-butanedione.
Description
Technical field
The invention belongs to the fine chemical technology field, relate to a kind of preparation 2, the method for 3-dimethyl diketone.
Background technology
2, the 3-dimethyl diketone, yellow oily liquid, natural being present in milk, fennel and the multiple leavened food, be mainly used in cream, oleomargarine, cheese, the sweetener of candy and drinks etc. also are used as the midbody of synthetic perfume and other Chemicals.At present, domestic and international Synthetic 2, the method for 3-dimethyl diketone mainly contains: 1, extraction method from natural goods, this method Product Safety is high, compliance with environmental protection requirements.But because scarcity of raw material, the product cost that makes is high, is not suitable for mass production; 2, glucose fermentation method, though the raw materials of glucose source is extensively, technology content requires high, needs specific bacterial classification and bigger industrial scale, facility investment is bigger, is difficult to industrial application; 3, methylethylketone oxidation style, methylethylketone oxidation style are that present domestic manufacturer produces 2, the main method of 3-dimethyl diketone, and this method technical maturity, but 2, the poor selectivity of 3-dimethyl diketone.Also having with the methyl vinyl ketone in addition is raw material, the hydrogen peroxide catalytic oxidation method; The isobutyric aldehyde air oxidation process; Perhaps there are environmental pollution in the silver-bearing copper catalytic air oxidation method of butyleneglycol, these methods or have 2, the low problem that waits of 3-dimethyl diketone yield.
Recently, the someone has reported method (Chinese patent, the application number: 200410021240.6) for preparing acetoin from the acetaldehyde coupling.Be raw material with the acetoin (3-hydroxyl-2-butanone) that newly distills again, use anhydrous FeCl
3Be oxygenant, through acetoin oxidation preparation 2,3-dimethyl diketone (one Chinese patent application number: 200510046107.0).This route not only needs synthetic completion of two steps, also need increase fractionation by distillation technology one, and the oxygenant consumption is 2 times (mol ratios) of acetoin raw material, the product separation purification difficult.Not only the acetoin raw materials cost is higher, production energy consumption is higher for this operational path, and product purity is not high etc., and problem causes it to be difficult in industry, obtaining to use.In addition, acetoin is than 2, and 3-dimethyl diketone market value is higher, if be raw material with the acetoin, through oxidation preparation 2, the 3-dimethyl diketone does not almost have industrial application value.Therefore, seek more economical, environmental protection, technological line is simple and technological operation is easy 2,3-dimethyl diketone synthesis route will have important use and be worth.
Summary of the invention
The invention provides that a kind of raw materials cost is cheap, selective oxidation catalyst for reaction consumption is few, reaction-ure conversion-age and selectivity of product are high and are suitable for 2 of suitability for industrialized production, 3-dimethyl diketone preparation method.
Technical scheme of the present invention is following: with substituted 5-hydroxy ethylthiazole salt is the catalyzer of acetaldehyde coupling condensation reaction, with MnO
2, Bi
2O
3, CuSO
4Or Fe
2(SO
4)
3In one or more be acetoin selective oxidation catalyst for reaction, preferred Bi
2O
3Perhaps Bi
2O
3And MnO
2Mixture is the catalyzer of acetoin oxidation, is feedstock production 2 with acetaldehyde, the 3-dimethyl diketone, and the mass ratio of the catalyzer of described replacement 5-hydroxy ethylthiazole salt and acetoin oxydehydrogenation is 10: 1-40: 1.
The mass ratio of raw material acetaldehyde and substituted 5-hydroxy ethylthiazole salt is 100: 2.5-100: 1.
Temperature of reaction is 100-160 ℃, and the reaction times is 2-6 hour.
Described substituted 5-hydroxy ethylthiazole salt catalyst structural formula is suc as formula 1, and R is C in the structural formula
1-C
10Short-chain hydrocarbon group, C
6-C
14Aryl or C
6-C
14Aralkyl, X
-Be Cl
-, Br
-Or I
-
R is preferably methyl, ethyl, propyl group, butyl, sec.-propyl, allyl group, phenyl, benzyl, styroyl, Heterocyclylalkyl, imidazolidyl or thiazolidyl.R further is preferably methyl, ethyl, propyl group, butyl, sec.-propyl, benzyl, allyl group.R most preferably is ethyl or benzyl, X
-Be preferably Br
-
Wherein working as R is ethyl, X
-Be Br
-The ethyl type thiazole salt that ion is formed, the catalyzer of acetoin oxydehydrogenation is Bi
2O
3The time, 2 of acquisition, 3-dimethyl diketone productive rate is best.
With acetaldehyde is raw material, in the autogenous pressure reaction kettle, adds the catalyzer of thiazole salt and acetoin oxidative dehydrogenation in proportion, adopts the method for " treating different things alike ", has realized by one step of acetaldehyde coupled oxidation preparation 2, the technology of 3-dimethyl diketone.This method has that the thiazole salt Preparation of Catalyst is simple, the catalyst levels of acetoin oxidative dehydrogenation is few, technological operation is simple and characteristics such as production cost is low; And the acetoin that this method makes need not separated from reaction system; Directly by dehydrogenation oxidation; The transformation efficiency of acetaldehyde and 2,3-dimethyl diketone selectivity is high.Be 2, the suitability for industrialized production of 3-dimethyl diketone provides a kind of novel method.
Though it is that raw material prepares 2 through oxidation with the acetoin that bibliographical information is arranged, the 3-dimethyl diketone, acetoin is than 2; 3-dimethyl diketone market value is higher, from considering almost there is not industrial application value economically, analyzes from Technology; Be raw material with the acetoin in the prior art, with FeCl
3Be oxygenant and since in this technology the oxidation acetoin to prepare this step oxygenant consumption of dimethyl diketone very big, not only increased oxidant feed and production technique cost, and owing to a large amount of FeCl in the reaction system
3Exist, product loss in separating purification process is bigger, causes 2, the separation difficulty of 3-dimethyl diketone product, and 2, the yield of 3-dimethyl diketone reduces.Is therefore the present invention 10: 1 through the optimum quality ratio that a large amount of tests draw thiazole salt and acetoin oxidative dehydrogenation catalyzer? 0: 1, the preferred Bi of the catalyzer of acetoin oxidative dehydrogenation
2O
3Or Bi
2O
3And MnO
2Mixed catalyst, neither can cause the isolating difficulty of subsequent products, also can reach good catalytic effect.
In addition, acetoin has more economic worth than dimethyl diketone, also is worthless in industry if come oxidation to prepare dimethyl diketone with it, and therefore, technology practicality in actually operating was not strong in the past.Generally speaking, restricting original difficult technique is with industrialized reason: 1, thiazole salt prepares complicacy and preparation cost height; 2, the oxygenant consumption is big, has increased the technology cost, and product separates difficult; 3, practicality is not strong.The invention solves these problems: the thiazole salt Preparation of Catalyst is simple and cost is low; The catalyst levels of acetoin oxidative dehydrogenation is few; Being easy to subsequent products separates; " treating different things alike " method of employing has been simplified technology, and practicality is extremely strong.
Know-why of the present invention is as shown in Figure 1; With acetaldehyde is raw material; In self autoclave pressure at first by acetaldehyde self coupling condensation reaction takes place immediately under the thiazole salt catalyst action; Generate acetoin, the acetoin that reaction produces under catalyst action immediately oxidative dehydrogenation obtain 2, the 3-dimethyl diketone.Be characterized in: in reaction process, acetaldehyde obtains acetoin through the coupling condensation, the selective oxidation dehydrogenation reaction takes place under catalyst action again produce 2; The 3-dimethyl diketone, the acetaldehyde feed stock conversion is high, and 2; The selectivity of 3-dimethyl diketone is good, thereby 2, the yield of 3-dimethyl diketone is high.Though with the acetoin is that raw material can prepare 2 through oxidation; The 3-dimethyl diketone, but acetoin has more economic worth than dimethyl diketone, also is worthless in industry if come oxidation to prepare dimethyl diketone with it; And in the acetoin oxidation reaction process, traditional technology is with FeCl
3Be oxygenant, consumption is very big, causes 2, the separation difficulty of 3-dimethyl diketone product, and practicality is not strong in actually operating.The thiazole salt Preparation of Catalyst is simple and cost is low among the present invention, and the catalyst levels of acetoin oxidative dehydrogenation is few, has stronger practicality.
The present invention is the raw material method catalysis Synthetic 2 of " treating different things alike " with acetaldehyde, and 3-dimethyl diketone, the transformation efficiency of acetaldehyde are 80-91%, 2, and the selectivity 80-90% of 3-dimethyl diketone, synthetic 2,3-dimethyl diketone product only need be through simple distillations, promptly separable purification.
Description of drawings
Fig. 1 is a know-why synoptic diagram of the present invention.
Embodiment
Below in conjunction with instance the present invention is done further detailed explanation, rather than limitation of the present invention.
Embodiment 1
With 20.0g acetaldehyde, 0.4g 3-ethyl-4-methyl-5-hydroxy ethylthiazole bromine salt and 0.04g MnO
2Join together in the autoclave, start and stir and slowly intensification, temperature of reaction is controlled at 140 ℃, and the reaction times is 2 hours, and reaction finishes the back naturally cooling, uses gas chromatographic analysis, the transformation efficiency 91.4%, 2 of acetaldehyde, the selectivity 69.6% of 3-dimethyl diketone.
Embodiment 2
With 20.0g acetaldehyde, 0.4g 3-ethyl-4-methyl-5-hydroxy ethylthiazole bromine salt and 0.04g MnO
2Join together in the autoclave, start and stir and slowly intensification, temperature of reaction is controlled at 130 ℃, and the reaction times is 4 hours, and reaction finishes the back naturally cooling, uses gas chromatographic analysis, the transformation efficiency 83.5%, 2 of acetaldehyde, the selectivity 72.8% of 3-dimethyl diketone.
Embodiment 3
With 20.0g acetaldehyde, 0.2g 3-ethyl-4-methyl-5-hydroxy ethylthiazole bromine salt and 0.02g MnO
2Join together in the autoclave, start and stir and slowly intensification, temperature of reaction is controlled at 140 ℃, and the reaction times is 2 hours, and reaction finishes the back naturally cooling, uses gas chromatographic analysis, the transformation efficiency 86.2%, 2 of acetaldehyde, the selectivity 73.4% of 3-dimethyl diketone.
Embodiment 4
With 20.0g acetaldehyde, 0.2g 3-ethyl-4-methyl-5-hydroxy ethylthiazole bromine salt and 0.01g MnO
2Join together in the autoclave, start and stir and slowly intensification, temperature of reaction is controlled at 140 ℃, and the reaction times is 2 hours, and reaction finishes the back naturally cooling, uses gas chromatographic analysis, the transformation efficiency 80.3%, 2 of acetaldehyde, the selectivity 75.1% of 3-dimethyl diketone.
Embodiment 5
With 20.0g acetaldehyde, 0.4g 3-ethyl-4-methyl-5-hydroxy ethylthiazole bromine salt and 0.01g Bi
2O
3Join together in the autoclave, start and stir and slowly intensification, temperature of reaction is controlled at 140 ℃, and the reaction times is 2 hours, and reaction finishes the back naturally cooling, uses gas chromatographic analysis, the transformation efficiency 90.7%, 2 of acetaldehyde, the selectivity 76.2% of 3-dimethyl diketone.
Embodiment 6
With 20.0g acetaldehyde, 0.2g 3-ethyl-4-methyl-5-hydroxy ethylthiazole bromine salt and 0.01g Bi
2O
3Join together in the autoclave, start and stir and slowly intensification, temperature of reaction is controlled at 140 ℃, and the reaction times is 2 hours, and reaction finishes the back naturally cooling, uses gas chromatographic analysis, the transformation efficiency 87.1%, 2 of acetaldehyde, the selectivity 80.5% of 3-dimethyl diketone.
Embodiment 7
With 20.0g acetaldehyde, 0.2g 3-benzyl-4-methyl-5-hydroxy ethylthiazole bromine salt and 0.02g Bi
2O
3Join together in the autoclave, start and stir and slowly intensification, temperature of reaction is controlled at 140 ℃, and the reaction times is 2 hours, and reaction finishes the back naturally cooling, uses gas chromatographic analysis, the transformation efficiency 80.7%, 2 of acetaldehyde, the selectivity 77.8% of 3-dimethyl diketone.
Embodiment 8
With 20.0g acetaldehyde, 0.2g 3-benzyl-4-methyl-5-hydroxy ethylthiazole bromine salt and 0.01g Bi
2O
3Join together in the autoclave, start and stir and slowly intensification, temperature of reaction is controlled at 140 ℃, and the reaction times is 2 hours, and reaction finishes the back naturally cooling, uses gas chromatographic analysis, the transformation efficiency 82.3%, 2 of acetaldehyde, the selectivity 79.1% of 3-dimethyl diketone.
Embodiment 9
With 20.0g acetaldehyde, 0.2g 3-benzyl-4-methyl-5-hydroxy ethylthiazole bromine salt and 0.01g CuSO
4Join together in the autoclave, start and stir and slowly intensification, temperature of reaction is controlled at 140 ℃, and the reaction times is 2 hours, and reaction finishes the back naturally cooling, uses gas chromatographic analysis, the transformation efficiency 85.7%, 2 of acetaldehyde, the selectivity 73.1% of 3-dimethyl diketone.
Embodiment 10
With 20.0g acetaldehyde, 0.2g 3-benzyl-4-methyl-5-hydroxy ethylthiazole bromine salt and 0.02g Bi
2O
3And MnO
2(mass ratio is 1: 1) joins in the autoclave together, starts to stir and slowly intensification, and temperature of reaction is controlled at 140 ℃; Reaction times is 2 hours, and reaction finishes the back naturally cooling, uses gas chromatographic analysis; The transformation efficiency 89.3%, 2 of acetaldehyde, the selectivity 83.2% of 3-dimethyl diketone.
Claims (3)
1. one kind prepares 2, and the method for 3-dimethyl diketone is characterized in that, is the catalyzer of acetaldehyde coupling condensation reaction with substituted 5-hydroxy ethylthiazole salt, with MnO
2, Bi
2O
3, CuSO
4Or Fe
2(SO
4)
3In one or more be the acetoin oxy-dehydrogenation catalyst, be feedstock production 2 with acetaldehyde, the 3-dimethyl diketone, the mass ratio of described substituted 5-hydroxy ethylthiazole salt and acetoin oxy-dehydrogenation catalyst is 10:1-40:1;
The mass ratio of raw material acetaldehyde and substituted 5-hydroxy ethylthiazole salt is 100:2.5-100:1;
Described substituted 5-hydroxy ethylthiazole salt is the substituted 4-methyl in ethyl or benzyl N position-5-hydroxy ethylthiazole bromine salt.
2. preparation 2 according to claim 1, the method for 3-dimethyl diketone is characterized in that, the acetoin oxy-dehydrogenation catalyst is Bi
2O
3, perhaps be Bi
2O
3And MnO
2Mixture.
3. preparation 2 according to claim 1, the method for 3-dimethyl diketone is characterized in that, and temperature of reaction is 100-160 ℃, and the reaction times is 26 hours.
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| CN 200910310246 CN101723817B (en) | 2009-11-23 | 2009-11-23 | Method for preparing 2, 3-butanedione |
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|---|---|---|---|
| CN 200910310246 CN101723817B (en) | 2009-11-23 | 2009-11-23 | Method for preparing 2, 3-butanedione |
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| CN101723817B true CN101723817B (en) | 2012-12-26 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130627B (en) * | 2013-02-28 | 2014-10-22 | 河南华龙香料有限公司 | Clean production technology of 2,3-pentanedione |
| CN105541588B (en) * | 2016-02-25 | 2017-12-01 | 济南悟通生物科技有限公司 | A kind of synthetic method of diacetyl |
| CN106905127B (en) * | 2017-03-09 | 2020-05-01 | 中国科学院山西煤炭化学研究所 | Method for synthesizing 2, 5-hexanedione by oxidative dehydrogenation coupling of acetone |
| CN107032967A (en) * | 2017-05-12 | 2017-08-11 | 淮阴工学院 | A kind of green synthesis method of 2,3 diacetyl |
| CN114950545B (en) * | 2022-03-28 | 2024-06-07 | 浙江恒逸石化研究院有限公司 | Oxazolium catalyst for acetaldehyde acyloin condensation reaction, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562934A (en) * | 2004-04-05 | 2005-01-12 | 大连金菊化工厂 | Method for synthesizing Yiyuyin through catalysis of acetaldehyde |
| CN1686992A (en) * | 2005-03-24 | 2005-10-26 | 大连来克精化有限公司 | Method for preparing butanedione through oxidating acetylmethylcarbinol |
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2009
- 2009-11-23 CN CN 200910310246 patent/CN101723817B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562934A (en) * | 2004-04-05 | 2005-01-12 | 大连金菊化工厂 | Method for synthesizing Yiyuyin through catalysis of acetaldehyde |
| CN1686992A (en) * | 2005-03-24 | 2005-10-26 | 大连来克精化有限公司 | Method for preparing butanedione through oxidating acetylmethylcarbinol |
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