CN111217704A - Method for preparing butyl butyrate by directly catalyzing and converting n-butyraldehyde - Google Patents
Method for preparing butyl butyrate by directly catalyzing and converting n-butyraldehyde Download PDFInfo
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- CN111217704A CN111217704A CN201811417678.4A CN201811417678A CN111217704A CN 111217704 A CN111217704 A CN 111217704A CN 201811417678 A CN201811417678 A CN 201811417678A CN 111217704 A CN111217704 A CN 111217704A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a method for preparing butyl butyrate by directly converting n-butyl aldehyde, which takes n-butyl aldehyde as a raw material, one or more of organic dibasic aluminum or organic tribasic aluminum such as aluminum oxalate, aluminum citrate, aluminum tartrate, aluminum malate, aluminum adipate, aluminum pimelate, aluminum dodecanedioate and the like as a catalyst, the dosage of the catalyst is 0.2-1.0% of the mass of the n-butyl aldehyde, the reaction temperature is 0-20 ℃, the reaction time is 0.5-2 hours, and the conversion rate of the n-butyl aldehyde and the selectivity of the butyl butyrate can reach more than 99%. The method has the advantages of short route, good atom economy, mild reaction conditions, recyclable catalyst, high raw material conversion rate, high product selectivity and the like.
Description
Technical Field
The invention belongs to the field of organic chemical industry, and particularly relates to a method for preparing butyl butyrate by directly catalyzing and converting n-butyraldehyde.
Background
Butyl butyrate, also known as n-butyl butyrate, is a colorless transparent liquid with banana and pineapple flavors and is found in fruits such as apples, bananas, grapes, pears, strawberries, plums and the like. Butyl butyrate is an edible spice which is allowed to be used in the food additive use standard of national food safety standard (GB 2760) in China, is widely used for foods such as candies, biscuits, bread, ice cream, carbonated drinks and the like, and can also be used as a solvent of nitrocellulose, shellac, coumarone resin, coating and the like. The butyl butyrate used in industry is prepared by the esterification reaction of n-butyric acid and n-butanol under the action of a catalyst. The catalyst used is mainly concentrated sulfuric acid. Because of strong acidity and strong oxidizing property of concentrated sulfuric acid, the concentrated sulfuric acid has serious corrosion to equipment, is easy to generate side reactions such as oxidation, dehydration and the like, has dark product color, complex post-treatment process, large discharge amount of three wastes and high production cost. In order to solve the above problems, research and development of a novel catalyst that replaces sulfuric acid have been receiving attention. The literature reports that catalysts replacing sulfuric acid are: organic acids such as p-toluenesulfonic acid and sulfamic acid; inorganic salts such as ammonium ferric sulfate, sodium hydrogen sulfate, titanium sulfate, ceric sulfate, ferric chloride, and stannic chloride; solid super acid; enzymes and phase transfer catalysts, etc. Compared with sulfuric acid, the catalysts have the advantages of low corrosivity and the like, but still have the problems of complex post-treatment process, large three-waste discharge, high production cost and the like, and some catalysts also need to use toluene as a water-carrying agent, so that the safety of the product butyl butyrate serving as an edible spice is reduced, and the industrial application value of the butyl butyrate is limited.
In another aspect, a method for synthesizing n-butyric acid comprises:
(1) a fermentation method: the n-butyric acid is prepared by fermentation of sugar and the like. The method has low yield and complicated post-treatment process, and is eliminated.
(2) N-pentanol oxidation: n-pentanol is oxidized by concentrated nitric acid to prepare n-butyric acid. The method is a laboratory preparation method of the n-butyric acid, has low atom economy, complex process, high cost and no industrial application value, and the n-butyric acid yield is only about 50 percent.
(3) N-butanol oxidation method: n-butyl alcohol is oxidized to obtain n-butyl aldehyde, and then further oxidized to obtain n-butyric acid. With the industrial application of the process for synthesizing n-butyraldehyde by propylene carbonylation, the method is eliminated.
(4) N-butyraldehyde oxidation method: the propylene is carbonylated to prepare n-butyl aldehyde, and then is oxidized to prepare n-butyric acid. The method has simple process route and high product yield, and is an industrial preparation method of the existing n-butyric acid.
The synthesis method of the n-butanol comprises the following steps:
(1) a fermentation method: the method comprises the steps of taking starch as a raw material, preparing n-butanol through processes of fermentation, rectification separation and the like, and obtaining acetone and ethanol as byproducts.
(2) Acetaldehyde aldol condensation method: performing aldol condensation and dehydration on acetaldehyde to obtain crotonaldehyde (2-butenal), and then hydrogenating to obtain n-butanol.
(3) N-butyraldehyde hydrogenation: the propylene is carbonylated to prepare n-butyl aldehyde, and then the n-butyl alcohol is prepared by hydrogenation. The method is the most important industrial production method of the n-butanol.
In summary, as shown in formula 1, butyl butyrate is prepared by oxidizing n-butyl aldehyde to obtain n-butyl acid, and then performing esterification reaction on the n-butyl acid and n-butyl alcohol prepared by hydrogenation of n-butyl aldehyde under the action of catalysts such as concentrated sulfuric acid.
The method takes n-butyraldehyde as a raw material, butyl butyrate is prepared through the processes of oxidation, hydrogenation, esterification and the like, and the method has the problems of long process route, serious equipment corrosion, more side reactions, deep product color, complex post-treatment process, large discharge amount of three wastes, high production cost and the like. In addition, the esterification reaction is a reversible reaction and is limited by reaction equilibrium, and the single-pass conversion rate is low. Water is generated in the reaction process, and in order to shift the reaction equilibrium to the direction of generating butyl butyrate, toluene can be used as a water-carrying agent, so that the conversion rate is improved. But the use of toluene reduces the safety of the product butyl butyrate as a food additive.
In order to solve the above problems, scientists have been exploring new methods for preparing butyl butyrate. The literature reports that n-butanol can be directly converted into butyl butyrate. Patent applicationEP0201105 reports that n-butanol conversion yields butyl butyrate, but the yield is only 6.6%. At 285 deg.C, 6.5MPa, N2As carrier gas, CuO/ZnO/Al2O3Catalytic n-butanol conversion, conversion 51%, butyl butyrate selectivity 56% (Elliott D.J., Pennella F., The formation of ketones in The presence of carbon monoxide over CuO/ZnO/Al)2O3J.Catal.,1989,119, 359-367). Under the conditions of 260 +/-5 ℃ and not less than 0.4MPa, the Cu-Cr-M catalyzes the conversion of n-butyl alcohol, the conversion rate is 64 percent, and the selectivity of the butyl butyrate is 73.8 percent (Wanhaijing, segmented Weiwei, one-step synthesis of the butyl butyrate by the n-butyl alcohol, fine petrochemical industry, 2013,1, 20-22). The reaction route is shown as formula 2.
In the reaction, the n-butanol is not only a product of hydrogenation of n-butyraldehyde, but also a raw material for preparing butyl butyrate by dehydrogenation, disproportionation and esterification; the hydrogen is not only a raw material for preparing the n-butyl alcohol by hydrogenating the n-butyl aldehyde, but also a product for preparing the butyl butyrate by dehydrogenating, disproportionating and esterifying the n-butyl alcohol. The net reaction result of the two-step reaction is shown as formula 3, namely, butyl butyrate is directly prepared by converting n-butyl aldehyde.
The n-butyraldehyde is directly converted to prepare the butyl butyrate, theoretically, atoms of the raw material n-butyraldehyde all enter the product butyl butyrate, byproducts such as water and the like are generated, and the atom economy reaches 100%. Compared with the n-butanol method, the method has simple route and can greatly reduce energy consumption. However, the method has great technical difficulty and few related research reports. The literature reports that the Cu/ZnO/Al is modified under the conditions of 255 ℃ and 0.7MPa2O3The conversion of n-butyraldehyde is catalyzed, the conversion rate is about 60 percent, the selectivity of butyl butyrate is very low, and the product contains about 20 percent of 4-heptanone, 20 percent of n-butanol and 6 percent of n-butyric acid. (Periweisen, a one-step synthesis of butyrate acetate from n-butanol or n-butyraldehyde, petrochemical, 1993,22(2), 111-114).
Disclosure of Invention
In order to solve the outstanding problems of serious equipment corrosion, more side reactions, deep product color, complex post-treatment process, large discharge amount of three wastes, high production cost and the like existing in the conventional butyl butyrate preparation route, the invention aims to: the method for preparing butyl butyrate by directly catalyzing and converting n-butyraldehyde has the advantages of short route, good atom economy, mild reaction conditions, recyclable catalyst, high raw material conversion rate and product selectivity and the like.
In order to achieve the purpose, the invention adopts the technical scheme that: taking n-butyraldehyde as a raw material, carrying out disproportionation esterification reaction in the presence of a catalyst to prepare butyl butyrate, wherein the reaction formula is as follows:
according to the invention, the catalyst is of great importance. When no catalyst is present or the catalyst activity is low, the conversion of n-butyraldehyde is very low. When the catalyst activity is high, the high conversion rate of n-butyraldehyde and the high selectivity of butyl butyrate can be obtained. The disproportionation esterification catalyst researched and developed by the invention is one or more than two of organic dibasic aluminum or organic tribasic aluminum such as aluminum oxalate, aluminum citrate, aluminum tartrate, aluminum malate, aluminum adipate, aluminum pimelate, aluminum dodecanedioate and the like.
According to the invention, the dosage of the catalyst is 0.2-1.0% of the mass of the n-butyl aldehyde, the reaction temperature is 0-20 ℃, and the reaction time is 0.5-2 hours.
The invention has the beneficial effects that: one or more than two of organic binary aluminum or organic ternary aluminum such as aluminum oxalate, aluminum citrate, aluminum tartrate, aluminum malate, aluminum adipate, aluminum pimelate, aluminum dodecanedioate and the like are used as catalysts, n-butyl aldehyde is directly catalyzed and converted to prepare butyl butyrate, and the conversion rate of the n-butyl aldehyde and the selectivity of the butyl butyrate can reach more than 99%. The method has the advantages of short route, good atom economy, mild reaction conditions, recyclable catalyst, high raw material conversion rate, high product selectivity and the like.
Detailed Description
The following examples are provided to aid in the understanding of the present invention, but the present disclosure is not limited thereto.
Example 1
20 g of n-butyraldehyde and 0.2 g of aluminum oxalate (accounting for 1 percent of the mass of the n-butyraldehyde) are added into a 100ml two-mouth round-bottom flask provided with a condenser tube, the mixture is uniformly stirred, the reaction temperature is controlled to be 10 ℃ through a refrigerating machine, the reaction is carried out for 2 hours, the mixture after the reaction is qualitatively and quantitatively analyzed through gas chromatography-mass spectrometry, and the conversion rate of the n-butyraldehyde and the selectivity of butyl butyrate are both more than 99 percent.
Examples 2 to 7
Examples 2-7 were performed similarly to example 1, and the specific reaction conditions and results are shown in Table 1. Aluminum citrate, aluminum tartrate, aluminum malate, aluminum adipate, aluminum pimelate, aluminum dodecanedioate and other organic binary aluminum or organic ternary aluminum are used as catalysts, the dosage of the catalysts is 0.2-1.0% of the mass of n-butyl aldehyde, the reaction temperature is 0-20 ℃, the reaction time is 0.5-2 hours, and the conversion rate of the n-butyl aldehyde and the selectivity of butyl butyrate can reach more than 99%.
TABLE 1 direct catalytic conversion of n-butyraldehyde to butyl butyrate
Example 8
The catalyst is recycled. After the reaction of example 1, the product was distilled and separated, the catalyst was left in the reaction flask, 20 g of n-butyraldehyde was added to the reaction flask for repeated reaction at 10 ℃ for 2 hours, and both the conversion of n-butyraldehyde and the selectivity of butyl butyrate were 99% or more.
Comparative examples 9 to 11
To investigate the effect of the catalyst and its composition on the reaction, comparative experiments were performed. A reaction was carried out under the same conditions as in example 1, using n-butyraldehyde as a starting material and without a catalyst, or using aluminum triacetate and aluminum diethylmalonate as a catalyst, and the results are shown in Table 2, similarly to example 1.
TABLE 2 reaction results of comparative examples for the direct conversion of n-butyraldehyde to butyl butyrate
In example 1, aluminum oxalate was used as a catalyst, and both the conversion rate of n-butyraldehyde and the selectivity of butyl butyrate were more than 99%. However, according to comparative example 9, it can be seen that n-butyraldehyde was not converted into butyl butyrate under the same reaction conditions without a catalyst. As is clear from comparative examples 10 and 11, it was found that the conversion of n-butyraldehyde and the selectivity of butyl butyrate were much lower than those of example 1 under the same reaction conditions using an organic aluminum monobasic acid such as aluminum acetate or aluminum lactate as a catalyst. As can be seen from comparative example 12, an attempt to use aluminum diethylmalonate as a catalyst resulted in a significantly lower n-butyraldehyde conversion and a much lower butyl butyrate selectivity than in example 1, indicating that not all aluminum organodialcohols gave good results. Comparative examples 9-12 show that the catalysts and their compositions have a very large influence on the reaction results according to the invention.
In the invention, one or more than two of organic dibasic aluminum or organic tribasic aluminum such as aluminum oxalate, aluminum citrate, aluminum tartrate, aluminum malate, aluminum adipate, aluminum pimelate, aluminum dodecanedioate and the like are used as catalysts, n-butyl aldehyde is directly catalytically converted to prepare butyl butyrate, and the conversion rate of the n-butyl aldehyde and the selectivity of the butyl butyrate can reach more than 99%. The method has the advantages of short route, good atom economy, mild reaction conditions, recyclable catalyst, high raw material conversion rate, high product selectivity and the like.
Claims (3)
1. A method for preparing butyl butyrate by directly converting n-butyraldehyde is characterized by comprising the following steps: butyl butyrate is prepared by taking n-butyraldehyde as a raw material in the presence of one or more than two catalysts of organic dibasic aluminum or organic tribasic aluminum;
the organic binary aluminum or organic ternary aluminum catalyst is one or more than two of aluminum oxalate, aluminum citrate, aluminum tartrate, aluminum malate, aluminum adipate, aluminum pimelate and aluminum dodecanedioate.
2. The method of claim 1, wherein: the reaction temperature is 0-20 ℃, and the reaction time is 0.5-2 hours.
3. The method of claim 1 or 2, wherein: the dosage of the catalyst is 0.2-1.0% of the mass of the n-butyl aldehyde.
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CN112079704A (en) * | 2020-10-15 | 2020-12-15 | 苏州亚科科技股份有限公司 | Preparation method of butyl butyrate and butyric acid |
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WO2003049855A1 (en) * | 2001-12-10 | 2003-06-19 | Showa Denko K.K. | Catalyst for producing carboxylic acid ester and process for producing the same |
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CN112079704A (en) * | 2020-10-15 | 2020-12-15 | 苏州亚科科技股份有限公司 | Preparation method of butyl butyrate and butyric acid |
CN112079704B (en) * | 2020-10-15 | 2022-09-13 | 苏州亚科科技股份有限公司 | Preparation method of butyl butyrate and butyric acid |
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