Method for producing 1,2,4-butanetriol

Abstract

The invention provides a method for producing 1,2,4-butanetriol. According to the method, a reaction of 2-butene-1,4-diol and hydrogen peroxide is catalyzed by a tungstate and secondary amine to generate 2,3-epoxy-1,4-butanediol; an epoxy reaction solution is treated by using catalase and then the epoxy reaction solution is directly used for a hydrogenation reaction without separation and purification; under action of a Raney nickel catalyst, the hydrogenation reaction is carried out by adopting a feeding method of slowly pressing the epoxy reaction solution into a hydrogenation kettle; and astabilizing agent is added in a rectification process of 1,2,4-butanetriol to inhibit side reactions such as oxidation, intramolecular dehydration and the like. Compared with the prior art, the preparation method of the 1,2,4-butanetriol provided by the invention has the advantages that the raw materials are easy to obtain, the reaction is stable and is easy to control, purity of the obtained product is high, and the method is very suitable for industrial production. According to the production method provided by the invention, the content of the obtained product 1,2,4-butanetriol is more than99.5%, the content of sensitive impurity 3-hydroxytetrahydrofuran is less than 0.05%, and the content of aldehydes and ketones is less than 10 [mu]g / mL.

Description

technical field [0001] The invention relates to a method for producing 1,2,4-butanetriol, which belongs to the technical field of fine chemicals. Background technique [0002] 1,2,4-Butanetriol, English name: 1,2,4-Trihydroxybutane, CASNo.: 3068-00-6, high-purity 1,2,4-Butanetriol is a colorless, odorless, transparent viscous Thick syrupy liquid, its molecular structure is as follows: [0003] [0004] 1,2,4-Butanetriol is an important chemical intermediate in organic synthesis, which is widely used in the fields of military industry, medicine, tobacco, cosmetics, papermaking, agriculture and polymer materials. The nitrate ester of 1,2,4-butanetriol can be used as explosive plasticizer and high-energy, high-tech propellant; in medicine, 1,2,4-butanetriol can also be used directly as an important intermediate As a sustained-release agent, control the release rate of the drug; as a cigarette additive, 1,2,4-butanetriol can reduce the content of nitro substances in cigaret...

AI Technical Summary

Problems solved by technology

In 2006, Degusa (EP 1671936) reported a kind of improved method: first use 3-buten-1-alcohol and hydrogen peroxide, formic acid reaction to prepare the triformate of 1,2,4-butanetriol, then use Methanol is subjected to an acid-catalyzed transesterification reaction to prepare 1,2,4-butanetriol with a purity of 96%. The yield of this method is 70%. Compared with the method reported in EP 0297444, this method greatly reduces the generation of waste water , but because the 3-buten-1-alcohol raw material is not easy to get, the price is more expensive, so the economic feasibility of this method is low

Because the solubility of tungstic acid in the reaction system is very poor, it is in the form of heterogeneous suspension, which requires a relatively large amount of addition, and when the concentration of hydrogen peroxide is low, the reaction rate is very slow, and a large amount of hydrogen peroxide is required to ensure complete reaction conversion.

Due to the large heat release of the reaction, large temperature fluctuations will occur during the dropwise addition of hydrogen peroxide, especially after amplification, the fluctuation effect is more obvious, which is not conducive to the safe progress of the reaction.

In the epoxidation reaction step, in order to make the reaction have a higher conversion rate, the method of excess hydrogen peroxide is used in the patent, and then manganese dioxide is added to remove the excess hydrogen peroxide, although this has improved the 1,4-butenediol conversion rate, but it also increases the cost of subsequent environmental protection treatment of heavy metal oxides, and studies have found that manganese ions can also catalyze the side reaction of epoxy ring opening, which greatly reduces the yield of subsequent reduction reactions

[0009] 2,3-epoxy-1,4-butanediol can be reduced to 1,2,4-butanetriol by chemical reduction method and catalytic hydrogenation method, CN101696157A discloses a method of chemical reduction, the method uses tetrahydrofuran As a solvent, the product is obtained by reduction with sodium borohydride. This method needs to first crystallize and purify 2,3-epoxy-1,4-butanediol to remove water and other impurities, and also use a large amount of expensive sodium borohydride, which not only makes The production and purification operations of the product are complicated, and because of the high production cost, it is not conducive to industrial production

Japanese patent JP5970632 adopts 10% palladium carbon as a catalyst, and ethanol is a solvent to carry out reduction under 150 ℃, 5.0Mpa conditions, although this method has reduced the pressure of reaction, the consumption of palladium carbon catalyst is very big, reaches 9% of raw material weight, Moreover, experiments have found that the catalytic activity of palladium carbon is relatively large under this condition. If repeated application will reduce the product yield due to intermolecular polymerization of raw materials, the catalyst needs to be reactivated to ensure a higher yield, which greatly increases the production cost.

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