CN111349008A

CN111349008A - Method for preparing glyoxylic acid

Info

Publication number: CN111349008A
Application number: CN202010299794.1A
Authority: CN
Inventors: 程青芳; 张超; 张思武; 王启发; 王仕高
Original assignee: Linyi Jinyimeng Biotechnology Co ltd; Jiangsu Ocean University
Current assignee: Linyi Jinyimeng Biotechnology Co ltd; Jiangsu Ocean University
Priority date: 2020-04-16
Filing date: 2020-04-16
Publication date: 2020-06-30
Anticipated expiration: 2040-04-16
Also published as: CN111349008B

Abstract

The invention discloses a method for preparing glyoxylic acid, which has the following reaction formula:

Description

Method for preparing glyoxylic acid

Technical Field

The invention belongs to the technical field of chemical product preparation, and particularly relates to a preparation method of glyoxylic acid.

Background

Glyoxylic acid is a simple aldehydic acid with double properties of aldehyde and carboxylic acid, and dozens of fine chemical products can be prepared by deriving from the glyoxylic acid, so the glyoxylic acid is widely applied to the fields of medicines, spices, pesticides, paints, papermaking, food additives and the like, and has large market demand.

At present, the industrial preparation methods of glyoxylic acid mainly comprise an oxalic acid electrolytic reduction method, a maleic anhydride ozone oxidation method, a glyoxal nitric acid oxidation method and the like. The oxalic acid electrolytic reduction method and the maleic anhydride ozone oxidation method have large energy consumption and equipment investment, higher production cost and less industrial application; the reaction condition of the glyoxal nitric acid oxidation method is mild, the process is simple and mature, the equipment investment is low, and the method is the most adopted by many manufacturers at home and abroad at present; however, the method is characterized in that the reaction is carried out in a homogeneous system, and strong acid nitric acid is used as an oxidant, in the homogeneous system, the nitric acid is easy to simultaneously oxidize two aldehyde groups in a reactant glyoxal molecule to generate a binary oxidation by-product oxalic acid, a low-concentration glyoxylic acid aqueous solution is obtained after the reaction, a large amount of water needs to be distilled at high temperature to obtain high-concentration or solid glyoxylic acid, and impurities such as oxalic acid and the like are also generated in the high-temperature distillation process, so that the reaction selectivity is poor, the product purity is low, and the quality is poor; in addition, waste acid separation and salt removal in post-treatment are difficult; the nitric acid has serious corrosion to equipment, and bumping is easy to occur when the concentration is high; the unreacted nitric acid makes the glyoxylic acid slowly oxidized and decomposed, and nitric oxide gas polluting the environment is easily generated; the unconverted glyoxal in the product interferes with the condensation reaction of glyoxylic acid, and limits the application range of the product. Therefore, the method for preparing the green, safe and efficient glyoxylic acid is urgent.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a safe, environment-friendly and efficient method for preparing glyoxylic acid, which adopts a metal heteropolyacid loaded SBA-15 mesoporous molecular sieve as a catalyst to catalyze hydrogen peroxide to oxidize glyoxal and prepare the glyoxylic acid with high yield. Therefore, the method for preparing the glyoxylic acid has the advantages of cheap and easily obtained raw materials, easy recovery of the catalyst, high utilization rate, high process safety, simple post-treatment, high yield, good selectivity and high product purity.

The technical scheme of the invention is summarized as follows:

adding raw materials of glyoxal, a certain amount of catalyst and a solvent into a reaction bottle, stirring for 0.5h at normal temperature, then dropwise adding 30 wt% hydrogen peroxide, and after dropwise adding, keeping a certain reaction temperature and continuing to react for a period of time. After the reaction is finished, cooling, and filtering, washing and drying the catalyst for the next reaction; separating and concentrating the filtrate to separate out the product glyoxylic acid.

The preparation route is as follows:

the catalyst is a metal heteropolyacid loaded SBA-15 mesoporous molecular sieve, and the general formula of the catalyst is as follows:

M-POM-octyl-NH₃SBA-15, wherein M is a metal such as iron, copper, cobalt, etc., preferably iron; POM is heteropoly acid, and the structure of M-POM is PW₁₁MO₄₀ ^n-(ii) a -octyl is n-octyltrimethoxysilane; SBA-15 is a mesoporous silica molecular sieve; the aperture of the catalyst is between 4.5 and 6.5 nm.

The preparation of the catalyst is relatively simple by a mature method.

The catalyst is high in catalytic efficiency, and the ratio of the mass of the catalyst to the quantity of the glyoxal material as the raw material is 2-5 g: 1 mol.

The catalyst is easy to recover, high in utilization rate and capable of being recycled for 6 times, and the yield is only reduced by 3-5%.

The reaction temperature is 40-60 ℃.

The solvent is one or more of n-amyl alcohol, n-butyl alcohol, isopropanol, ethanol and tetrahydrofuran, wherein n-amyl alcohol is preferred.

The method provides an efficient, simple and safe method for preparing the glyoxylic acid.

Detailed Description

The present invention will be further described with reference to the following specific examples; it should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

The raw materials or reagents used in the examples were, unless otherwise specified, analytical or industrial products.

Example 1

100mmol of 40 wt% ethanediAldehyde, 0.5g of Fe heteropoly acid loaded SBA-15 mesoporous molecular sieve Fe-POM-octyl-NH₃Adding SBA-15 and 200mL of n-amyl alcohol into a reaction bottle, stirring for 0.5h at normal temperature, dropwise adding 180mmol of 30 wt% hydrogen peroxide, controlling the dropwise adding within 1h, heating to 60 ℃ after the dropwise adding, and keeping the temperature to continue the reaction for 2 h. Stopping the reaction, cooling the reaction solution at 0 ℃ for 2 hours, filtering the solid and the catalyst, and washing and drying the catalyst for the next reaction; separating the n-amyl alcohol layer from the filtrate, extracting the water layer with n-amyl alcohol, combining the n-amyl alcohol layers, drying, concentrating under reduced pressure, and separating out white solid, namely the product glyoxylic acid, wherein the yield is 82% and the purity is 99%.

Example 2

100mmol of 40 wt% glyoxal and 0.5g of cobalt heteropolyacid loaded SBA-15 mesoporous molecular sieve Co-POM-octyl-NH₃Adding SBA-15 and 200mL of n-amyl alcohol into a reaction bottle, stirring for 0.5h at normal temperature, dropwise adding 180mmol of 30 wt% hydrogen peroxide, controlling the dropwise adding within 1h, heating to 60 ℃ after the dropwise adding, and keeping the temperature to continue the reaction for 2 h. Stopping the reaction, cooling the reaction solution at 0 ℃ for 2 hours, filtering the solid and the catalyst, and washing and drying the catalyst for the next reaction; separating the n-amyl alcohol layer from the filtrate, extracting the water layer with n-amyl alcohol, combining the n-amyl alcohol layers, drying, concentrating under reduced pressure, and separating out white solid, namely the product glyoxylic acid, wherein the yield is 76%, and the purity is 98.7%.

Example 3

100mmol of 40 wt% glyoxal and 0.5g of copper heteropoly acid loaded SBA-15 mesoporous molecular sieve Cu-POM-octyl-NH₃Adding SBA-15 and 200mL of n-amyl alcohol into a reaction bottle, stirring for 0.5h at normal temperature, dropwise adding 180mmol of 30 wt% hydrogen peroxide, controlling the dropwise adding within 1h, heating to 60 ℃ after the dropwise adding, and keeping the temperature to continue reacting for 3 h. Stopping the reaction, cooling the reaction solution at 0 ℃ for 2 hours, filtering the solid and the catalyst, and washing and drying the catalyst for the next reaction; separating the n-amyl alcohol layer from the filtrate, extracting the water layer by using n-amyl alcohol, combining the n-amyl alcohol layers, drying, concentrating under reduced pressure, and separating out white solid, namely the product glyoxylic acid, wherein the yield is 67%, and the purity is 98.9%.

Example 4

100mmol40 wt% glyoxal, 0.4g iron heteropoly acid loaded SBA-15 mesoporous molecular sieve Fe-POM-octyl-NH₃Adding SBA-15 and 200mL of n-butanol into a reaction bottle, stirring for 0.5h at normal temperature, dropwise adding 200mmol of 30 wt% hydrogen peroxide, controlling the dropwise adding within 1h, heating to 50 ℃ after the dropwise adding, and keeping the temperature to continue reacting for 3 h. Stopping the reaction, cooling the reaction solution at 0 ℃ for 2 hours, filtering the solid and the catalyst, and washing and drying the catalyst for the next reaction; separating out n-butanol layer in the filtrate, extracting water layer with n-butanol, mixing n-butanol layers, drying, concentrating under reduced pressure to obtain white solid, i.e. glyoxylic acid product with yield of 70% and purity of 99%.

Example 5

100mmol of 40 wt% glyoxal and 0.5g of Fe-POM-octyl-NH supported SBA-15 mesoporous molecular sieve recovered in the example 1₃Adding SBA-15 and 200mL of n-amyl alcohol into a reaction bottle, stirring for 0.5h at normal temperature, dropwise adding 180mmol of 30 wt% hydrogen peroxide, controlling the dropwise adding within 1h, heating to 60 ℃ after the dropwise adding, and keeping the temperature to continue the reaction for 2 h. Stopping the reaction, cooling the reaction solution at 0 ℃ for 2 hours, filtering the solid and the catalyst, and washing and drying the catalyst for the next reaction; separating the n-amyl alcohol layer from the filtrate, extracting the water layer with n-amyl alcohol, combining the n-amyl alcohol layers, drying, concentrating under reduced pressure, and separating out white solid, namely the product glyoxylic acid, wherein the yield is 81.5 percent, and the purity is 99 percent.

Claims

1. A method for preparing glyoxylic acid, characterized in that the reaction formula of the preparation method is as follows:

the method comprises the following steps: adding glyoxal, a certain amount of catalyst and a solvent into a reaction bottle, stirring at normal temperature for 0.5h, then dropwise adding 30 wt% hydrogen peroxide, and after dropwise adding, keeping a certain reaction temperature and continuing to react for a period of time. After the reaction is finished, cooling, and filtering, washing and drying the catalyst for the next reaction; separating and concentrating the filtrate to separate out the product glyoxylic acid;

the catalyst in the step is a metal heteropoly acid loaded SBA-15 mesoporous molecular sieve which catalyzesThe general formula of the agent is: M-POM-octyl-NH₃-SBA-15, wherein M is iron, copper, cobalt; POM is heteropoly acid, and the structure of M-POM is PW₁₁MO₄₀ ^n-(ii) a -octyl is n-octyltrimethoxysilane; SBA-15 is a mesoporous silica molecular sieve.

2. The method for preparing glyoxylic acid according to claim 1, wherein: the pore diameter of the metal heteropoly acid loaded SBA-15 mesoporous molecular sieve catalyst is 4.5-6.5nm, and the ratio of the mass of the catalyst to the amount of a raw material glyoxal substance is 2-5 g: 1 mol.

3. The method for preparing glyoxylic acid according to claim 1, wherein: the reaction temperature in the step is 40-60 ℃.

4. The method for preparing glyoxylic acid according to claim 1, wherein: the solvent in the step is one or a mixture of several of n-amyl alcohol, n-butyl alcohol, isopropanol, ethanol and tetrahydrofuran.