CN115894194A

CN115894194A - Method for preparing glutaraldehyde by taking cyclopentane epoxide as raw material

Info

Publication number: CN115894194A
Application number: CN202111108160.4A
Authority: CN
Inventors: 秦技强; 黄勇; 常慧; 叶军明; 曹强; 陆鑫; 瞿卫国
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Petrochemical Co Ltd
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Petrochemical Co Ltd
Priority date: 2021-09-22
Filing date: 2021-09-22
Publication date: 2023-04-04

Abstract

The invention relates to a method for preparing glutaraldehyde by taking cyclopentane epoxide as a raw material. The method comprises the following steps: 1) Mixing raw materials of cyclopentane epoxide, a solvent, a catalyst and cumyl peroxide, and then feeding the mixture into a first oxidation reactor for oxidation reaction; 2) Mixing the obtained material, hydrogen peroxide and a catalyst, and then carrying out a second oxidation reactor for reaction; 3) Introducing steam into the material, and purifying the glutaraldehyde by normal pressure steam distillation; 4) Concentrating the obtained material, and removing part of water to obtain 50% glutaraldehyde product. The method of the invention takes the cyclopentane epoxide as the raw material, adopts a proper high boiling point solvent and a segmented experiment to control the reaction process, not only improves the selectivity of the reaction, but also reduces the rectification recovery process of the solvent, and effectively reduces the energy consumption and the equipment investment; under mild conditions, the selectivity of the glutaraldehyde exceeds 80%, and the glutaraldehyde product is obtained by a proper refining method.

Description

Method for preparing glutaraldehyde by taking cyclopentane epoxide as raw material

Technical Field

The invention belongs to the technical field of preparing glutaraldehyde by solid-liquid catalysis, and particularly relates to a heterogeneous catalysis process technology for preparing glutaraldehyde by taking cyclopentane epoxide as a raw material.

Background

Glutaraldehyde (GA for short) is an important fine chemical product and intermediate, and has the functions of crosslinking and solidifying protein. Can be used as high-efficiency low-toxicity sterilization disinfectant, excellent leather tanning agent, color kinescope film hardener, organic synthesis agent and the like, and is widely applied to the fields of biomedical engineering, cellular immunology, biochemistry, leather chemistry, histochemistry, microbial industry, environmental protection and the like. Currently, the main synthesis methods of glutaraldehyde include a pyridine method, an acrolein method, a polyol oxidation method, a glutaric acid reduction method, a cyclopentene oxidation method, and the like. The pyridine method is used for industrial production at first, but is eliminated due to large consumption of raw materials, high cost, large pollution and poor product quality. Although the reaction route of the pentanediol oxidation method is short, the oxidation depth is not easy to control, the yield is low, the raw materials are in short supply, the production cost is high, and the possibility of realizing industrialization is not high. Therefore, in the prior art, the heterogeneous catalytic oxidation method has the advantages of abundant raw materials, easily realized reaction conditions and the like.

For the heterogeneous catalytic oxidation method, the current research focuses on the preparation of a tungsten-containing catalyst by using cyclopentene as a raw material, for example, as described in CN1425498, tiO2 microspheres prepared by closed crystallization are used as a carrier, and the yield of glutaraldehyde is 69.4% at most; CN107652170A discloses a technology that [ C6H5CH2N (CH 3) 2 (CH 2) 3SO3H ] Ti0.5PW4O16 is adopted as a catalyst and acetone is adopted as a solvent to react for 3H under the condition that the temperature is 35 ℃, and the yield of glutaraldehyde is 70 percent. But the defects are that the reaction is generally carried out under the condition of being lower than the boiling point (45 ℃), the reaction time is long, the industrial production is not facilitated, the selectivity of the target product is relatively low, and the average yield of the glutaraldehyde is generally below 70%; in addition, as the glutaraldehyde is active in chemical property and easy to polymerize, the boiling point of main byproducts of 1, 2-cyclopentanediol, epoxy compounds, glutaric acid and the like for preparing the glutaraldehyde by oxidation is higher than that of the glutaraldehyde, the separation process needs higher temperature, and the concentration of the glutaraldehyde is increased after the solvent is recovered, so that the reaction is easy to occur, the separation difficulty is greatly increased, and the glutaraldehyde product suitable for medical use is difficult to prepare by the existing process.

In summary, the existing production technologies of glutaraldehyde all have various defects, another production raw material of glutaraldehyde, 1, 2-epoxycyclopentane, is easily available, as disclosed in patents CN103554059B, CN201410429150.4, etc., cyclopentene is used as a raw material, the conversion rate generally reaches more than 90% under a mild condition, and the selectivity of epoxy products can reach more than 99% at most.

Disclosure of Invention

The invention provides a method for preparing glutaraldehyde by taking cyclopentane epoxide as a raw material. The preparation method of the invention takes the supported heteropoly acid as the catalyst, adopts a method combining step-by-step oxidation and reactive distillation, strengthens the control of the reaction, and improves the selectivity of the reaction on the premise of ensuring good conversion rate so as to make up for the defects in the prior art.

The following is a specific technical scheme of the invention:

the invention provides a method for preparing glutaraldehyde by taking cyclopentane epoxide as a raw material, which comprises the following steps:

1) Mixing raw materials of cyclopentane epoxide, a solvent, a catalyst and cumyl peroxide, and then feeding the mixture into a first oxidation reactor for oxidation reaction; wherein the dosage of the catalyst is 2.0-8.0 wt% of the epoxy cyclopentane, the reaction temperature is 40-55 ℃, the mass ratio of the epoxy cyclopentane to the cumyl peroxide is 1: 0.5-1.5, the mass ratio of the epoxy cyclopentane to the solvent is 1: 2-10, and the reaction time is 3-10 hours;

2) Mixing the material obtained in the step 1), hydrogen peroxide and a catalyst, and then carrying out a second oxidation reactor for reaction; wherein, the dosage of the catalyst is 2.0 to 8.0 weight percent of the cyclopentane epoxide, the reaction temperature is 35 to 45 ℃, the mass ratio of the materials to the hydrogen peroxide is (5 to 10) to 1, and the reaction time is 4 to 12 hours;

3) Introducing water vapor into the material obtained in the step 2), purifying the glutaraldehyde by adopting normal-pressure steam distillation, carrying out entrainment on the glutaraldehyde by the water vapor, wherein the reaction pressure is normal pressure, the temperature of a tower kettle is 100-110 ℃, the mass ratio of the water vapor to the material is (2-10) to 1, and the rest material is circulated to the first oxidation reactor for continuous use;

4) Concentrating the material obtained in the step 3), and removing part of water to obtain a 50% glutaraldehyde product.

Further, the solvent in step 1) is a high-boiling alcohol solvent, such as ethylene glycol, 1, 3-propylene glycol, and the like.

Furthermore, the dosage of the catalyst in the step 1) is preferably 3.0-6.0 wt% of the weight of the cyclopentane epoxide, the reaction temperature is preferably 45-51 ℃, the mass ratio of the cyclopentane epoxide to the hydrogen peroxide is preferably 1 to (0.7-1.3), the mass ratio of the cyclopentane epoxide to the solvent is preferably 1 to (4-8), and the reaction time is preferably 5-8 hours.

Further, the catalyst in the step 1) is M (II)/M (III) -WO prepared by an ion exchange method ₄ ^2- LDH hydrotalcite solid catalyst, wherein M (II) is Mg ²⁺ Or Cu ²⁺ M (III) is Fe ³⁺ 、Cr ³⁺ Or Al ³⁺ M (II)/M (III) molar ratio is 1, and tungsten loading is 20-25%.

Furthermore, the dosage of the catalyst in the step 2) is preferably 3.0-6.0 wt% of the weight of the cyclopentane epoxide, the reaction temperature is preferably 38-42 ℃, the feeding mass ratio of the materials to the hydrogen peroxide is preferably (6-8): 1, and the reaction time is preferably 6-9 hours.

Further, the catalyst in the step 2) is M (II)/M (III) -WO prepared by an ion exchange method ₄ ^2- LDH hydrotalcite solid catalyst, wherein M (II) is Mg ²⁺ Or Cu ²⁺ M (III) is Fe ³⁺ 、Cr ³⁺ Or Al ³⁺ M (II)/M (III) molar ratio of 110-15%;

further, the mass concentration of hydrogen peroxide in the step 2) is 50wt%.

Further, the temperature of the tower kettle in the step 3) is preferably 103-106 ℃, and the mass ratio of the water vapor to the material is preferably (3-6) to 1.

The inventor discovers through a great deal of experimental researches that the oxidation reaction is influenced by the interaction of peroxytungstic acid and cyclopentane epoxide and the intermediate process of the series reaction, especially the concentration of hydrogen peroxide on the surface of the catalyst has obvious influence on the reaction process and the yield of glutaraldehyde, and adopts a proper preparation process route of glutaraldehyde on the basis.

The invention has the beneficial effects that:

1) The cyclopentane epoxide is used as a raw material, so that the reaction temperature can be properly increased, and the reaction time can be effectively shortened;

2) Cumene peroxide is used as an oxidant in the initial stage, so that the side reaction of generating 1, 2-cyclopentanediol by hydrolysis can be reduced, and glutaraldehyde is carried out as a reaction product in time in the second stage, so that deep oxidation to glutaric acid is avoided, and the selectivity is obviously improved.

3) By adopting a segmental experiment, catalysts with different acid strengths are used, and the addition of hydrogen peroxide and the concentration of hydrogen peroxide on the surface of the catalyst are adjusted, so that the reaction process is controlled, and the aim of improving the selectivity can be fulfilled.

4) The solvent with high boiling point is adopted, the rectification recovery process of the solvent is reduced, the energy consumption and the equipment investment are effectively reduced, the benefit is increased, and the self-polymerization caused by overhigh concentration of the glutaraldehyde due to solvent removal in the rectification process is prevented.

Drawings

FIG. 1 is a process flow diagram of the present invention.

Detailed Description

The preparation method of glutaraldehyde according to the present invention is described in further detail below with reference to the accompanying drawings and specific examples. It should be noted that technical features or combinations of technical features described in the following embodiments should not be considered in isolation, and they may be combined with each other to achieve better technical effects.

[ examples 1 to 10 ]

The process flow of the examples 1 to 10 is shown in figure 1, the raw material W1 and the solvent and the like are sequentially reacted in two oxidation reactors and are subjected to steam stripping and simple rectification in a stripping tower to obtain a glutaraldehyde product W2, and the rest material is circulated to the first oxidation reactor for continuous use, wherein different catalysts and oxidants are added into each reactor according to a certain proportion.

The specific preparation process is as follows:

1) Mixing raw materials of cyclopentane epoxide, a solvent, a catalyst and cumyl peroxide, and then feeding the mixture into a first oxidation reactor for oxidation reaction;

2) Mixing the material obtained in the step 1), hydrogen peroxide and a catalyst, and then carrying out a second oxidation reactor for reaction;

3) Introducing water vapor into the material obtained in the step 2), purifying the glutaraldehyde by adopting normal-pressure steam distillation, carrying out entrainment on the glutaraldehyde by the water vapor, wherein the reaction pressure is normal pressure, and circulating the rest material to the first oxidation reactor for continuous use;

The raw material W1 is high-purity cyclopentane epoxide, the process conditions of the first oxidation reactor, the second oxidation reactor and the stripping tower in each example are shown in tables 1,2 and 3 respectively, the composition of the product is analyzed by gas chromatography after the reaction is finished, and the selectivity and yield of glutaraldehyde are shown in table 4. The yield and selectivity of glutaraldehyde are defined as:

TABLE 1 reaction conditions in the first oxidation reactor of the examples

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TABLE 2 reaction conditions in the second oxidation reactor of each example

TABLE 3 reaction conditions in the stripping column of the examples

TABLE 4 glutaraldehyde yields and selectivities obtained in the examples

	Total yield of glutaraldehyde (%)	Glutaraldehyde selectivity (%)
			Example 1	79.7	80.8
Example 2	81.5	82.9
			Example 3	82.0	84.7
Example 4	82.5	84.0
			Example 5	83.6	85.1
Example 6	84.1	86.2
			Example 7	86.0	88.3
Example 8	84.8	86.5
			Example 9	81.6	83.3
Example 10	79.9	81.9

The preparation method of the invention takes the cyclopentane epoxide as the raw material, adopts a proper high boiling point solvent and a segmented experiment to control the reaction process, not only improves the selectivity of the reaction, but also reduces the rectification recovery process of the solvent, and effectively reduces the energy consumption and the equipment investment; under mild conditions, the selectivity of the glutaraldehyde exceeds 80%, and the glutaraldehyde product is obtained by a proper refining method.

While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full scope of the invention.

Claims

1. A method for preparing glutaraldehyde by taking cyclopentane epoxide as a raw material comprises the following steps:

3) Introducing steam into the material obtained in the step 2), purifying glutaraldehyde by adopting normal-pressure steam distillation, carrying out entrainment on the glutaraldehyde by the steam, wherein the reaction pressure is normal pressure, the temperature of a tower kettle is 100-110 ℃, the mass ratio of the steam to the material is (2-10) to 1, and the rest material is circulated to the first oxidation reactor for continuous use;

2. The method of claim 1, wherein: the solvent in the step 1) is ethylene glycol or 1, 3-propylene glycol.

3. The method of claim 1, wherein: the amount of the catalyst in the step 1) is 3.0-6.0 wt% of the weight of the epoxy cyclopentane, the reaction temperature is 45-51 ℃, the mass ratio of the epoxy cyclopentane to the hydrogen peroxide is 1: 0.7-1.3, the mass ratio of the epoxy cyclopentane to the solvent is 1: 4-8, and the reaction time is 5-8 hours.

4. A method according to claim 1 or 3, characterized in that: the catalyst in the step 1) is M (II)/M (III) -WO prepared by an ion exchange method ₄ ^2— LDH hydrotalcite solid catalyst, wherein M (II) is Mg ²⁺ Or Cu ²⁺ M (III) is Fe ³⁺ 、Cr ³ ⁺ Or Al ³⁺ The molar ratio of M (II)/M (III) is 1.

5. The method of claim 1, wherein: the dosage of the catalyst in the step 2) is 3.0 to 6.0 weight percent of the cyclopentane epoxide, the reaction temperature is 38 to 42 ℃, the mass ratio of the materials to the hydrogen peroxide is (6 to 8) to 1, and the reaction time is 6 to 9 hours.

6. The method according to claim 1 or 5, characterized in that: the catalyst in the step 2) is M (II)/M (III) -WO prepared by an ion exchange method ₄ ^2— LDH hydrotalcite solid catalyst, wherein M (II) is Mg ²⁺ Or Cu ²⁺ M (III) is Fe ³⁺ 、Cr ³ ⁺ Or Al ³⁺ The molar ratio of M (II)/M (III) is 1, and the tungsten loading is 10-15%.

7. The method of claim 1, wherein: the mass concentration of the hydrogen peroxide in the step 2) is 50wt%.

8. The method of claim 1, wherein: the temperature of the tower kettle in the step 3) is 103-106 ℃, and the mass ratio of the water vapor to the material is (3-6) to 1.