CN115806489A

CN115806489A - Process for preparing 3-acetoxypropionaldehyde

Info

Publication number: CN115806489A
Application number: CN202111076568.8A
Authority: CN
Inventors: 徐向亚; 张明森; 邵芸; 刘红梅; 冯静; 邬娇娇; 刘东兵
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2021-09-14
Filing date: 2021-09-14
Publication date: 2023-03-17

Abstract

The invention relates to a method for preparing 3-acetoxy propionaldehyde. The invention provides a method for preparing 3-acetoxy propionaldehyde, which comprises the step of contacting acrolein and acetic acid in the presence of a polymerization inhibitor and reacting at 0.1-10 MPa. The method of the invention does not need to add combustible gas, can reduce the occurrence of accidents, simultaneously, the adopted raw materials are easy to obtain, and the method does not need catalysts and solvents, overcomes the problems of difficult preparation of the catalysts and high energy consumption of solvent recovery, and can reduce the production cost of the 3-acetoxy propionaldehyde.

Description

Process for preparing 3-acetoxypropionaldehyde

Technical Field

The invention particularly relates to a method for preparing 3-acetoxy propionaldehyde.

Background

The 3-acetoxy propionaldehyde is a compound which is very stable, easy to store and separate and is an ideal raw material for synthesizing the 1, 3-propylene glycol. CN105585435A discloses a method for producing 3-acetoxy propionaldehyde, which takes vinyl acetate, carbon monoxide and hydrogen as raw materials, and performs hydroformylation reaction in the presence of a hydroformylation catalyst to obtain 3-acetoxy propionaldehyde; the hydroformylation catalyst comprises a main catalyst and an accelerant, wherein a carrier in the main catalyst is silicon dioxide of which the surface contains an aluminum coating and is modified by modified metal elements, an active component in the main catalyst adopts a germanium compound, and the accelerant is selected from organic amine or organic phosphorus with a complex structure. The method adopts carbon monoxide and hydrogen which are easy to explode, the synthesis route is complex and has higher cost, and the product is not single and needs to be separated.

Disclosure of Invention

The invention aims to overcome the problems in the prior art and provides a method for preparing 3-acetoxy propionaldehyde, which has a simple synthetic route and is suitable for industrial application.

Because the production technology of acrolein in China is well-developed and the production capacity is large, the inventor tries to prepare the 3-acetoxy propionaldehyde by taking the acrolein as the raw material in the process of preparing the 3-acetoxy propionaldehyde by researching, and unexpectedly finds that the 3-acetoxy propionaldehyde is obtained by taking the acrolein and the acetic acid as the raw materials and reacting under the condition of inert gas with certain pressure, the conversion rate of the acrolein is higher than 80 percent, and the selectivity of the 3-acetoxy propionaldehyde is high.

In order to achieve the above object, the present invention provides a process for producing 3-acetoxypropionaldehyde, which comprises contacting acrolein and acetic acid in the presence of a polymerization inhibitor at 0.1 to 10MPa to react.

The method of the invention does not need to add combustible gas, can reduce the occurrence of accidents, simultaneously, the adopted raw materials are easy to obtain, and catalysts and solvents are not needed, thereby overcoming the problems of difficult preparation of the catalysts and high energy consumption of solvent recovery, and reducing the production cost of the 3-acetoxy propionaldehyde.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In the present invention, the pressures mentioned are gauge pressures.

The invention provides a method for preparing 3-acetoxy propionaldehyde, which comprises the step of contacting acrolein and acetic acid in the presence of a polymerization inhibitor and reacting at 0.1-10 MPa.

According to the invention, in order to increase the conversion of acrolein, the reaction is preferably carried out at 0.3 to 2 MPa.

According to the present invention, the kind of the polymerization inhibitor is not particularly limited, and in order to further increase the conversion rate of acrolein, it is preferable that the polymerization inhibitor includes a phenolic polymerization inhibitor and/or a quinone polymerization inhibitor; more preferably, the phenolic polymerization inhibitor comprises at least one of hydroquinone, 2-t-butylhydroquinone, and 2, 5-di-t-butylhydroquinone; more preferably, the quinone type polymerization inhibitor includes benzoquinone and/or methyl hydroquinone.

According to the invention, the molar ratio of the polymerization inhibitor to acrolein can be selected within a wide range, preferably the molar ratio of the polymerization inhibitor to acrolein is between 0 and 1:1, preferably 0.001 to 0.2:1.

according to the invention, preferably, the molar ratio between acrolein and acetic acid is between 1:1-10; preferably 1:1-5.

According to the invention, the reaction temperature is preferably between 0 ℃ and 200 ℃, preferably between 25 ℃ and 150 ℃.

According to the invention, the reaction time is preferably between 0.1 and 10h, preferably between 1 and 6h.

According to the invention, preferably, the reaction takes place under an inert gas atmosphere; the inert gas includes at least one of nitrogen, helium, and argon.

According to the present invention, preferably, the reaction does not require the addition of solvents and catalysts. In the prior art, a solvent is required to be added for synthesizing the 3-acetoxy propionaldehyde, so that the solvent is required to be separated, recycled and reused, and the energy consumption and the cost in the production process are increased; in the prior art, a catalyst is required to be added for synthesizing the 3-acetoxy propionaldehyde, the technical difficulty of preparing the catalyst is high, and the metal active component is generally expensive, so that the production cost of the 3-acetoxy propionaldehyde is further increased.

According to a particularly preferred embodiment of the present invention, the process for the preparation of 3-acetoxypropionaldehyde comprises the steps of:

(1) Polymerization inhibitor hydroquinone and acrolein are mixed according to the weight ratio of 0.001-0.01:1 to obtain a mixture.

(2) Mixing the mixture of the step (1) and acetic acid according to the ratio of 1:1-2, and then reacting at 100-120 ℃ and 0.3-0.5MPa, wherein the reaction atmosphere is nitrogen atmosphere.

The present invention will be described in detail below by way of examples. In the following examples of the present invention,

the starting materials used in the following examples and comparative examples are commercially available.

Room temperature was about 25 ℃ and atmospheric pressure was about 0.1MPa.

Conversion of acrolein = mole of acrolein participating in the reaction ÷ feed mole of acrolein × 100%.

Selectivity to 3-acetoxypropionaldehyde = moles of 3-acetoxypropionaldehyde in the product ÷ moles of acrolein participating in the reaction × 100%.

The yield of 3-acetoxypropionaldehyde = conversion of acrolein x 3-acetoxypropionaldehyde x 100% selectivity.

Example 1

This example illustrates a process for preparing 3-acetoxypropionaldehyde

(1) Polymerization inhibitor (hydroquinone) and acrolein were mixed according to a ratio of 0.001:1 to obtain a mixture.

(2) In a 100mL autoclave, the mixture of step (1) in which the number of moles of acrolein was 0.18mol and 10.714g of glacial acetic acid (0.18 mol) were charged as starting materials for the reaction, and the autoclave was sealed. The mixture is replaced by nitrogen for three times, the temperature is raised to 150 ℃, the nitrogen pressure is set to 1MPa, and the reaction is started for 4 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, the pressure is reduced to 0.1MPa, the reaction kettle is opened, the composition of a reaction product is analyzed by using gas chromatography, an internal standard method (an internal standard substance is ethyl propionate) is used for quantification, the conversion rate of acrolein is calculated to be 87.1%, and the selectivity of the 3-acetoxy propionaldehyde is calculated to be 100%.

Example 2

This example illustrates a process for preparing 3-acetoxypropionaldehyde

(1) Polymerization inhibitor (hydroquinone) and acrolein were mixed according to a ratio of 0.01:1 to obtain a mixture.

(2) In a 100mL autoclave, the mixture of step (1) in which the number of moles of acrolein was 0.18mol and 10.714g of glacial acetic acid (0.18 mol) were charged as starting materials for the reaction, and the autoclave was sealed. The mixture is replaced by nitrogen for three times, the temperature is increased to 120 ℃, the nitrogen pressure is set to 0.5MPa, and the reaction is started for 4 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, the pressure is reduced to 0.1MPa, the reaction kettle is opened, the composition of a reaction product is analyzed by using gas chromatography, an internal standard method (an internal standard substance is ethyl propionate) is used for quantification, the conversion rate of the acrolein is calculated to be 92.7%, and the selectivity of the 3-acetoxy propionaldehyde is calculated to be 100%.

Example 3

This example illustrates a process for preparing 3-acetoxypropionaldehyde

(1) Polymerization inhibitor (hydroquinone) and acrolein were mixed according to a ratio of 0.1:1 to obtain a mixture.

(2) In a 100mL autoclave, the mixture of step (1) in which the number of moles of acrolein was 0.18mol and 10.714g of glacial acetic acid (0.18 mol) were charged as starting materials for the reaction, and the autoclave was sealed. The mixture is replaced by nitrogen for three times, the temperature is raised to 100 ℃, the nitrogen pressure is set to be 0.3MPa, and the reaction is started for 4 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, the pressure is reduced to 0.1MPa, the reaction kettle is opened, the composition of a reaction product is analyzed by using gas chromatography, an internal standard method (an internal standard substance is ethyl propionate) is used for quantification, the conversion rate of the acrolein is calculated to be 96.5%, and the selectivity of the 3-acetoxy propionaldehyde is calculated to be 100%.

Example 4

This example illustrates a process for preparing 3-acetoxypropionaldehyde

The preparation of 3-acetoxypropionaldehyde was carried out as in example 1, except that the polymerization inhibitor hydroquinone was replaced with nitrobenzene and the conversion of acrolein was calculated to be 90.7% and the selectivity of 3-acetoxypropionaldehyde was calculated to be 38.9%.

Example 5

This example illustrates a process for preparing 3-acetoxypropionaldehyde

The preparation of 3-acetoxypropionaldehyde was carried out as in example 1, except that in step (1), the molar ratio of (hydroquinone) to acrolein was 5:1. the conversion of acrolein was calculated to be 87.0% and the selectivity for 3-acetoxypropionaldehyde was calculated to be 42.6%.

Example 6

This example illustrates a process for preparing 3-acetoxypropionaldehyde

The preparation of 3-acetoxypropionaldehyde was carried out as in example 1, except that the reaction temperature was 50 ℃ and the pressure was 1MPa, and the nitrogen reaction atmosphere was replaced with the air reaction atmosphere. The conversion of acrolein was calculated to be 90.3% and the selectivity for 3-acetoxypropionaldehyde was calculated to be 66.3%.

Comparative example 1

The preparation of 3-acetoxypropionaldehyde is described in the literature (Journal of the Chemical Society Perkin Transaction: organic and biological Chemistry (1972-1999), (8), 2315-2322, 1988).

The method specifically comprises the following steps: using sodium acetate as a catalyst, 56g of acrolein (1 mol), 120g of glacial acetic acid (2 mol) and 8.2g of sodium acetate (0.1 mol) were reacted at room temperature for 16h. The acetic acid was removed by distillation under reduced pressure, the remaining organic was precipitated as a white solid by adding 100mL of diethyl ether, filtered, and the organic phase was distilled under reduced pressure to give 50.2g of 3-acetoxypropionaldehyde as a product, with a yield of 38.6%.

Comparative example 2

The preparation of 3-acetoxypropionaldehyde was carried out by a method reported in the literature (Tetrahedron 67 (2011) 1654-1664).

The method specifically comprises the following steps: using ion exchange resin as catalyst, add acrolein (0.8 mol), glacial acetic acid (0.82 mol), 200mL of IRA-420 ion exchange resin, and react for 48h at room temperature. Ethyl acetate (300 mL) was added, the ion exchange resin was extracted, and saturated NaHCO was used for the organic layer ₃ (200 mL), washed with saturated brine (100 mL) and anhydrous Na ₂ SO ₄ Drying and distillation under reduced pressure gave 15g of the product 3-acetoxypropionaldehyde in 16% yield.

Comparative example 3

This comparative example is for explaining the preparation of 3-acetoxypropionaldehyde

The preparation of 3-acetoxypropionaldehyde was carried out as in example 1, except that no polymerization inhibitor was added, and the nitrogen pressure during the reaction was set to 0.1MPa. The conversion of acrolein was calculated to be 99.7%, and acrolein was polymerized, and the product contained almost no 3-acetoxypropionaldehyde.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A process for preparing 3-acetoxypropionaldehyde, which comprises reacting acrolein and acetic acid in contact at 0.1 to 10MPa in the presence of a polymerization inhibitor.

2. The process according to claim 1, wherein the reaction is carried out at 0.3-2 MPa.

3. A process according to claim 1 or 2, wherein the polymerisation inhibitor comprises a phenolic polymerisation inhibitor and/or a quinone polymerisation inhibitor.

4. The process of claim 3, wherein the phenolic polymerization inhibitor comprises at least one of hydroquinone, 2-t-butylhydroquinone, and 2, 5-di-t-butylhydroquinone;

and/or the quinone polymerization inhibitor comprises benzoquinone and/or methyl hydroquinone.

5. A process according to any one of claims 1 to 4, wherein the molar ratio of inhibitor to acrolein is from 0 to 1:1, preferably 0.001 to 0.2:1.

6. a process according to any one of claims 1 to 5, wherein the molar ratio of acrolein to acetic acid is from 1:1-10; preferably 1:1-5.

7. The process according to any one of claims 1 to 6, wherein the temperature of the reaction is between 0 ℃ and 200 ℃, preferably between 25 ℃ and 150 ℃.

8. The process according to any one of claims 1 to 7, wherein the reaction time is between 0.1 and 10h, preferably between 1 and 6h.

9. The method of any one of claims 1-8, wherein the reaction occurs under an inert gas environment;

preferably, the inert gas includes at least one of nitrogen, helium, and argon.

10. The process of any one of claims 1-9, wherein the reaction does not require the addition of a solvent and a catalyst.