CN111018812B - Process for chlorinating esters and process for separating chloroesters - Google Patents
Process for chlorinating esters and process for separating chloroesters Download PDFInfo
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- CN111018812B CN111018812B CN201911385709.7A CN201911385709A CN111018812B CN 111018812 B CN111018812 B CN 111018812B CN 201911385709 A CN201911385709 A CN 201911385709A CN 111018812 B CN111018812 B CN 111018812B
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention provides a chlorination process of an esterified product and a method for separating chloro-ester, relating to the technical field of chlorination processes of esterified products, wherein the chlorination process of the esterified product comprises the following steps: mixing the ester with water, introducing chlorine, and carrying out chlorination reaction on the ester and the chlorine to obtain chlorine ester, wherein the mass ratio of the chlorine to the water is (10-30): 100; according to the chlorination process of the esterified substance, the mass ratio of the chlorine to the water is set, so that the hydrogen chloride generated by chlorination reaction of the esterified substance is completely absorbed by the water, the consumption of sodium bicarbonate is not needed, the energy is saved, meanwhile, the sodium bicarbonate is not used as a raw material, carbon dioxide is not generated, the chlorine is prevented from being carried by the carbon dioxide and discharged into the atmosphere, and the environmental pressure is reduced.
Description
Technical Field
The invention relates to the technical field of esterification chlorination processes, in particular to a chlorination process of an esterification product and a separation method of chlorine ester.
Background
In the prior art, chlorine is introduced into a reactor provided with alpha-acetyl-gamma-butyrolactone, sodium bicarbonate and water, so that the alpha-acetyl-gamma-butyrolactone is chlorinated, a large amount of sodium bicarbonate is consumed in the preparation process, meanwhile, a large amount of carbon dioxide is also generated in the reaction process of the sodium bicarbonate and a byproduct hydrogen chloride generated by chlorination of the alpha-acetyl-gamma-butyrolactone, and the carbon dioxide carries the chlorine into the atmosphere in the emission process, thereby causing environmental pollution.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
One of the purposes of the invention is to provide a chlorination process of an esterified product, which aims to relieve the technical problems that the existing method for preparing alpha-chloro-alpha-acetyl-gamma-butyrolactone by using alpha-acetyl-gamma-butyrolactone, chlorine, sodium bicarbonate and water as raw materials not only needs to consume a large amount of chlorine and sodium bicarbonate, but also can generate a large amount of carbon dioxide, and the carbon dioxide can carry chlorine into the atmosphere in the discharge process to cause environmental pollution.
The chlorination process of the esterified substance provided by the invention comprises the following steps: and mixing the ester with water, introducing chlorine, and carrying out chlorination reaction on the ester and the chlorine to obtain the chlorine ester, wherein the mass ratio of the chlorine to the water is (10-30):100, preferably (20-30): 100.
Further, the molar ratio of the ester to the chlorine gas is (0.85-0.95): 1, preferably (0.9-0.92): 1.
further, the temperature of the chlorination reaction is 0 to 20 ℃, preferably 5 to 15 ℃.
Further, the esterified compound comprises alpha-acetyl-gamma-butyrolactone.
Further, after the chlorination reaction is finished, a mixture of the chlorine ester and water is obtained, and the chlorine ester and the water are separated to obtain the chlorine ester.
The invention also aims to provide a method for separating the chloro-ester, which comprises the following steps: and (3) carrying out chlorination reaction on the esterified substance, water and chlorine to obtain a mixture of the chlorine ester and the water, and sequentially carrying out standing layering and organic solvent extraction to separate the chlorine ester from the water.
Further, the time for standing and layering is 1.5 to 2.5 hours, preferably 1.8 to 2.2 hours.
Further, the organic solvent includes at least one of ethyl ether, ethanol, acetone, chloroform and dichloromethane, preferably dichloromethane.
Further, the extracted organic solvent is recovered by negative pressure distillation.
Further, the mass ratio of the esterified substance to the organic solvent is (90-100):100, preferably (94-98): 100;
preferably, the esterified substance comprises α -acetyl- γ -butyrolactone.
According to the chlorination process of the esterified substance, the mass ratio of the chlorine to the water is set, so that the hydrogen chloride generated by chlorination reaction of the esterified substance is completely absorbed by the water, the consumption of sodium bicarbonate is not needed, the energy is saved, meanwhile, the sodium bicarbonate is not used as a raw material, carbon dioxide is not generated, the chlorine is prevented from being carried by the carbon dioxide and discharged into the atmosphere, and the environmental pressure is reduced.
The method for separating the chloro-ester provided by the invention has the advantages that the standing and the organic solvent extraction are sequentially carried out, the separation time of the chloro-ester is shortened, the yield of the chloro-ester is improved, the method is suitable for industrial mass production, and the separation cost is reduced.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to one aspect of the invention, the invention provides a chlorination process of an esterified product, which comprises the following steps: mixing the esterified substance with water, introducing chlorine, and carrying out chlorination reaction on the esterified substance and the chlorine to obtain chloro-ester; wherein the mass ratio of the chlorine to the water is (10-30): 100.
In the invention, the esterification and chlorine gas are subjected to chlorination reaction to generate chlorine ester and hydrogen chloride, and the hydrogen chloride is dissolved in water to obtain hydrochloric acid. In addition, the mass ratio of the chlorine to the water is (10-30):100, therefore, the mass concentration of the obtained hydrochloric acid is not higher than 23.1 percent, and the hydrochloric acid is difficult to volatilize under the mass concentration of lower than 23.1 percent, thereby avoiding the environmental pollution caused by the volatilization of the hydrogen chloride, and simultaneously, the water completely dissolves the generated hydrogen chloride, which is also beneficial to the chlorination reaction.
Typically, but not by way of limitation, the mass ratio of chlorine to water is, for example, 10:100, 12:100, 15:100, 18:100, 20:100, 22:100, 25:100, 28:100, or 30: 100.
According to the chlorination process of the esterified substance, the mass ratio of the chlorine to the water is set, so that the hydrogen chloride generated by chlorination reaction of the esterified substance is completely absorbed by the water, the consumption of sodium bicarbonate is not needed, the energy is saved, meanwhile, the sodium bicarbonate is not used as a raw material, carbon dioxide is not generated, the chlorine is prevented from being carried by the carbon dioxide and discharged into the atmosphere, and the environmental pressure is reduced.
In a preferred embodiment of the present invention, the chlorination is carried out such that the mass ratio of chlorine to water is (20-30): 100.
when the mass ratio of the chlorine to the water is lower than 20:100, a large amount of water resources are wasted, and when the mass ratio of the chlorine to the water is higher than 30:100, the mass concentration of the hydrochloric acid obtained after the hydrogen chloride is dissolved in water is increased, so that the hydrogen chloride is easy to volatilize into the air to cause air pollution, therefore, when the mass ratio of the chlorine to the water is (20-30): 100, the chlorination reaction can be ensured without wasting water resources, and environmental pollution caused by volatilization of hydrogen chloride can be avoided.
In a preferred embodiment of the present invention, the chlorination reaction is carried out in such a manner that the molar ratio of the ester to the chlorine gas is (0.85 to 0.95): 1, preferably (0.9-0.92): 1.
typically, but not by way of limitation, the chlorination is carried out such that the molar ratio of ester to chlorine is, for example, 0.85:1, 0.88:1, 0.9:1, 0.91:1 or 0.92: 1.
During the chlorination reaction, the chlorine gas is introduced slightly in excess of the ester to improve the yield of the chloro ester. When the molar ratio of the ester to the chlorine is less than 0.85:1, waste of the chlorine is caused, and when the molar ratio of the ester to the chlorine is more than 0.95:1, incomplete chlorination of the ester is easily caused, resulting in low yield of the chlorine ester.
When the chlorination reaction is carried out, if the molar ratio of the ester to the chlorine is (0.9-0.92):1, the dosage of the chlorine is better, the yield of the chlorine ester can be ensured, and the waste of the chlorine can be avoided.
In a preferred embodiment of the invention, the temperature of the chlorination reaction is between 0 and 20 ℃.
Typically, but not by way of limitation, the temperature of the chlorination reaction is 0 deg.C, 2 deg.C, 5 deg.C, 8 deg.C, 10 deg.C, 12 deg.C, 15 deg.C, 18 deg.C or 20 deg.C.
The temperature of the chlorination reaction is controlled to be 0-20 ℃, so that the chlorination reaction is more favorably carried out, and the phenomenon that hydrochloric acid volatilizes hydrogen chloride to pollute the environment due to overhigh temperature can be avoided.
In a preferred embodiment of the present invention, when the temperature of the chlorination reaction is 5 to 15 ℃, it is more advantageous to accelerate the chlorination reaction and shorten the chlorination time on the basis of ensuring the chlorination reaction.
In a preferred embodiment of the present invention, the ester includes an ester capable of undergoing a chlorination reaction with chlorine gas, including but not limited to substituted or unsubstituted fatty acid esters, such as fatty acid methyl ester, fatty acid ethyl ester or fatty acid butyl ester.
In a further preferred embodiment of the present invention, the esterified compound includes but is not limited to α -acetyl- γ -butyrolactone, and other esterified compounds requiring chlorination with chlorine gas can also be prepared by referring to the technical scheme provided by the present invention.
In a preferred embodiment of the present invention, after completion of the chlorination reaction, a mixture of the chlorinated ester and water is obtained, and the chlorinated ester and water are separated to obtain the chlorinated ester. The water contains hydrogen chloride dissolved therein.
The method for separating the chlorine ester from the water comprises various modes of centrifugation, distillation and extraction. In the industrial production, chlorine ester and water are separated by centrifugation, a large amount of energy is required, and the yield of chlorine ester is low. The chlorine ester and the water are separated by distillation, so that potential safety hazards exist, and because hydrogen chloride is dissolved in the water, the hydrogen chloride overflows in the heating process, so that the environmental pollution is caused. The separation of the chloroester by extraction requires the consumption of a large amount of organic solvent, resulting in energy waste.
According to a second aspect of the present invention, there is provided a process for the separation of a chloroester, comprising the steps of:
and (3) carrying out chlorination reaction on the esterified substance, water and chlorine to obtain a mixture of the chlorine ester and the water, and sequentially carrying out standing layering and organic solvent extraction to separate the chlorine ester from the water.
In the present invention, a mixture of a chlorinated ester and water, in which hydrochloric acid is dissolved.
The traditional mixture of the chlorine ester and the water needs a long time for completely separating the chlorine ester and the water through standing and layering separation, and meanwhile, partial chlorine ester can not be completely recovered at the layering part of the chlorine ester and the water, so that the waste of the chlorine ester is caused.
According to the method for separating the chloro-ester, the chloro-ester and the water are firstly layered by standing for a short time, and then the water is extracted by adopting the organic solvent, so that the chloro-ester in the water is extracted and recovered, the separation time of the chloro-ester is shortened, the yield of the chloro-ester is improved, and the separation cost of the chloro-ester is favorably reduced.
In a preferred embodiment of the invention, the time for the standing to stratify is 1.5 to 2.5 hours, preferably 1.8 to 2.2 hours.
The method has the advantages that the chlorine ester and the water are separated by adopting a mode of combining standing layering with organic solvent extraction, the standing time can be shortened when the standing layering is carried out, the chlorine ester which is not completely separated in the water is recovered by an extraction mode, the method is more convenient and more beneficial to improving the yield of the chlorine ester.
Typically but not limitatively, the standing and layering time is 1.5, 1.8, 2, 2.2 or 2.5 hours, if the standing time is less than 1.5 hours, the chlorine ester contained in the water is too much, and the organic solvent needs to be adopted for multiple extractions, which is not favorable for saving energy and shortening the separation period, and when the standing time exceeds 2.5 hours, the standing time is too long, which is not favorable for shortening the separation period, especially when the standing and layering time is 1.8-2.2 hours, the use of the organic solvent can be reduced on the basis of ensuring the shortening of the separation period, and the energy can be saved.
In a preferred embodiment of the present invention, the organic solvent includes at least one of diethyl ether, ethanol, acetone, chloroform and dichloromethane.
The above-mentioned "at least one" means that the organic solvent may include diethyl ether, ethanol, acetone, chloroform or dichloromethane, or a mixed solution of two or more of diethyl ether, ethanol, acetone, chloroform or dichloromethane.
In a preferred embodiment of the present invention, when the organic solvent is dichloromethane, the extraction of the chloro-ester is more facilitated, and the cost is lower, so that the recovery with low cost is more facilitated.
In a preferred embodiment of the present invention, the extracted organic solvent is recovered by negative pressure distillation, so as to reduce the waste of the organic solvent and avoid environmental pollution.
In a preferred embodiment of the present invention, the mass ratio of the ester to the organic solvent is (90-100): 100, so as to be beneficial to organic solvent extraction, standing and layering of the chlorine ester in the water phase.
Typically, but not limitatively, the mass ratio of the ester to the organic solvent is, for example, 90:100, 91:100, 92:100, 93:100, 94:100, 95:100, 96:100, 97:100, 98:100, 99:100 or 100: 100.
In a preferred embodiment of the present invention, the esterified compound includes but is not limited to α -acetyl- γ -butyrolactone, and other esterified compounds can be chlorinated and then the chlorinated ester can be separated according to the method for separating chlorinated ester provided by the present invention.
In a preferred embodiment of the present invention, the extraction of the chlorinated ester in water with the organic solvent can be performed in multiple steps to further increase the yield of chlorinated ester. Especially, when the extraction is carried out by dividing into three times, the yield of the chloro-ester can be ensured, and the separation period of the chloro-ester can be shortened.
In order to facilitate the understanding of the technical scheme provided by the invention for those skilled in the art, the technical scheme provided by the invention is further explained by combining the examples and the comparative examples.
Example 1
The embodiment provides a preparation process of alpha-chloro-alpha-acetyl-gamma-butyrolactone, which comprises the following steps:
96g of alpha-acetyl-gamma-butyrolactone and 200g of water were placed in a flask, introducing 58.5g of chlorine gas at 15 ℃, standing for 2 hours to obtain a layered solution of alpha-chloro-alpha-acetyl-gamma-butyrolactone and water, wherein hydrogen chloride generated by chlorination is dissolved in water, the alpha-chloro-alpha-acetyl-gamma-butyrolactone is recovered, extracting the upper layer water solution by adopting dichloromethane, wherein the extraction is carried out for three times, the dosage of the dichloromethane extracted each time is 50g, and finally, combining the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by standing separation and the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by extracting dichloromethane, thus obtaining the alpha-chloro-alpha-acetyl-gamma-butyrolactone prepared by the embodiment.
In this example, the mass ratio of chlorine to water was 29.25: 100.
Example 2
The embodiment provides a preparation process of alpha-chloro-alpha-acetyl-gamma-butyrolactone, which comprises the following steps:
96g of alpha-acetyl-gamma-butyrolactone and 585g of water are put into a flask, introducing 58.5g of chlorine gas at the temperature of 20 ℃, standing for 2 hours to obtain a layered solution of alpha-chloro-alpha-acetyl-gamma-butyrolactone and water, wherein hydrogen chloride generated by chlorination is dissolved in water, the alpha-chloro-alpha-acetyl-gamma-butyrolactone is recovered, extracting the upper layer water solution by adopting dichloromethane, wherein the extraction is carried out for three times, the dosage of the dichloromethane extracted each time is 50g, and finally, combining the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by standing separation and the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by extracting dichloromethane, namely, the α -chloro- α -acetyl- γ -butyrolactone prepared in this example was obtained.
In this example, the mass ratio of chlorine to water was 10: 100.
Example 3
The embodiment provides a preparation process of alpha-chloro-alpha-acetyl-gamma-butyrolactone, which comprises the following steps:
96g of alpha-acetyl-gamma-butyrolactone and 300g of water were placed in a flask, introducing 58.5g of chlorine gas at the temperature of 20 ℃, standing for 2 hours to obtain a layered solution of alpha-chloro-alpha-acetyl-gamma-butyrolactone and water, wherein hydrogen chloride generated by chlorination is dissolved in water, the alpha-chloro-alpha-acetyl-gamma-butyrolactone is recovered, extracting the upper layer water solution by adopting dichloromethane, wherein the extraction is carried out for three times, the dosage of the dichloromethane extracted each time is 50g, and finally, combining the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by standing separation and the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by extracting dichloromethane, namely, the α -chloro- α -acetyl- γ -butyrolactone prepared in this example was obtained.
In this example, the mass ratio of chlorine to water was 20: 100.
Example 4
The embodiment provides a preparation process of alpha-chloro-alpha-acetyl-gamma-butyrolactone, which comprises the following steps:
96g of alpha-acetyl-gamma-butyrolactone and 300g of water were placed in a flask, introducing 62.6g of chlorine gas at the temperature of 20 ℃, standing for 2 hours to obtain a layered solution of alpha-chloro-alpha-acetyl-gamma-butyrolactone and water, wherein hydrogen chloride generated by chlorination is dissolved in water, the alpha-chloro-alpha-acetyl-gamma-butyrolactone is recovered, extracting the upper layer water solution by adopting dichloromethane, wherein the extraction is carried out for three times, the dosage of the dichloromethane extracted each time is 50g, and finally, combining the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by standing separation and the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by extracting dichloromethane, namely, the α -chloro- α -acetyl- γ -butyrolactone prepared in this example was obtained.
In this example, the molar ratio of α -acetyl- γ -butyrolactone to chlorine was 0.85: 1.
Example 5
The embodiment provides a preparation process of alpha-chloro-alpha-acetyl-gamma-butyrolactone, which comprises the following steps:
96g of alpha-acetyl-gamma-butyrolactone and 300g of water were placed in a flask, introducing 56.1g of chlorine gas at the temperature of 20 ℃, standing for 2 hours to obtain a layered solution of alpha-chloro-alpha-acetyl-gamma-butyrolactone and water, wherein hydrogen chloride generated by chlorination is dissolved in water, the alpha-chloro-alpha-acetyl-gamma-butyrolactone is recovered, extracting the upper layer water solution by adopting dichloromethane, wherein the extraction is carried out for three times, the dosage of the dichloromethane extracted each time is 50g, and finally, combining the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by standing separation and the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by extracting dichloromethane, namely, the α -chloro- α -acetyl- γ -butyrolactone prepared in this example was obtained.
In this example, the molar ratio of α -acetyl- γ -butyrolactone to chlorine was 0.95: 1.
Example 6
The embodiment provides a preparation process of alpha-chloro-alpha-acetyl-gamma-butyrolactone, which comprises the following steps:
96g of alpha-acetyl-gamma-butyrolactone and 300g of water were placed in a flask, introducing 59.2g of chlorine gas at the temperature of 20 ℃, standing for 2 hours to obtain a layered solution of alpha-chloro-alpha-acetyl-gamma-butyrolactone and water, wherein hydrogen chloride generated by chlorination is dissolved in water, the alpha-chloro-alpha-acetyl-gamma-butyrolactone is recovered, extracting the upper layer water solution by adopting dichloromethane, wherein the extraction is carried out for three times, the dosage of the dichloromethane extracted each time is 50g, and finally, combining the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by standing separation and the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by extracting dichloromethane, namely, the α -chloro- α -acetyl- γ -butyrolactone prepared in this example was obtained.
In this example, the molar ratio of α -acetyl- γ -butyrolactone to chlorine was 0.9: 1.
Example 7
The embodiment provides a preparation process of alpha-chloro-alpha-acetyl-gamma-butyrolactone, which comprises the following steps:
96g of alpha-acetyl-gamma-butyrolactone and 300g of water were placed in a flask, introducing 57.8g of chlorine gas at the temperature of 20 ℃, standing for 2 hours to obtain a layered solution of alpha-chloro-alpha-acetyl-gamma-butyrolactone and water, wherein hydrogen chloride generated by chlorination is dissolved in water, the alpha-chloro-alpha-acetyl-gamma-butyrolactone is recovered, extracting the upper layer water solution by adopting dichloromethane, wherein the extraction is carried out for three times, the dosage of the dichloromethane extracted each time is 50g, and finally, combining the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by standing separation and the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by extracting dichloromethane, namely, the α -chloro- α -acetyl- γ -butyrolactone prepared in this example was obtained.
In this example, the molar ratio of α -acetyl- γ -butyrolactone to chlorine was 0.92: 1.
Example 8
This example is different from example 1 in that the chlorination reaction is carried out at a temperature of 5 deg.C, and the rest of the steps are the same as example 1, and are not described herein again.
Example 9
This example is different from example 1 in that the chlorination reaction is carried out at a temperature of 0 ℃, and the rest of the steps are the same as example 1, and are not described again.
Example 10
This example is different from example 1 in that the chlorination reaction is carried out at a temperature of 10 ℃, and the rest of the steps are the same as example 1, and are not described again.
Example 11
This example is different from example 1 in that after the completion of the chlorination reaction, the reaction mixture was left to stand for 5 hours to completely separate α -chloro- α -acetyl- γ -butyrolactone from water, and then α -chloro- α -acetyl- γ -butyrolactone was directly recovered.
Comparative example 1
The comparative example provides a process for the preparation of α -chloro- α -acetyl- γ -butyrolactone, comprising the steps of:
96g of alpha-acetyl-gamma-butyrolactone, 126g of water and 62.5 g of sodium bicarbonate are placed in a flask, 58.5g of chlorine gas is introduced at 20 ℃, then the flask is kept stand for 5 hours, so that the alpha-chloro-alpha-acetyl-gamma-butyrolactone and water are completely separated, and then the alpha-chloro-alpha-acetyl-gamma-butyrolactone is directly recovered.
Comparative example 2
The comparative example provides a process for the preparation of α -chloro- α -acetyl- γ -butyrolactone, comprising the steps of:
Putting 96g of alpha-acetyl-gamma-butyrolactone, 126g of water and 62.5 g of sodium bicarbonate into a flask, introducing 58.5g of chlorine at 20 ℃, standing for 2 hours to obtain a layered solution of the alpha-chloro-alpha-acetyl-gamma-butyrolactone and water, wherein the water is dissolved with hydrogen chloride generated by chlorination, recovering the alpha-chloro-alpha-acetyl-gamma-butyrolactone, extracting the upper aqueous solution with dichloromethane for three times, wherein the amount of the dichloromethane extracted each time is 50g, and finally combining the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by standing separation and the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained by dichloromethane extraction to obtain the alpha-chloro-alpha-acetyl-gamma-butyrolactone prepared in the embodiment And (3) an ester.
Test example 1
The total yields of α -chloro- α -acetyl- γ -butyrolactone obtained in examples 1 to 11 and comparative examples 1 to 2 were measured, respectively, in which each example and comparative example was performed three times, and the results are shown in table 1 below, taking the average of the three total yields.
TABLE 1 data table of the yield of α -chloro- α -acetyl- γ -butyrolactone
| Total yield (%) | |
| Example 1 | 99.57 |
| Example 2 | 99.23 |
| Example 3 | 99.43 |
| Example 4 | 99.60 |
| Example 5 | 99.46 |
| Example 6 | 99.59 |
| Example 7 | 99.51 |
| Example 8 | 99.62 |
| Example 9 | 99.61 |
| Example 10 | 99.63 |
| Example 11 | 99.05 |
| Comparative example 1 | 97.12 |
| Comparative example 2 | 99.73 |
As can be seen by comparing examples 1-10 with comparative example 2, the total yield of the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained in examples 1-10 and the total yield of the alpha-chloro-alpha-acetyl-gamma-butyrolactone obtained in comparative example 2 have no obvious difference, which indicates that the hydrogen chloride generated by the chlorination reaction of the alpha-acetyl-gamma-butyrolactone is completely absorbed by water by setting the mass ratio of chlorine to water in examples 1-10, the consumption of sodium bicarbonate is not needed, the energy is saved, the yield of the alpha-chloro-alpha-acetyl-gamma-butyrolactone is not obviously influenced, and the chlorine carried by carbon dioxide is prevented from entering the atmosphere, and the environmental pollution is reduced.
As can be seen by comparing examples 1-10 with example 11, the yields of α -chloro- α -acetyl- γ -butyrolactone obtained in examples 1-10 are slightly higher than the total yield of α -chloro- α -acetyl- γ -butyrolactone obtained in example 1, which demonstrates that recovery of α -chloro- α -acetyl- γ -butyrolactone by a combination of standing and extraction both shortens the separation time of chloro ester and increases the yield of chloro ester.
As can be seen from comparison of examples 1-10 with comparative example 1, the yield of the α -chloro- α -acetyl- γ -butyrolactone obtained in examples 1-10 is higher than the total yield of the α -chloro- α -acetyl- γ -butyrolactone obtained in comparative example 1, which shows that the chlorination reaction is performed by setting the mass ratio of chlorine to water, and the α -chloro- α -acetyl- γ -butyrolactone is recovered by a combination of standing and extraction, not only can the yield of the chlorine ester be increased, but also the separation time of the chlorine ester can be shortened, and simultaneously, sodium bicarbonate is not consumed, and environmental pollution caused by the fact that carbon dioxide carries chlorine into the atmosphere is avoided.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A chlorination process of an esterified product is characterized by comprising the following steps: mixing the esterified substance with water, introducing chlorine, carrying out chlorination reaction on the esterified substance and the chlorine to obtain a mixture of chlorine ester and water after the chlorination reaction is finished, and separating the chlorine ester from the water to obtain the chlorine ester;
wherein the mass ratio of chlorine to water is (20-30) to 100;
the molar ratio of the esterified substance to the chlorine gas is (0.9-0.92) to 1;
the temperature of chlorination reaction is 5-15 ℃;
the esterified product is alpha-acetyl-gamma-butyrolactone.
2. The process for chlorinating the ester according to claim 1, wherein the mixture of chlorine ester and water is subjected to standing layering and organic solvent extraction in sequence to separate chlorine ester and water.
3. The process for chlorinating the ester according to claim 2, wherein the time for standing and layering is 1.5 to 2.5 hours.
4. The process for chlorinating the ester according to claim 2, wherein the time for standing and layering is 1.8 to 2.2 hours.
5. The process for chlorinating the ester according to claim 2, wherein the organic solvent comprises at least one of ethyl ether, ethanol, acetone, chloroform and dichloromethane.
6. The process for chlorinating the ester according to claim 2, wherein the organic solvent is dichloromethane.
7. The process for chlorinating the ester according to claim 2, wherein the extracted organic solvent is recovered by negative pressure distillation.
8. The process for chlorinating the esterified product according to any one of claims 2 to 7, wherein the mass ratio of the esterified product to the organic solvent is (90-100): 100.
9. The chlorination process of an esterified substance according to claim 8, wherein the mass ratio of the esterified substance to the organic solvent is (94-98): 100.
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