CN109721488B - Low-temperature synthesis method of isovaleryl chloride - Google Patents
Low-temperature synthesis method of isovaleryl chloride Download PDFInfo
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Abstract
The invention discloses a low-temperature synthesis method of isovaleryl chloride, which takes isovaleric acid as a main raw material, adds a chlorinating agent into the isovaleric acid, and then synthesizes the isovaleryl chloride under the action of a catalyst and at a low reaction temperature. The invention has the advantages that: the synthesis process is completed under the low temperature condition, so that the energy consumption required in the generation process of the target product can be reduced; the generated tail gas is frozen, and the byproduct hydrochloric acid of the malodorous gas is condensed into liquid state, so that the volatilization and entrainment of the malodorous gas in the tail gas can be reduced; the generated tail gas is frozen, so that the entrainment of the isovaleryl chloride in the tail gas can be reduced, and the product yield of the isovaleryl chloride is further improved.
Description
Technical Field
The invention relates to the field of industrial production, in particular to a low-temperature synthesis method of isovaleryl chloride.
Background
The basic process route for industrially producing the isovaleryl chloride at present is to use isovaleric acid as a raw material and phosphorus pentachloride, thionyl chloride and the like as chlorinating agents to perform heating reflux reaction to prepare the isovaleryl chloride. The process route has high reaction temperature and large energy consumption, and a large amount of byproduct hydrochloric acid with foul smell can be generated after tail gas is absorbed by water.
Disclosure of Invention
In order to solve the technical field, the invention provides a low-temperature synthesis method of isovaleryl chloride, which is used for carrying out reaction under a low-temperature condition, and freezing and cooling tail gas, so that the entrainment of the isovaleryl chloride in the tail gas can be reduced, and the odor of byproduct hydrochloric acid can be reduced.
The technical scheme adopted by the invention is as follows:
a low-temperature synthesis method of isovaleryl chloride takes isovaleric acid as a main raw material, adds a chlorinating agent into the isovaleric acid, and then synthesizes the isovaleryl chloride under the action of a catalyst and under the condition of low reaction temperature.
Further, the chlorinating agent is thionyl chloride, titanium tetrachloride, phosphorus trichloride, phosphorus oxychloride, phosgene or triphosgene.
Further, the chlorinating agent is preferably thionyl chloride.
Further, the catalyst is N, N-dimethylformamide, dimethylacetamide, pyridine, 4-dimethylaminopyridine or triethylene diamine.
Further, the catalyst is preferably N, N-dimethylformamide.
Further, the weight ratio of the isovaleric acid, the catalyst and the chlorinating agent is in the range of 1: 0.002-0.003: 1.23-1.24.
Further, the low reaction temperature is 0-5 ℃.
Further, the method comprises the following operation steps:
a. dropwise addition of thionyl chloride: firstly, putting a certain amount of isovaleric acid and a catalyst into a reaction kettle, controlling the temperature in the reaction kettle to be 0-5 ℃, dropwise adding thionyl chloride, then starting a tail gas absorption device, simultaneously starting brine ice in a tail gas condenser, and controlling the gas phase temperature to be below 0 ℃ until the dropwise adding of the thionyl chloride is finished;
b. generation of the target product: after the dropwise addition of the thionyl chloride in the step a is finished, controlling the temperature in the reaction kettle to be 5-10 ℃, maintaining the temperature for 3.5-4.5h, then adjusting the temperature in the reaction kettle to be 10-20 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 20-30 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 30-40 ℃, maintaining the temperature for 3.5-4.5h, finally adjusting the temperature in the reaction kettle to be 40-50 ℃, maintaining the temperature for 1.5-2.5h, and obtaining an isovaleryl chloride material after the reaction is finished;
c. and (3) rectification of a target product: and c, transferring the isovaleryl chloride material obtained by the reaction in the step b into a rectifying still for normal pressure rectification, rectifying recyclable front-end distillate, finishing rectification when the content of the isovaleryl chloride in the residual distillate in the rectifying still meets the requirement of a finished product, namely more than or equal to 99%, collecting the finished product and packaging.
Further, the tail gas absorption device comprises a third-stage absorption device, and water is filled in the third-stage absorption device.
Further, the components in the front-end fraction comprise isovaleryl chloride, isovaleric acid, thionyl chloride, HCl and SO2。
The invention has the beneficial effects that: 1. the synthesis process is completed under the low temperature condition, so that the energy consumption required in the generation process of the target product can be reduced; 2. the generated tail gas is frozen, and the byproduct hydrochloric acid of the malodorous gas is condensed into liquid state, so that the volatilization and entrainment of the malodorous gas in the tail gas can be reduced; 3. the generated tail gas is frozen, so that the entrainment of the isovaleryl chloride in the tail gas can be reduced, and the product yield of the isovaleryl chloride is further improved.
Detailed Description
For the purpose of enhancing the understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
A low-temperature synthesis method of isovaleryl chloride comprises the following specific operation steps of taking isovaleric acid as a main raw material, adding a chlorinating agent into the isovaleric acid, and synthesizing the isovaleryl chloride under the action of a catalyst and at a low reaction temperature:
example 1
a. Dropwise addition of thionyl chloride: firstly, adding 1020Kg of isovaleric acid and 3Kg of catalyst N, N-dimethylformamide into a reaction kettle, controlling the temperature in the reaction kettle at 0-5 ℃, dropwise adding 1260Kg of thionyl chloride, then starting a tail gas absorption device, wherein the tail gas absorption device comprises a three-stage absorption device, the three-stage absorption device is filled with water, simultaneously starting brine ice in a tail gas condenser, controlling the gas phase temperature below 0 ℃, and finishing the dropwise adding of the thionyl chloride after 4-5 hours;
b. generation of the target product: after the dropwise addition of the thionyl chloride in the step a is finished, controlling the temperature in the reaction kettle to be 5-10 ℃, maintaining the temperature for 3.5-4.5h, then adjusting the temperature in the reaction kettle to be 10-20 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 20-30 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 30-40 ℃, maintaining the temperature for 3.5-4.5h, finally adjusting the temperature in the reaction kettle to be 40-50 ℃, maintaining the temperature for 1.5-2.5h, and obtaining an isovaleryl chloride material after the reaction is finished;
c. and (3) rectification of a target product: b, transferring the isovaleryl chloride material obtained by the reaction in the step b into a rectifying still for normal pressure rectification, and rectifying to obtain a front cut fraction of 367.3Kg, wherein the front cut fraction comprises isovaleryl chloride, isovaleric acid, thionyl chloride, HCl and SO2The method can be recycled, when the content of the isovaleryl chloride in the residual fraction in the rectifying still meets the requirement of a finished product, namely is more than or equal to 99 percent, the rectification is finished, the finished product is collected and packaged, 1109.1Kg of finished product is obtained, the content is 99.5 percent, and the yield is 92.0 percent.
Example 2
a. Dropwise addition of thionyl chloride: firstly, adding 1020Kg of isovaleric acid and 2.1Kg of catalyst N, N-dimethylformamide into a reaction kettle, controlling the temperature in the reaction kettle at 0-5 ℃, dropwise adding 1255Kg of thionyl chloride, then starting a tail gas absorption device, wherein the tail gas absorption device comprises three-stage absorption devices, the three-stage absorption devices are filled with water, simultaneously starting brine ice in a tail gas condenser, controlling the gas phase temperature below 0 ℃, and finishing the dropwise adding of the thionyl chloride after 4-5 hours;
b. generation of the target product: after the dropwise addition of the thionyl chloride in the step a is finished, controlling the temperature in the reaction kettle to be 5-10 ℃, maintaining the temperature for 3.5-4.5h, then adjusting the temperature in the reaction kettle to be 10-20 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 20-30 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 30-40 ℃, maintaining the temperature for 3.5-4.5h, finally adjusting the temperature in the reaction kettle to be 40-50 ℃, maintaining the temperature for 1.5-2.5h, and obtaining an isovaleryl chloride material after the reaction is finished;
c. and (3) rectification of a target product: b, transferring the isovaleryl chloride material obtained by the reaction in the step b into a rectifying still for normal pressure rectification, and rectifying to obtain a front cut of 365.2Kg, wherein the front cut comprises the components of isovaleryl chloride, isovaleric acid, thionyl chloride, HCl and SO2The method can be recycled, when the content of the isovaleryl chloride in the residual fraction in the rectifying still meets the requirement of a finished product, namely is more than or equal to 99 percent, the rectification is finished, the finished product is collected and packaged, 1103.1Kg of finished product is obtained, the content is 99.3 percent, and the yield is 91.3 percent.
Example 3
a. Dropwise addition of thionyl chloride: firstly, adding 1020Kg of isovaleric acid and 2.5Kg of catalyst N, N-dimethylformamide into a reaction kettle, controlling the temperature in the reaction kettle to be 0-5 ℃, dropwise adding 1265Kg of thionyl chloride, then starting a tail gas absorption device, wherein the tail gas absorption device comprises three stages of absorption devices, all the three stages of absorption devices are filled with water, simultaneously starting brine ice in a tail gas condenser, controlling the gas phase temperature to be below 0 ℃, and finishing the dropwise adding of the thionyl chloride after 4-5 hours;
b. generation of the target product: after the dropwise addition of the thionyl chloride in the step a is finished, controlling the temperature in the reaction kettle to be 5-10 ℃, maintaining the temperature for 3.5-4.5h, then adjusting the temperature in the reaction kettle to be 10-20 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 20-30 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 30-40 ℃, maintaining the temperature for 3.5-4.5h, finally adjusting the temperature in the reaction kettle to be 40-50 ℃, maintaining the temperature for 1.5-2.5h, and obtaining an isovaleryl chloride material after the reaction is finished;
c. and (3) rectification of a target product: d, transferring the isovaleryl chloride material obtained by the reaction in the step b into a rectifying still for normal pressure rectification, firstly rectifying 369.7Kg of front cut, wherein the front cut comprises the components of isovaleryl chloride, isovaleric acid, thionyl chloride, HCl and SO2The method can be recycled, when the content of the isovaleryl chloride in the residual fraction in the rectifying still meets the requirement of a finished product, namely is more than or equal to 99 percent, the rectification is finished, the finished product is collected and packaged, 1110.5Kg of finished product is obtained, the content is 99.6 percent, and the yield is 92.2 percent.
Claims (3)
1. A low-temperature synthesis method of isovaleryl chloride is characterized in that isovaleric acid is used as a main raw material, a chlorinating agent is added into the isovaleric acid, and then the isovaleryl chloride is synthesized under the action of a catalyst and under the condition of low reaction temperature, and the specific operation steps are as follows:
a. dropwise addition of thionyl chloride: firstly, adding 1020Kg of isovaleric acid and 3Kg of catalyst N, N-dimethylformamide into a reaction kettle, controlling the temperature in the reaction kettle at 0-5 ℃, dropwise adding 1260Kg of thionyl chloride, then starting a tail gas absorption device, wherein the tail gas absorption device comprises a three-stage absorption device, the three-stage absorption device is filled with water, simultaneously starting brine ice in a tail gas condenser, controlling the gas phase temperature below 0 ℃, and finishing the dropwise adding of the thionyl chloride after 4-5 hours;
b. generation of the target product: after the dropwise addition of the thionyl chloride in the step a is finished, controlling the temperature in the reaction kettle to be 5-10 ℃, maintaining the temperature for 3.5-4.5h, then adjusting the temperature in the reaction kettle to be 10-20 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 20-30 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 30-40 ℃, maintaining the temperature for 3.5-4.5h, finally adjusting the temperature in the reaction kettle to be 40-50 ℃, maintaining the temperature for 1.5-2.5h, and obtaining an isovaleryl chloride material after the reaction is finished;
c. and (3) rectification of a target product: b, transferring the isovaleryl chloride material obtained by the reaction in the step b into a rectifying still for normal pressure rectification, and rectifying to obtain a front cut fraction of 367.3Kg, wherein the front cut fraction comprises isovaleryl chloride, isovaleric acid, thionyl chloride, HCl and SO2The method can be recycled, when the content of the isovaleryl chloride in the residual fraction in the rectifying still meets the requirement of a finished product, namely is more than or equal to 99 percent, the rectification is finished, the finished product is collected and packaged, 1109.1Kg of finished product is obtained, the content is 99.5 percent, and the yield is 92.0 percent.
2. A low-temperature synthesis method of isovaleryl chloride is characterized in that isovaleric acid is used as a main raw material, a chlorinating agent is added into the isovaleric acid, and then the isovaleryl chloride is synthesized under the action of a catalyst and under the condition of low reaction temperature, and the specific operation steps are as follows:
a. dropwise addition of thionyl chloride: firstly, adding 1020Kg of isovaleric acid and 2.1Kg of catalyst N, N-dimethylformamide into a reaction kettle, controlling the temperature in the reaction kettle at 0-5 ℃, dropwise adding 1255Kg of thionyl chloride, then starting a tail gas absorption device, wherein the tail gas absorption device comprises three-stage absorption devices, the three-stage absorption devices are filled with water, simultaneously starting brine ice in a tail gas condenser, controlling the gas phase temperature below 0 ℃, and finishing the dropwise adding of the thionyl chloride after 4-5 hours;
b. generation of the target product: after the dropwise addition of the thionyl chloride in the step a is finished, controlling the temperature in the reaction kettle to be 5-10 ℃, maintaining the temperature for 3.5-4.5h, then adjusting the temperature in the reaction kettle to be 10-20 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 20-30 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 30-40 ℃, maintaining the temperature for 3.5-4.5h, finally adjusting the temperature in the reaction kettle to be 40-50 ℃, maintaining the temperature for 1.5-2.5h, and obtaining an isovaleryl chloride material after the reaction is finished;
c. and (3) rectification of a target product: b, transferring the isovaleryl chloride material obtained by the reaction in the step b into a rectifying still for normal pressure rectification, and rectifying to obtain a front cut of 365.2Kg, wherein the front cut comprises the components of isovaleryl chloride, isovaleric acid, thionyl chloride, HCl and SO2The method can be recycled, when the content of the isovaleryl chloride in the residual fraction in the rectifying still meets the requirement of a finished product, namely is more than or equal to 99 percent, the rectification is finished, the finished product is collected and packaged, 1103.1Kg of finished product is obtained, the content is 99.3 percent, and the yield is 91.3 percent.
3. A low-temperature synthesis method of isovaleryl chloride is characterized in that isovaleric acid is used as a main raw material, a chlorinating agent is added into the isovaleric acid, and then the isovaleryl chloride is synthesized under the action of a catalyst and under the condition of low reaction temperature, and the specific operation steps are as follows:
a. dropwise addition of thionyl chloride: firstly, adding 1020Kg of isovaleric acid and 2.5Kg of catalyst N, N-dimethylformamide into a reaction kettle, controlling the temperature in the reaction kettle to be 0-5 ℃, dropwise adding 1265Kg of thionyl chloride, then starting a tail gas absorption device, wherein the tail gas absorption device comprises three stages of absorption devices, all the three stages of absorption devices are filled with water, simultaneously starting brine ice in a tail gas condenser, controlling the gas phase temperature to be below 0 ℃, and finishing the dropwise adding of the thionyl chloride after 4-5 hours;
b. generation of the target product: after the dropwise addition of the thionyl chloride in the step a is finished, controlling the temperature in the reaction kettle to be 5-10 ℃, maintaining the temperature for 3.5-4.5h, then adjusting the temperature in the reaction kettle to be 10-20 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 20-30 ℃, maintaining the temperature for 1.5-2.5h, then adjusting the temperature in the reaction kettle to be 30-40 ℃, maintaining the temperature for 3.5-4.5h, finally adjusting the temperature in the reaction kettle to be 40-50 ℃, maintaining the temperature for 1.5-2.5h, and obtaining an isovaleryl chloride material after the reaction is finished;
c. and (3) rectification of a target product: b, transferring the isovaleryl chloride material obtained by the reaction in the step b into a concentrateRectifying under normal pressure in a rectifying still to obtain 369.7Kg of front cut fraction, which comprises isovaleryl chloride, isovaleric acid, thionyl chloride, HCl and SO2The method can be recycled, when the content of the isovaleryl chloride in the residual fraction in the rectifying still meets the requirement of a finished product, namely is more than or equal to 99 percent, the rectification is finished, the finished product is collected and packaged, 1110.5Kg of finished product is obtained, the content is 99.6 percent, and the yield is 92.2 percent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1740132A (en) * | 2005-08-29 | 2006-03-01 | 上海华谊丙烯酸有限公司 | Synthesis and purification process of (2-methyl)-3-chloropropionyl chloride |
| CN101255108A (en) * | 2007-11-16 | 2008-09-03 | 西北师范大学 | Method for preparing aliphatic acyl chloride without solvent |
| CN103193621A (en) * | 2013-03-26 | 2013-07-10 | 安徽海顺化工有限公司 | Acylation reaction method for preparing 2-4-(chlorophenyl)-3-methylbutyryl chloride |
| CN103864600A (en) * | 2014-03-13 | 2014-06-18 | 东力（南通）化工有限公司 | Anti-hydrolysis production process of isovaleryl chloride |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1740132A (en) * | 2005-08-29 | 2006-03-01 | 上海华谊丙烯酸有限公司 | Synthesis and purification process of (2-methyl)-3-chloropropionyl chloride |
| CN101255108A (en) * | 2007-11-16 | 2008-09-03 | 西北师范大学 | Method for preparing aliphatic acyl chloride without solvent |
| CN103193621A (en) * | 2013-03-26 | 2013-07-10 | 安徽海顺化工有限公司 | Acylation reaction method for preparing 2-4-(chlorophenyl)-3-methylbutyryl chloride |
| CN103864600A (en) * | 2014-03-13 | 2014-06-18 | 东力（南通）化工有限公司 | Anti-hydrolysis production process of isovaleryl chloride |
Non-Patent Citations (1)
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