CN112300001A - Production method for co-production of ethyl chloroformate and ethyl chloride - Google Patents
Production method for co-production of ethyl chloroformate and ethyl chloride Download PDFInfo
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- CN112300001A CN112300001A CN202011243538.7A CN202011243538A CN112300001A CN 112300001 A CN112300001 A CN 112300001A CN 202011243538 A CN202011243538 A CN 202011243538A CN 112300001 A CN112300001 A CN 112300001A
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- ethyl chloroformate
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Abstract
The invention discloses a production method for co-producing ethyl chloroformate and chloroethane, which takes phosgene and ethanol as raw materials to prepare ethyl chloroformate, and byproducts are hydrogen chloride and chloroethane; removing gas from the ethyl chloroformate synthetic solution, and refining to obtain ethyl chloroformate and diethyl carbonate finished products; liquefying chloroethane and unreacted phosgene by a condenser, flowing into a low-level tank, feeding the liquefied chloroethane and unreacted phosgene into a heating kettle through a pipeline, heating and gasifying, removing acid gas in the gas by sequentially passing through alkali liquor, and then introducing concentrated sulfuric acid for drying and dewatering, wherein the dried gas is a chloroethane finished product; the hydrogen chloride gas produced by the synthesis side preparation of ethyl chloroformate enters a next-stage reaction kettle and reacts with ethanol under the action of a catalyst to prepare ethyl chloride. And respectively carrying out alkali washing and drying on the condensed crude chloroethane gas, and then compressing to obtain the finished chloroethane. The co-production scheme provided by the invention reduces the tail gas treatment cost, reduces the tail gas emission, realizes the resource utilization of the waste gas, reduces the waste gas by more than 90%, and has obvious economic effect.
Description
Technical Field
The invention relates to a production process of ethyl chloroformate and chloroethane, in particular to a production method for co-producing chloroethane by ethyl chloroformate. The method effectively utilizes the byproduct chloroethane in the ethyl chloroformate production process, and simultaneously, the byproduct hydrogen chloride is used for co-producing chloroethane. The process is clean, the byproduct hydrogen chloride is effectively utilized, and the process has high industrial application value.
Background
Ethyl chloroformate, also known as ethyl chlorocarbonate, ethyl chloroformate. The synthesis method mainly comprises a reaction route of ethanol and phosgene. There are generally two methods, the solid phosgene method and the gaseous phosgene method. Ethyl chloroformate is used as an intermediate for producing various products, organic synthesis, chemical solvents, chemical products for producing medicines and herbicides, such as cefazolin (pioneer 5), tetrazoleacetic acid, nicosulfuron, and the like. In recent years, ethyl chloroformate has been used as a main raw material for synthesizing agricultural chemicals such as fungicides, herbicides, and insecticides.
Patent CN201420748231 describes an ethyl chloroformate tail gas treatment device, and the tail gas is treated by an alkali absorption device with a metal net. The byproduct hydrogen chloride is not effectively utilized, a large amount of liquid caustic soda is consumed, the salt-containing wastewater is more, and the environmental protection pressure is high.
Patent CN109593038A describes a method for treating tail gas of ethyl chloroformate, which comprises introducing excess phosgene in the reaction into ethanol to continue the reaction. Meanwhile, a treatment process during parking is introduced, nitrogen is blown into the reaction tower, and tail gas containing light is absorbed by alkali liquor. The patent does not describe the effective utilization of by-produced hydrogen chloride and ethyl chloride.
Ethyl chloride, also known as ethyl chloride, is a colorless combustible gas with an ether-like odor. The method is mainly used for synthesizing dye intermediates, perfume intermediates, ethyl cellulose, antibacterial agents, insecticides and the like, and has very wide application. The industrial production of ethyl chloride is carried out by reacting ethanol with hydrochloric acid or hydrogen chloride. In the last 10 years, with the rapid increase of the output of the products such as dye, spice, ethyl aluminum, ethyl chlorosilane and the like in China, the demand of the ethyl chloride is greatly increased.
Phosgene and ethanol are industrially used for synthesizing ethyl chloroformate, and hydrogen chloride and chloroethane are byproducts. The byproduct is usually destroyed by alkali liquor, which not only increases the cost of ethyl chloroformate, but also has more salt-containing wastewater and large environmental protection pressure.
Disclosure of Invention
The invention solves the problems of high cost, high salt-containing wastewater and high environmental protection pressure of ethyl chloroformate in the process of synthesizing ethyl chloroformate by industrially reacting phosgene with ethanol in the prior art, and provides a production method for co-producing ethyl chloroformate and chloroethane.
The invention is realized by the following technical scheme:
a production method for co-producing ethyl chloroformate and chloroethane comprises the following production process steps: step a, preparing ethyl chloroformate by using phosgene and ethanol as raw materials, and obtaining byproducts of hydrogen chloride and chloroethane; b, removing gas from the ethyl chloroformate synthetic solution, and refining to obtain ethyl chloroformate and diethyl carbonate finished products; step c, liquefying chloroethane and unreacted phosgene by a condenser, flowing into a low-level tank, feeding the liquefied chloroethane and unreacted phosgene into a heating kettle through a pipeline, heating and gasifying, removing acid gas in the gas by sequentially passing through alkali liquor, and then introducing concentrated sulfuric acid for drying and dewatering, wherein the dried gas is a chloroethane finished product; co-production preparation of chloroethane: and d, feeding hydrogen chloride gas produced by the synthesis side preparation of ethyl chloroformate into a next-stage reaction kettle, and reacting with ethanol under the action of a catalyst to prepare ethyl chloride. And respectively carrying out alkali washing and drying on the condensed crude chloroethane gas, and then compressing to obtain the finished chloroethane.
Further, the production method for co-producing ethyl chloroformate and ethyl chloride comprises the following steps of (a) enabling the molar ratio of phosgene and ethanol as reactants in the step a to be 1.0-1.2, enabling the reaction temperature to be 0-50 ℃, and enabling phosgene: the ethanol molar ratio is 0.8-1.6, and the reaction time is 2-8 h.
Further, a production method for co-producing ethyl chloroformate and ethyl chloride comprises the following steps: the ethanol molar ratio is preferably 1.0-1.2, the reaction temperature is preferably 5-40 ℃, and the reaction time is preferably 3-6 h.
Further, a production method for co-producing ethyl chloroformate and chloroethane, wherein the ethyl chloroformate gas removing mode in the step b is heating gas removing or introducing inert gas to remove gas, the temperature is 40-90 ℃, preferably 50-80 ℃, and the inert gas is preferably nitrogen.
Further, a method for co-producing ethyl chloroformate and ethyl chloride, wherein the ethyl chloroformate in the step b is rectified under reduced pressure, and the vacuum degree is 10-600 mmHg, preferably 100-300 mmHg.
Further, the production method for co-producing ethyl chloroformate and chloroethane comprises the step c of liquefying phosgene and chloroethane at the condenser temperature of-20-0 ℃, preferably-20-10 ℃; the temperature of the low tank is-20 to 0 ℃, and-20 to-10 ℃; the temperature of the heating kettle is 20-60 ℃; preferably 30 to 50 ℃.
Further, in the production method of ethyl chloroformate and chloroethane, the byproduct hydrogen chloride in the step d is 80-90% of the molar weight of ethanol in the step a.
Further, a production method of ethyl chloroformate with co-production of ethyl chloride, wherein hydrogen chloride during preparation of ethyl chloride in step d: the ethanol molar ratio is 1.0-1.1, and the reaction temperature is 60-80 ℃.
Further, a method for co-producing ethyl chloroformate and ethyl chloride is provided, wherein the catalyst reacted in the step d is one or a combination of three of FeCl3, ZnCl2 and AlCl 3.
Further, in the production method of ethyl chloroformate and co-production of ethyl chloride, the temperature of the condenser of the reaction kettle in the step d is 15-40 ℃, and preferably 15-30 ℃.
At present, in the process of synthesizing ethyl chloroformate by industrially using phosgene and ethanol to react, the cost of ethyl chloroformate, a lot of salt-containing wastewater and high environmental protection pressure are needed, so the application provides a production method for co-producing ethyl chloroformate and chloroethane. The tail gas absorption liquid of the present invention is not particularly limited, and any absorption liquid known to those skilled in the art that can be used for absorbing hydrogen chloride gas can be used, for example, any one or a combination of at least two of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, ammonia water, etc., wherein a typical non-limiting combination is: a combination of sodium hydroxide solution and potassium hydroxide solution, a combination of sodium hydroxide solution and sodium carbonate solution, a combination of potassium hydroxide solution and sodium carbonate solution, a combination of sodium hydroxide solution and ammonia.
In summary, the following beneficial effects of the invention are:
1. the invention relates to a production method for co-producing ethyl chloroformate and chloroethane, which can recycle the byproduct chloroethane of the ethyl chloroformate.
2. According to the production method for co-producing ethyl chloroformate and chloroethane, hydrogen chloride as a byproduct of ethyl chloroformate can be used as a raw material for synthesizing chloroethane, so that the tail gas treatment cost is greatly reduced, and the resource utilization of waste gas is realized.
3. The production method for co-producing ethyl chloroformate and chloroethane provided by the invention greatly reduces the emission of tail gas, reduces the waste gas by more than 90%, and has a remarkable economic effect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Examples
Example 1
As shown in fig. 1, this embodiment provides a method for co-producing ethyl chloroformate and ethyl chloride, which specifically includes the following steps:
(1) adding 20mol of ethanol, phosgene: the hydrogen chloride is 1:1, the reaction temperature is 15 ℃, and the reaction time is 3 h.
(2) Adding 16.2mol of ethanol, hydrogen chloride: ethanol is 1.05:1, the reaction temperature is 60 ℃, ZnCl 2-AlCl 3 is used as a catalyst, the molar ratio of the catalyst to the ethanol is 0.2:1, the condensation temperature of a reaction kettle is controlled at 25 ℃, and synthetic chloroethane gas is subjected to alkali washing, concentrated sulfuric acid drying and condensation under 0.8MPa to obtain a finished chloroethane product.
(3) Heating the ethyl chloroformate synthetic solution to 85 ℃ to expel gas for 4h, and rectifying under 500mmHg to obtain the finished products of ethyl chloroformate and diethyl carbonate.
Example 2
This example provides a method for co-producing ethyl chloroformate and ethyl chloride, which is the same as in example 1 except that the reaction temperature in step (1) is 25 ℃.
Example 3
This example provides a method for co-producing ethyl chloroformate and ethyl chloride, which is the same as in example 1 except that the reaction temperature in step (1) is 35 ℃.
Example 4
The embodiment provides a production method for co-producing ethyl chloroformate and ethyl chloride, which comprises the following steps of: the procedure of example 1 was repeated except that the molar ratio of ethanol was 1.1: 1.
Example 5
This example provides a method for co-producing ethyl chloroformate and ethyl chloride, which is the same as in example 1 except that the reaction time in step (1) is 5 hours.
Example 6
The present embodiment provides a method for co-producing ethyl chloroformate and ethyl chloride, where the flow diagram is shown in fig. 1, and the method specifically includes the following steps:
(1) adding 20mol of ethanol, phosgene: the ethanol ratio is 1.1:1, the reaction temperature is 25 ℃, and the reaction time is 5 h.
(2) Adding 15.8mol of ethanol, hydrogen chloride: ethanol is 1.07:1, the reaction temperature is 60 ℃, ZnCl 2-A lCl3 is used as a catalyst, the molar ratio of the catalyst to the ethanol is 0.2:1, the outlet temperature of a reaction kettle is controlled at 25 ℃, synthetic chloroethane gas is subjected to alkali washing, concentrated sulfuric acid drying and condensation under 0.8MPa to obtain a chloroethane finished product.
(3) Heating the ethyl chloroformate synthetic solution to 85 ℃ to expel gas for 4h, and rectifying under 500mmHg to obtain the finished products of ethyl chloroformate and diethyl carbonate.
Example 7
This example provides a method for co-producing ethyl chloroformate and ethyl chloride, which comprises the following steps, except that in step (2), 15.4mol of ethanol and hydrogen chloride are added: the procedure of example 6 was repeated except that the molar ratio of ethanol was 1.1: 1.
Example 8
This example provides a method for co-producing ethyl chloroformate and ethyl chloride, which is the same as in example 6 except that the catalyst in step (2) is FeCl 3.
Example 9
This example provides a method for co-producing ethyl chloroformate and ethyl chloride, which is the same as in example 6 except that the catalyst in step (2) is ZnCl 2.
Example 10
This example provides a method for co-producing ethyl chloroformate and ethyl chloride, which is the same as in example 6 except that the catalyst in step (2) is AlCl 3.
Example 11
The present embodiment provides a method for co-producing ethyl chloroformate and ethyl chloride, where the flow diagram is shown in fig. 1, and the method specifically includes the following steps:
(1) adding 20mol of ethanol, phosgene: the ethanol ratio is 1.1:1, the reaction temperature is 25 ℃, and the reaction time is 5 h.
(2) Adding 15.4mol of ethanol, hydrogen chloride: ethanol is 1.1:1, the reaction temperature is 69 ℃, ZnCl 2-A lCl3 is used as a catalyst, the molar ratio of the catalyst to the ethanol is 0.2:1, the outlet temperature of a reaction kettle is controlled at 25 ℃, synthetic chloroethane gas is subjected to alkali washing, concentrated sulfuric acid drying and condensation under 0.8MPa to obtain a chloroethane finished product.
(3) Heating the ethyl chloroformate synthetic solution to 85 ℃ to expel gas for 4h, and rectifying under 500mmHg to obtain the finished products of ethyl chloroformate and diethyl carbonate.
Example 12
This example provides a method for co-producing ethyl chloroformate and ethyl chloride, which is the same as in example 11 except that the reaction temperature in step (2) is 75 ℃.
Example 13
This example provides a method for co-producing ethyl chloroformate and ethyl chloride, which comprises the following steps: the procedure of example 11 was repeated except that the molar ratio of ethanol was 0.3: 1.
Example 14
This example provides a method for co-producing ethyl chloroformate and ethyl chloride, which comprises the following steps: the procedure is as in example 11 except that the molar ratio of ethanol is 0.4: 1.
And (3) testing and results: and (3) carrying out gas chromatography analysis on the reactants to divide the total amount of the generated ethyl chloroformate and the diethyl carbonate by the total amount of the added ethanol to calculate the ethanol conversion rate, calculating the phosgene utilization rate according to the ethyl chloroformate selectivity, and calculating the hydrogen chloride utilization rate according to the synthesized chloroethane.
The results of examples 1 to 14 are shown in the following table.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A production method for co-producing ethyl chloroformate and chloroethane is characterized by comprising the following production process steps:
step a, preparing ethyl chloroformate by using phosgene and ethanol as raw materials, and obtaining byproducts of hydrogen chloride and chloroethane;
b, removing gas from the ethyl chloroformate synthetic solution, and refining to obtain ethyl chloroformate and diethyl carbonate finished products;
step c, liquefying chloroethane and unreacted phosgene by a condenser, flowing into a low-level tank, feeding the liquefied chloroethane and unreacted phosgene into a heating kettle through a pipeline, heating and gasifying, removing acid gas in the gas by sequentially passing through alkali liquor, and then introducing concentrated sulfuric acid for drying and dewatering, wherein the dried gas is a chloroethane finished product;
and d, feeding the hydrogen chloride gas as a byproduct in the synthesis of ethyl chloroformate into a next-stage reaction kettle, reacting with ethanol under the action of a catalyst to prepare ethyl chloride, carrying out alkali washing and drying on the condensed crude ethyl chloride gas, and then compressing to obtain the finished product of ethyl chloride.
2. The production method of co-production of ethyl chloroformate and ethyl chloride according to claim 1, wherein the molar ratio of the reactant phosgene and ethanol in step a is 1.0-1.2, the reaction temperature is 0-50 ℃, and the molar ratio of phosgene: the ethanol molar ratio is 0.8-1.6, and the reaction time is 2-8 h.
3. The method for co-producing ethyl chloroformate and ethyl chloride according to claim 2, wherein the phosgene ratio is phosgene: the ethanol molar ratio is preferably 1.0-1.2, the reaction temperature is preferably 5-40 ℃, and the reaction time is preferably 3-6 h.
4. The production method for co-production of ethyl chloroformate and chloroethane according to claim 1, wherein the ethyl chloroformate gas-removing manner in step b is to heat up to remove gas or introduce inert gas to remove gas, the temperature is 40-90 ℃, preferably 50-80 ℃, and the inert gas is preferably nitrogen.
5. The method for co-producing ethyl chloroformate and ethyl chloride according to claim 1, wherein the ethyl chloroformate in the step b is rectified under reduced pressure with a vacuum degree of 10-600 mmHg, preferably 100-300 mmHg.
6. The production method for co-producing ethyl chloroformate and ethyl chloride according to claim 1, wherein the temperature of a condenser for liquefying phosgene and ethyl chloride in the step c is-20 to 0 ℃, and is preferably-20 to-10 ℃; the temperature of the low tank is-20 to 0 ℃, and-20 to-10 ℃; the temperature of the heating kettle is 20-60 ℃; preferably 30 to 50 ℃.
7. The method for producing ethyl chloroformate and co-producing ethyl chloride according to claim 1, wherein the hydrogen chloride byproduct in step d is 80 to 90% of the molar amount of ethanol in step a.
8. The method for co-producing ethyl chloroformate and ethyl chloride according to claim 1, wherein the hydrogen chloride used in the preparation of ethyl chloride in step d: the ethanol molar ratio is 1.0-1.1, and the reaction temperature is 60-80 ℃.
9. The method for co-producing ethyl chloroformate and ethyl chloride according to claim 1, wherein the catalyst used in the reaction in step d is one or a combination of three of FeCl3, ZnCl2 and AlCl 3.
10. The method for producing ethyl chloroformate and co-producing ethyl chloride according to claim 1, wherein the temperature of the condenser of the reaction kettle in the step d is 15-40 ℃, preferably 15-30 ℃.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1379977A (en) * | 1972-02-04 | 1975-01-08 | Eszakmagyar Vegyimuevek | Method and apparatus for producing chloroformates |
| CN102850178A (en) * | 2012-08-24 | 2013-01-02 | 江苏振方医药化工有限公司 | Method for synthesizing ethyl chloride by using gas phase hydrogen chloride and ethanol |
| CN105254469A (en) * | 2015-10-28 | 2016-01-20 | 浙江迪邦化工有限公司 | Chloroethane clean production process and device |
| CN109096111A (en) * | 2018-09-11 | 2018-12-28 | 安徽东至广信农化有限公司 | A kind of synthetic method of chloro-methyl-chloroformate |
| CN109503312A (en) * | 2019-01-15 | 2019-03-22 | 浙江迪邦化工有限公司 | A kind of technique of the by-product hydrogen chloride continuous production chloroethanes using chlorobenzene production |
| CN109663477A (en) * | 2018-12-30 | 2019-04-23 | 安徽广信农化股份有限公司 | A kind of method for treatment of waste material preparing ethyl chloroformate |
| CN109694309A (en) * | 2019-01-18 | 2019-04-30 | 淮阴工学院 | The method that chloroethanes is prepared by chlorination reaction byproduct hydrogen chloride |
| CN111689858A (en) * | 2020-06-24 | 2020-09-22 | 江苏蓝丰生物化工股份有限公司 | Method for preparing ethyl chloroformate |
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2020
- 2020-11-10 CN CN202011243538.7A patent/CN112300001A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1379977A (en) * | 1972-02-04 | 1975-01-08 | Eszakmagyar Vegyimuevek | Method and apparatus for producing chloroformates |
| CN102850178A (en) * | 2012-08-24 | 2013-01-02 | 江苏振方医药化工有限公司 | Method for synthesizing ethyl chloride by using gas phase hydrogen chloride and ethanol |
| CN105254469A (en) * | 2015-10-28 | 2016-01-20 | 浙江迪邦化工有限公司 | Chloroethane clean production process and device |
| CN109096111A (en) * | 2018-09-11 | 2018-12-28 | 安徽东至广信农化有限公司 | A kind of synthetic method of chloro-methyl-chloroformate |
| CN109663477A (en) * | 2018-12-30 | 2019-04-23 | 安徽广信农化股份有限公司 | A kind of method for treatment of waste material preparing ethyl chloroformate |
| CN109503312A (en) * | 2019-01-15 | 2019-03-22 | 浙江迪邦化工有限公司 | A kind of technique of the by-product hydrogen chloride continuous production chloroethanes using chlorobenzene production |
| CN109694309A (en) * | 2019-01-18 | 2019-04-30 | 淮阴工学院 | The method that chloroethanes is prepared by chlorination reaction byproduct hydrogen chloride |
| CN111689858A (en) * | 2020-06-24 | 2020-09-22 | 江苏蓝丰生物化工股份有限公司 | Method for preparing ethyl chloroformate |
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