CN113956136B - Recycling method of 2-chloro-4- (4-chlorophenoxy) acetophenone residues - Google Patents
Recycling method of 2-chloro-4- (4-chlorophenoxy) acetophenone residues Download PDFInfo
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- CN113956136B CN113956136B CN202111204199.6A CN202111204199A CN113956136B CN 113956136 B CN113956136 B CN 113956136B CN 202111204199 A CN202111204199 A CN 202111204199A CN 113956136 B CN113956136 B CN 113956136B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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Abstract
The invention discloses a recycling method of 2-chloro-4- (4-chlorophenoxy) acetophenone residues, which comprises the following steps: mixing a certain amount of residues, water and liquid alkali, and carrying out heat preservation treatment under a certain pressure; then layering, extracting the water phase, merging organic phases, washing with water, separating phases, recovering under reduced pressure, and evaporating under high vacuum to obtain the 3,4' -dichloro diphenyl ether. The invention converts 2-chloro-4- (4-chlorophenoxy) acetophenone and isomers into raw material 3,4' -dichloro diphenyl ether, which can be reused for synthesizing 2-chloro-4- (4-chlorophenoxy) acetophenone, thereby realizing solid waste recycling, economy and environmental protection.
Description
Technical Field
The invention relates to the technical field of waste residue treatment processes, in particular to a recycling method of 2-chloro-4- (4-chlorophenoxy) acetophenone residues.
Background
The difenoconazole, also called as oxaether azole, is an ultra-efficient broad-spectrum systemic triazole fungicide, can strongly inhibit the sporulation of plant pathogenic bacteria, has three effects of preventing, treating and eradicating diseases in the process of preventing and controlling diseases, and is widely applied to various crops such as grains, cotton, melons, fruits, vegetables and the like. The 2-chloro-4- (4-chlorophenoxy) acetophenone is a key intermediate for effectively synthesizing the agricultural pesticide, namely the oxaether azole, and is the core for synthesizing the oxaether azole.
At present, various synthetic methods of 2-chloro-4- (4-chlorophenoxy) acetophenone are adopted, namely, 3,4' -dichloro diphenyl ether and an acylating agent acetic anhydride or acetyl chloride are adopted for carrying out acylation reaction, and 5% of isomer is generated in the synthetic process. In the actual production process, 3,4' -dichloro diphenyl ether and an acylating reagent acetic anhydride or acetyl chloride are subjected to acylation reaction, and then are subjected to operations such as evaporation, suction filtration and drying to generate a 2-chloro-4- (4-chlorophenoxy) acetophenone crude product, wherein the 2-chloro-4- (4-chlorophenoxy) acetophenone crude product also needs further refining, and at present, domestic manufacturers mostly carry out recrystallization refining through solvents such as petroleum ether, heptane and methanol to obtain a 2-chloro-4- (4-chlorophenoxy) acetophenone refined product, and the content of the produced 2-chloro-4- (4-chlorophenoxy) acetophenone product reaches 99 percent, and the yield reaches about 90 percent.
In the process of producing and refining 2-chloro-4- (4-chlorophenoxy) acetophenone refined products by adopting a recrystallization mode, 2-chloro-4- (4-chlorophenoxy) acetophenone residues are separated, and the 2-chloro-4- (4-chlorophenoxy) acetophenone residues contain a large amount of valuable components, about 23% -25% of isomers and 72% -75% of 2-chloro-4- (4-chlorophenoxy) acetophenone. In actual production, the general treatment mode of the residue by domestic manufacturers is that the residue is hydrolyzed by being introduced into water and then treated according to dangerous wastes, so that the site environment is very easy to be substandard, the resource is wasted, and a part of 2-chloro-4- (4-chlorophenoxy) acetophenone products are lost.
Disclosure of Invention
In view of the above, the invention provides a recycling method of 2-chloro-4- (4-chlorophenoxy) acetophenone residues, which aims to solve the problem of recycling 2-chloro-4- (4-chlorophenoxy) acetophenone residues, and the method converts 2-chloro-4- (4-chlorophenoxy) acetophenone and isomers into raw materials 3,4' -dichloro diphenyl ether under a certain pressure in the presence of strong alkali, so that the 2-chloro-4- (4-chlorophenoxy) acetophenone residues can be reused for synthesizing 2-chloro-4- (4-chlorophenoxy) acetophenone, thereby realizing solid waste recycling, economy and environmental protection; the conversion of 2-chloro-4- (4-chlorophenoxy) acetophenone and isomers is shown below:
a recycling method of 2-chloro-4- (4-chlorophenoxy) acetophenone residues comprises the following steps:
(1) Putting 530 g-650 g of residue, 300 g-500 g of water and 250 g-400 g of liquid alkali into a 2000ml autoclave, replacing 3 times with nitrogen, introducing nitrogen to fill the pressure to 0.5 MPa-0.8 MPa, then heating to 80-110 ℃, heating to 0.4 MPa-0.8 MPa, preserving the temperature for 6-10 hours under the pressure and the temperature, and sampling and analyzing;
(2) Cooling the system to 25-30 ℃ and layering to obtain an organic layer and a water layer;
(3) Extracting the water layer with 100 g-120 g toluene, and separating the toluene layer; and (3) combining the toluene layer and the organic layer in the step (2), washing with 50-100 g of water, separating phases, recovering toluene under reduced pressure until no flow exists, and steaming out under high vacuum to obtain the 3,4' -dichloro diphenyl ether.
Preferably, in the step (1), the content of 2-chloro-4- (4-chlorophenoxy) acetophenone in the residue is 70% -79% and the content of isomer is 20% -25%.
Preferably, in the step (1), the concentration of the liquid alkali is 30-45 wt%.
Preferably, the recycling method of the 2-chloro-4- (4-chlorophenoxy) acetophenone residues comprises the following steps:
(1) Putting 530 g-620 g of residue, 300 g-400 g of water and 300 g-350 g of liquid alkali into a 2000ml autoclave, replacing 3 times with nitrogen, introducing nitrogen to fill the pressure to 0.5 MPa-0.7 MPa, then heating to 80-100 ℃, heating to 0.4 MPa-0.6 MPa, preserving the temperature for 6-8 hours under the pressure and the temperature, and sampling and analyzing;
(2) Cooling the system to 30 ℃ and layering to obtain an organic layer and a water layer;
(3) Extracting the water layer with 100-110 g toluene, and separating the toluene layer; and (3) combining the toluene layer and the organic layer in the step (2), washing with 50-80 g of water, separating phases, recovering toluene under reduced pressure until no flow exists, and steaming out under high vacuum to obtain the 3,4' -dichloro diphenyl ether.
Preferably, in the step (3), the content of the 3,4' -dichloro diphenyl ether is 98.8% -99.5%.
From the technical scheme, the beneficial effects of the invention are as follows:
(1) The method for recycling the 2-chloro-4- (4-chlorophenoxy) acetophenone residues is adopted, and after the residues undergo the processes of alkalization, separation, water washing and the like, the recovery rate of the corresponding 3,4' -dichloro diphenyl ether reaches more than 93 percent, and the content reaches more than 98.8 percent.
(2) The 3,4' -dichloro diphenyl ether recovered by the method is used as a raw material for synthesizing 2-chloro-4- (4-chlorophenoxy) acetophenone, can be recycled in the synthesis process, and achieves the purposes of recycling, energy saving and consumption reduction.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, in order to make the objects, technical solutions and advantages of the present invention more apparent. The exemplary embodiments of the present invention and the descriptions thereof are used herein to explain the present invention, but are not intended to limit the invention.
Example 1
Recycling method of 2-chloro-4- (4-chlorophenoxy) acetophenone residues
The recycling method of the 2-chloro-4- (4-chlorophenoxy) acetophenone residues comprises the following steps:
(1) Putting 530g of residue, 300g of water and 250g of 30wt% liquid alkali into a 2000ml autoclave, replacing 3 times with nitrogen, introducing nitrogen to charge the pressure to 0.5MPa, then heating to 80 ℃, and raising the pressure to 0.55MPa, and at the pressure and the temperature, preserving heat for 8 hours, sampling and analyzing, wherein the content of 2-chloro-4- (4-chlorophenoxy) acetophenone and isomers is less than 3%;
(2) Cooling the system to 30 ℃ and layering to obtain an organic layer and a water layer;
(3) The aqueous layer was extracted with 100g of toluene, and then the toluene layer was separated; and (3) combining the toluene layer and the organic layer in the step (2), washing the combined organic layer once with 50g of water, separating phases, recovering toluene under reduced pressure until no flow exists, and steaming out the toluene under high vacuum to obtain the 3,4' -dichloro diphenyl ether.
In the step (1), the content of 2-chloro-4- (4-chlorophenoxy) acetophenone in the residue was 73% and the content of the isomer was 25%.
In this example, the mass of the recovered 3,4' -dichlorodiphenyl ether was 416.4g, the content was 99.2%, and the recovery rate was 93.5%.
Example 2
Recycling method of 2-chloro-4- (4-chlorophenoxy) acetophenone residues
The recycling method of the 2-chloro-4- (4-chlorophenoxy) acetophenone residues comprises the following steps:
(1) Putting 530g of residue, 300g of water and 300g of 30wt% liquid alkali into a 2000ml autoclave, replacing 3 times with nitrogen, introducing nitrogen to charge the pressure to 0.5MPa, then heating to 100 ℃, raising the pressure to 0.6MPa, preserving the temperature for 6 hours under the pressure and the temperature, and carrying out sampling analysis, wherein the content of 2-chloro-4- (4-chlorophenoxy) acetophenone and isomers is less than 1%;
(2) Cooling the system to 30 ℃ and layering to obtain an organic layer and a water layer;
(3) The aqueous layer was extracted with 100g of toluene, and then the toluene layer was separated; and (3) combining the toluene layer and the organic layer in the step (2), washing with 50g of water, separating phases, recovering toluene under reduced pressure until no flow exists, and steaming out under high vacuum to obtain the 3,4' -dichloro diphenyl ether.
In the step (1), the content of 2-chloro-4- (4-chlorophenoxy) acetophenone in the residue was 74% and the content of isomer was 23%.
In this example, the mass of the recovered 3,4' -dichlorodiphenyl ether was 414.8g, the content was 99.0%, and the recovery rate was 93.9%.
Example 3
Recycling method of 2-chloro-4- (4-chlorophenoxy) acetophenone residues
The recycling method of the 2-chloro-4- (4-chlorophenoxy) acetophenone residues comprises the following steps:
(1) Adding 580g of residue, 350g of water and 300g of 35wt% liquid alkali into a 2000ml autoclave, replacing for 3 times with nitrogen, introducing nitrogen to charge the pressure to 0.6MPa, then heating to 90 ℃, heating to 0.5MPa, preserving the temperature for 7 hours under the pressure and the temperature, and sampling and analyzing;
(2) Cooling the system to 30 ℃ and layering to obtain an organic layer and a water layer;
(3) The aqueous layer was extracted with 100g of toluene, and then the toluene layer was separated; and (3) combining the toluene layer and the organic layer in the step (2), washing with 65g of water, separating phases, recovering toluene under reduced pressure until no flow exists, and steaming out under high vacuum to obtain the 3,4' -dichloro diphenyl ether.
In the step (1), the content of 2-chloro-4- (4-chlorophenoxy) acetophenone in the residue was 76% and the content of isomer was 23%.
In this example, the mass of the recovered 3,4' -dichlorodiphenyl ether was 418.3g, the content was 99.2%, and the recovery rate was 93.7%.
Example 4
Recycling method of 2-chloro-4- (4-chlorophenoxy) acetophenone residues
The recycling method of the 2-chloro-4- (4-chlorophenoxy) acetophenone residues comprises the following steps:
(1) Adding 620g of residues, 400g of water and 350g of 40wt% liquid alkali into a 2000ml autoclave, replacing for 3 times by nitrogen, introducing nitrogen to charge the pressure to 0.7MPa, then heating to 100 ℃, heating the pressure to 0.6MPa, preserving the temperature for 8 hours under the pressure and the temperature, and sampling and analyzing;
(2) Cooling the system to 30 ℃ and layering to obtain an organic layer and a water layer;
(3) The aqueous layer was extracted with 105g of toluene, and then the toluene layer was separated; and (3) combining the toluene layer and the organic layer in the step (2), washing with 70g of water, separating phases, recovering toluene under reduced pressure until no flow exists, and steaming out under high vacuum to obtain the 3,4' -dichloro diphenyl ether.
In the step (1), the content of 2-chloro-4- (4-chlorophenoxy) acetophenone in the residue was 73% and the content of isomer was 22%.
In this example, the mass of the recovered 3,4' -dichlorodiphenyl ether was 421.3g, the content was 99.1%, and the recovery rate was 94.1%.
Example 5
Recycling method of 2-chloro-4- (4-chlorophenoxy) acetophenone residues
The recycling method of the 2-chloro-4- (4-chlorophenoxy) acetophenone residues comprises the following steps:
(1) Putting 650g of residue, 500g of water and 400g of 45wt% liquid alkali into a 2000ml autoclave, replacing for 3 times with nitrogen, introducing nitrogen to charge the pressure to 0.8MPa, then heating to 110 ℃, heating the pressure to 0.8MPa, preserving the temperature for 10 hours under the pressure and the temperature, and sampling and analyzing;
(2) Cooling the system to 30 ℃ and layering to obtain an organic layer and a water layer;
(3) The aqueous layer was extracted with 120g of toluene, and then the toluene layer was separated; and (3) combining the toluene layer and the organic layer in the step (2), washing with 100g of water, separating phases, recovering toluene under reduced pressure until no flow exists, and steaming out under high vacuum to obtain the 3,4' -dichloro diphenyl ether.
In the step (1), the content of 2-chloro-4- (4-chlorophenoxy) acetophenone in the residue was 79% and the content of isomer was 20%.
In this example, the mass of the recovered 3,4' -dichlorodiphenyl ether was 423.6g, the content was 99.4%, and the recovery rate was 94.2%.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and various modifications and variations can be made to the embodiments of the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. The method for recycling the 2-chloro-4- (4-chlorophenoxy) acetophenone residues is characterized by comprising the following steps of:
(1) Putting 530 g-650 g of residue, 300 g-500 g of water and 250 g-400 g of liquid alkali into a 2000ml pressure kettle, replacing 3 times with nitrogen, introducing nitrogen to fill the pressure to 0.5 MPa-0.8 MPa, then heating to 80-110 ℃, heating to 0.4 MPa-0.8 MPa, preserving the temperature for 6-10 hours under the pressure and the temperature, and sampling and analyzing;
(2) Cooling the system to 25-30 ℃ and layering to obtain an organic layer and a water layer;
(3) Extracting the water layer with 100 g-120 g of toluene, and separating a toluene layer; combining the toluene layer and the organic layer in the step (2), washing with 50-100 g of water, separating phases, recovering toluene under reduced pressure until no flow is generated, and evaporating under high vacuum to obtain 3,4' -dichloro diphenyl ether;
in the step (1), the content of 2-chloro-4- (4-chlorophenoxy) acetophenone in the residue is 70% -79% and the content of isomers is 20% -25%;
in the step (3), the content of the 3,4' -dichloro diphenyl ether is 98.8% -99.5%.
2. The method for recycling 2-chloro-4- (4-chlorophenoxy) acetophenone residue according to claim 1, wherein in the step (1), the concentration of the liquid alkali is 30wt% to 45wt%.
3. The method for recycling 2-chloro-4- (4-chlorophenoxy) acetophenone residues according to claim 1, wherein the method for recycling 2-chloro-4- (4-chlorophenoxy) acetophenone residues comprises the following steps:
(1) Putting 530 g-620 g of residue, 300 g-400 g of water and 300 g-350 g of liquid alkali into a 2000ml pressure kettle, replacing 3 times with nitrogen, introducing nitrogen to fill the pressure to 0.5 MPa-0.7 MPa, then heating to 80-100 ℃, heating to 0.4 MPa-0.6 MPa, preserving the temperature for 6-8 hours under the pressure and the temperature, and sampling and analyzing;
(2) Cooling the system to 30 ℃ and layering to obtain an organic layer and a water layer;
(3) Extracting the water layer with 100 g-110 g of toluene, and separating a toluene layer; and (3) combining the toluene layer and the organic layer in the step (2), washing with 50-80 g of water, separating phases, recovering toluene under reduced pressure until no flow exists, and steaming out under high vacuum to obtain the 3,4' -dichloro diphenyl ether.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434528A (en) * | 2007-11-15 | 2009-05-20 | 中国中化集团公司 | Method for preparing 2-chlorine-4-(4-chlorophenoxy)-hypnone |
| CN112479824A (en) * | 2020-12-25 | 2021-03-12 | 安徽润衍科技有限公司 | Method for recovering crystallization mother liquor in production process of 4-chloro-3, 5-dimethylphenol |
| CN112707799A (en) * | 2020-12-28 | 2021-04-27 | 杭州宇龙化工有限公司 | Method for preparing 3,4' -dichlorodiphenyl ether from difenoconazole isomer |
| CN113307721A (en) * | 2021-06-16 | 2021-08-27 | 浙江禾本科技股份有限公司 | Recovery and utilization of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone |
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- 2021-10-15 CN CN202111204199.6A patent/CN113956136B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434528A (en) * | 2007-11-15 | 2009-05-20 | 中国中化集团公司 | Method for preparing 2-chlorine-4-(4-chlorophenoxy)-hypnone |
| CN112479824A (en) * | 2020-12-25 | 2021-03-12 | 安徽润衍科技有限公司 | Method for recovering crystallization mother liquor in production process of 4-chloro-3, 5-dimethylphenol |
| CN112707799A (en) * | 2020-12-28 | 2021-04-27 | 杭州宇龙化工有限公司 | Method for preparing 3,4' -dichlorodiphenyl ether from difenoconazole isomer |
| CN113307721A (en) * | 2021-06-16 | 2021-08-27 | 浙江禾本科技股份有限公司 | Recovery and utilization of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone |
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