CN1297788A - Liquid catalyst for producing high-purity chloroacetic acid and catalytic synthesis of chloroacetic acid - Google Patents
Liquid catalyst for producing high-purity chloroacetic acid and catalytic synthesis of chloroacetic acid Download PDFInfo
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Abstract
The catalyst is one mixture of multiple components including acetyl chloride, disulfur dichloride, chloroacetic chloride, thionyl chloride, N,N-dimethyl formamide, inorganic acid, iron salt, zinc salt, manganese salt, etc. It has the features of high activity and high selectivity. When the catalyst is used in the chlorination of acetic acid at 383 K, the reaction period is only 8 hr; the chlorinated liquid has a monochloroacetic acid content greater than 94.0 wt%, dichloroacetic acid content less than 4.5 wt%; and after crystallization and vacuum suction filtering, the product has chloroacetic acid content greater than 98 wt% and dichloroacetic acid content less than 0.5 wt% reaching high purity chloroacetic acid grade.
Description
The invention relates to a catalyst for producing chloroacetic acid by taking acetic acid and chlorine as raw materials and a method for catalytically synthesizing chloroacetic acid by using the catalyst.
Chloroacetic Acid (MCA), also known as monochloroacetic acid, is one of important basic chemical raw materials and is widely used in the synthesis of pesticides, medicines, dyes and various fine chemical products. The main methods for producing chloroacetic acid at present are: acetic acid chlorination process, trichloroethylene hydrolysis process, chlorohydrin oxidation process and tetrachloroethane hydrolysis process. The most competitive of these is the catalytic acetic acid chlorination process. In the catalytic acetic acid chlorination process, the process is mainly divided into a sulfur catalytic process and an acetic anhydride catalytic process according to different catalysts. Although the sulfur catalysis method is an early process, the process is mature, but the sulfur catalyst has poor activity, low selectivity and long reaction time, the chlorination reaction is generally over 20 hours, and sulfur is remained in the product and the byproduct hydrochloric acid, so that the production of the high-purity chloroacetic acid product is difficult. The acetic anhydride catalytic method is the prior chloroacetic acid production method at present, the catalyst has the advantages of good catalytic activity, high selectivity, no sulfur in the product and the like, some publications also disclose that acetic anhydride is used as an acetic acid chlorination reaction catalyst, for example, as Xuyanli in 1998 period 5 of petrochemical industry, a composite catalyst consisting of acetic anhydride and acetyl chloride is introduced, and the composite catalyst reacts for 12 hours at 105 ℃ to obtain a chlorination liquid with the chloroacetic acid content of 93.38% and the dichloroacetic acid content of 3.86%. 97103686, Chinese patent also reports that the catalytic activity and selectivity of the catalyst are higher than those of pure sulfur or acetic anhydride, the chlorination reaction period is shortened by more than one time than that of the sulfur catalytic method, and the purity of the product reaches 99%, but after crystallization and suction filtration, the process must use carbon tetrachloride to drip the surface of chloroacetic acid crystals to clean dichloroacetic acid adsorbed on the surfaces of chloroacetic acid crystals, and the highly toxic carbon tetrachloride makes the process complicated to operate, increases the equipment investment, increases the cost, and the residue caused by the introduced carbon tetrachloride affects the deep processing of chloroacetic acid products.
The invention aims to provide a catalyst for producing chloroacetic acid with high activity and high selectivity and a method for catalytically synthesizing chloroacetic acid by using the catalyst.
The research and analysis show that the sulfur catalyzes the chlorination of acetic acid to synthesize chloroacetic acid, and the synthesis process comprises the following steps:
the acetic anhydride catalyzed chlorination reaction is carried out by the following processes:
the above mechanism research shows that, no matter the sulfur catalyst or the acetic anhydride catalyst, the key species for catalyzing acetic acid chlorination are acetyl chloride and chloroacetyl chloride, so that the chemical substances for promoting the generation of the species will be the preferable auxiliary agents of the catalyst, and on the basis of a large number of experiments and in combination with the mechanism of acetic acid chlorination reaction, the inventor finds a catalyst for producing chloroacetic acid by acetic acid chlorination, and the compound components and the weight contents of the catalyst are as follows:
acetyl chloride (1-15%), dithio dichloride (1-10%), thionyl chloride (0.1-1%), N N-dimethylformamide (0.1-15%), inorganic acid (0.1-5%), chloroacetyl chloride (50-95%), iron salt (0.1-10%), zinc salt (0.1-10%) and manganese salt (0.1-10%).
The inorganic acid is selected from sulfuric acid, nitric acid, chlorosulfonic acid, or their mixture; iron salts in Fe3(SO4)2、FeCl3、Fe(NO3)3Selecting; zinc salt in ZnSO4、ZnCl2、Zn(NO3)2Selecting; manganese salts in Mn (Cl)2、Mn(NO3)2、MnSO4Selecting.
The method for producing chloroacetic acid by using the catalyst to catalyze chlorination of acetic acid is to mix the components of the catalyst and put the mixture into a chlorination reaction kettle, and to put glacial acetic acid into the chlorination reaction kettle, and to introduce chlorine into the chlorination reaction kettle. The chlorination reaction temperature is 263-400K, the medium temperature in the condenser is-243-255K, the reaction time is about 5-7 hours, when the specific gravity of the chlorination solution is 353K, the reaction time is 1.35-1.37, namely the reaction end point, the chlorine is closed, the temperature is kept for 0.5-2 hours, the product is obtained through crystallization and separation, the material is fed again in the empty kettle, and the cycle operation is carried out.
The function of the auxiliary agent in the catalyst can be known according to mechanism research and related experiments. The acetyl chloride and the chloracetyl chloride form a cyclic process of generating the chloracetic acid through chlorination reaction, namely:
however, the boiling point of acetyl chloride is only 52 ℃, and the acetyl chloride is easily carried away by tail gas flow, so the reaction system must automatically generate the acetyl chloride to keep the high rate of the acetic chlorination reaction.
The enol structure of acetyl chloride is important in the reaction of acetyl chloride with chlorine, and the presence of acid stabilizes the enol structure of acetyl chloride. Proper amount of iron salt, zinc salt and manganese salt can inhibit the side reaction of acetic acid deep chlorination to produce dichloroacetic acid, so proper amount of iron salt, zinc salt and manganese salt can raise the selectivity of the catalyst.
The preparation of the catalyst of the invention does not need special conditions and special equipment, and the components of the catalyst composition are prepared according to the proportion, and are put into an enamel reaction kettle at normal temperature and normal pressure and stirred uniformly.
Compared with the prior art, the invention has the prominent substantive characteristics and remarkable progresses that:
1. the catalyst has high activity, the chlorination reaction time is greatly shortened, the average reaction time is more than 20 hours according to the existing sulfur catalysis method, the average reaction time of the acetic anhydride catalysis method is 12 hours, and the chlorination reaction time of the invention is 8 hours, thereby greatly shortening the production period, reducing the energy consumption and improving the utilization rate of equipment;
2. the catalyst has high selectivity to chloroacetic acid, the chloroacetic acid content of the obtained chlorination solution is more than 94%, and the dichloroacetic acid content is less than 4.5%, so that the utilization rate of raw materials is greatly improved, the consumption of acetic acid is reduced, and the economic benefit of a chloroacetic acid production plant is improved;
3. the product has high purity, the chloroacetic acid content is more than 98 percent, and the dichloroacetic acid content is less than 0.5 percent, no residual sulfur exists, the grade of the high-purity chloroacetic acid product is achieved, and the application field of the product is not limited;
4. the catalyst has the advantages of high chlorination reaction speed, high chlorine absorption speed of a reaction system, capability of greatly adjusting chlorine according to the production requirement of chlor-alkali and important function of balancing chlorine in chlor-alkali production.
The effect of two components of the catalyst on the catalytic reaction is described below with reference to the accompanying drawings:
FIG. l is the effect of N, N-Dimethylformamide (DMF) on catalyst performance;
FIG. 2 is a graph of the effect of strong acid on catalyst performance.
As can be seen from fig. 1, when the amount of DMF added is less than 4%, the reaction speed is significantly increased with the addition of DMF, and the chloroacetic acid content increases with the increase of DMF content, but when the DMF content is greater than 4%, the chloroacetic acid content does not increase and hardly changes, indicating that 4% is the optimum amount of DMF added.
As can be seen from FIG. 2, as the reaction proceeds, the content of dichloroacetic acid in the material gradually increases, but the growth amplitude of dichloroacetic acid in the reaction of the catalyst added with chlorosulfonic acid is greatly reduced, which indicates that chlorosulfonic acid can inhibit the generation of dichloroacetic acid, and the selectivity of the catalyst is obviously improved.
The following are examples of the present invention:
example 1
Respectively feeding acetyl chloride (13%), disulfide dichloride (2%), thionyl chloride (0.5%), NN-dimethylformamide (5%), sulfuric acid or chlorosulfonic acid (1%), chloroacetyl chloride (74%), manganese sulfate or manganese chloride (0.5%), ferric sulfate or ferric trichloride (2%) and zinc sulfate or zinc chloride (2%) into a round-bottom flask with a stirring device according to the mass ratio, uniformly mixing under stirring, and transferring into a reagent bottle for storage to obtain the catalyst for later use. Closing the direct passage of 1000ml main and auxiliary two-necked round-bottomed flasks connected in series, 650ml glacial acetic acid and 98ml of the above catalyst were added to the flasks, respectivelyAnd (3) opening cooling media of the primary condenser and the secondary condenser, starting temperature rise after the temperature of the secondary condensing medium is reduced to 253K, introducing chlorine when the temperature of the main bottle is raised to 353K, introducing unreacted chlorine into the auxiliary bottle, and controlling the temperature of materials in the auxiliary bottle to 363 +/-5K. The temperature of the main bottle is changed, the temperature of the main bottle material is controlled to 378 +/-5K within 2 hours of reaction, the temperature of the main bottle material is controlled to 383 +/-5K after the reaction is carried out for 2 hours, and when the specific gravity of the material in the bottle rises to d353KAnd the temperature of the main bottle material is reduced to 378 +/-3K by = 1.32. When the specific gravity d of the materials in the main bottle353KAnd when the chlorine is not less than 1.36, closing the chlorine, keeping the temperature for 1 hour, and then pumping out the chlorination solution in the main bottle for crystallization. The monochloroacetic acid content in the obtained chlorination solution is 95.1 (wt)%, the dichloroacetic acid content is 3.0 (wt)%, 300ml of mother solution is added into a beaker in which the chlorination solution is put, and temperature programmed crystallization is carried out under stirring. After the crystallization is completed, the mother liquor is separated by vacuum suction filtration, and the product is obtained.
And after the main bottle is unloaded, the materials are fed again according to the proportion, the materials are used as auxiliary bottles, the original auxiliary bottles are used as the main bottles, and the circular operation is carried out. The average reaction period was 6.7 hours, the yield was 93%, the monochloroacetic acid content of the product was 99.4 (wt)%, and the dichloroacetic acid content was 0.2 (wt)%. Example 2
According to the mass ratio, respectively, acetyl chloride (10%), disulfide dichloride (1%), thionyl chloride (0.5%), NN-dimethylformamide (4%), nitric acid or chlorosulfonic acid (1%), chloroacetyl chloride (81%), manganese nitrate or manganese chloride (0.5%), ferric nitrate or ferric trichloride (1%) and zinc nitrate or zinc chloride (1%) are fed into an enamel reaction kettle with a stirring device, and after the materials are uniformly mixed under stirring, the materials are transferred to an enamel tank for storage, and the catalyst is obtained for later use. Closing direct channels of a main chlorination reaction kettle and an auxiliary chlorination reaction kettle which are connected in series, respectively putting 200 liters of glacial acetic acid and 30 liters of the catalyst into the main chlorination reaction kettle and the auxiliary chlorination reaction kettle which are 300 liters, starting a two-stage condenser, starting heating after the temperature of a second-stage low-temperature condensing medium is reduced to 253K, introducing chlorine when the temperature of the main kettle is increased to 353K, introducing unreacted chlorine into the auxiliary kettle, and controlling the material temperature of the auxiliary kettle to be 363 +/-5K. The temperature of the main kettle is changed, the temperature of the materials is controlled to be 378 +/-5K within 2 hours of reaction, and the temperature of the materials is controlled to be 383 +/-5K after the reaction is carried out for 2 hours. When the main kettle is chlorinatedIncrease of specific gravity of the liquid to d353K=1.32, the temperature of the chloridized liquid in the main kettle is reduced to 378 +/-3K when the specific gravity d of the chloridized liquid is353KAnd when the chlorine is kept at 1.35, closing the chlorine, keeping the temperature for 1 hour, and then discharging the main kettle to the crystallization kettle. The monochloroacetic acid content of the obtained chlorination solution is 95.1 wt%, and the dichloroacetic acid content is 4.0 wt%. Adding 95 liters of mother liquor into a crystallization kettle in which the chlorination liquid is put, and carrying out temperature reduction crystallization under the stirring program. After the crystallization is completed, the mother liquor is separated by vacuum suction filtration, and the product is obtained.
And after the main kettle is unloaded, the materials are fed again according tothe proportion, and the materials are used as an auxiliary kettle, and the original auxiliary kettle is used as the main kettle for cyclic operation. The average reaction period was 7.5 hours, the yield was 91%, the monochloroacetic acid content of the product was 99.1 (wt)%, and the dichloroacetic acid content was 0.4 (wt)%.
Example 3
According to the mass ratio, respectively, acetyl chloride (8%), disulfide dichloride (1.5%), thionyl chloride (0.2%), NN-dimethylformamide (4%), sulfuric acid or chlorosulfonic acid (1%), chloroacetyl chloride (82%), manganese sulfate or manganese chloride (0.5%), ferric sulfate or ferric trichloride (1%) and zinc sulfate or zinc chloride (2%) are fed into an enamel reaction kettle with a stirring device, and after being uniformly mixed under stirring, the mixture is transferred to an enamel tank for storage, so that the catalyst is obtained for later use. Closing direct channels of a main chlorination reaction kettle and an auxiliary chlorination reaction kettle which are connected in series, respectively putting 200 liters of glacial acetic acid and 24 liters of the catalyst into the main chlorination reaction kettle and the auxiliary chlorination reaction kettle which are 300 liters, starting a two-stage condenser, starting heating after the temperature of a second-stage low-temperature condensing medium is reduced to 253K, introducing chlorine when the temperature of the main kettle is increased to 353K, introducing unreacted chlorine into the auxiliary kettle, and controlling the material temperature of the auxiliary kettle to be 363 +/-5K. The temperature of the main kettle is changed, the temperature of the materials is controlled to be 378 +/-5K within 2 hours of reaction, and the temperature of the materials is controlled to be 383 +/-5K after the reaction is carried out for 2 hours. When the specific gravity of the chlorination liquid in the main kettle rises to d353K=1.32, the temperature of the chloridized liquid in the main kettle is reduced to 378 +/-3K when the specific gravity d of the chloridized liquid is353KAnd when the chlorine is not less than 1.355, closing the chlorine, keeping the temperature for 1 hour, and then discharging the main kettle to the crystallization kettle. The monochloroacetic acid content in the obtained chlorination solution is 94.3 wt%, and the dichloroacetic acid content is 4.2 wt%. Adding 92 liters of mother liquor into a crystallization kettle in which the chlorination liquid is put, and carrying out temperature reduction crystallization under the stirring program. After the crystallization is completed, vacuum suction filtration separation is carried outAnd (5) mother liquor to obtain the product.
And after the main kettle is unloaded, the materials are fed again according to the proportion, and the materials are used as an auxiliary kettle, and the original auxiliary kettle is used as the main kettle for cyclic operation. The average reaction period was 8 hours, the yield was 90%, the monochloroacetic acid content of the product was 99.0 (wt)%, and the dichloroacetic acid content was 0.7 (wt)%.
Claims (6)
1. A liquid catalyst for producing high-purity chloroacetic acid is characterized in that the components and the weight contents of the composition of the liquid catalyst comprise: acetyl chloride (1-15%), dithio dichloride (1-10%), thionyl chloride (0.1-1%), N, N-dimethylformamide (0.1-15%), inorganic acid (0.1-5%), chloroacetyl chloride (50-95%), iron salt (0.1-10%), zinc salt (0.1-10%) and manganese salt (0.1-10%);
2. the catalyst of claim 1, wherein the inorganic acid is selected from sulfuric acid, nitric acid, chlorosulfonic acid, or a mixture thereof;
3. the catalyst of claim 1, wherein the iron salt is Fe3(SO4)2、FeCl3、Fe(NO3)3Selecting;
4. catalyst according to claim 1, characterized in that the zinc salt is in ZnSO4、ZnCl2、Zn(NO3)2Selecting;
5. catalyst according to claim 1, characterized in that the manganese salt is in MnCl2、Mn(NO3)2、MnSO4Selecting;
6. the method for producing chloroacetic acid by using the catalyst of claim 1 for catalyzing chlorination of acetic acid is characterized in that the catalyst components are mixed according to a certain proportion and then put into a chlorination reaction kettle, glacial acetic acid is put into the chlorination reaction kettle, chlorine gas is introduced, the chlorination reaction temperature is 363-400K, the medium temperature in a condenser is 243-255K, when the chlorination solution ratio is 1.35-1.37 when the chlorination solution ratio is 353K, the reaction end point is reached, the chlorine gas is closed, the temperature is kept for 0.5-2 hours, the product is obtained through crystallization and separation, the materials are put again in an empty kettle, and the cycle operation is carried out.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 00131152 CN1108192C (en) | 2000-11-13 | 2000-11-13 | Liquid catalyst for producing high-purity chloroacetic acid and catalytic synthesis of chloroacetic acid |
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| CN 00131152 CN1108192C (en) | 2000-11-13 | 2000-11-13 | Liquid catalyst for producing high-purity chloroacetic acid and catalytic synthesis of chloroacetic acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386574B (en) * | 2007-09-10 | 2013-01-23 | 张天德 | Method for preparing chloracetic acid using acetyl chloride as catalyst |
| CN109529798A (en) * | 2018-11-26 | 2019-03-29 | 上海建安化工设计有限公司 | One kind preparing chloroacetic catalyst and its preparation and application for being catalyzed acetic acid |
| CN110818558A (en) * | 2019-12-17 | 2020-02-21 | 山东民基化工有限公司 | Method and device for continuously preparing chloro pivaloyl chloride by using micro-channel |
-
2000
- 2000-11-13 CN CN 00131152 patent/CN1108192C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386574B (en) * | 2007-09-10 | 2013-01-23 | 张天德 | Method for preparing chloracetic acid using acetyl chloride as catalyst |
| CN109529798A (en) * | 2018-11-26 | 2019-03-29 | 上海建安化工设计有限公司 | One kind preparing chloroacetic catalyst and its preparation and application for being catalyzed acetic acid |
| CN109529798B (en) * | 2018-11-26 | 2021-12-07 | 上海市安装工程集团有限公司 | Catalyst for catalyzing acetic acid to prepare chloroacetic acid, and preparation and application thereof |
| CN110818558A (en) * | 2019-12-17 | 2020-02-21 | 山东民基化工有限公司 | Method and device for continuously preparing chloro pivaloyl chloride by using micro-channel |
| CN110818558B (en) * | 2019-12-17 | 2023-09-08 | 山东民基新材料科技有限公司 | Method and device for continuously preparing chloro-pivaloyl chloride by utilizing micro-channel |
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