CN110878037A - High-value utilization method of tail liquid in thiourethane production - Google Patents
High-value utilization method of tail liquid in thiourethane production Download PDFInfo
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- CN110878037A CN110878037A CN201911361979.4A CN201911361979A CN110878037A CN 110878037 A CN110878037 A CN 110878037A CN 201911361979 A CN201911361979 A CN 201911361979A CN 110878037 A CN110878037 A CN 110878037A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
Abstract
The invention discloses a high-value utilization method of a tail liquid in thiourethane production, which can be used for separating and obtaining a high-purity thioglycollic acid product. The invention uses a small amount of extractant to extract thioglycollic acid in the enriched tail solution, removes impurities in the primary extraction liquid by adding reaction liquid to react in one step to separate out intermediate thioglycollic acid, then prepares the filtered thioglycollic acid into solution to be acidified, and carries out secondary extraction and then carries out reduced pressure distillation to obtain a high-purity thioglycollic acid product. The method solves the problem of difficult treatment of the tail liquid in the production of thiourethane, realizes high-value utilization of wastes, simplifies the production process and reduces the production cost.
Description
Technical Field
The invention relates to a high-value utilization method of chemical production waste liquid, in particular to a method for separating thiourethane tail liquid to obtain high-purity thioglycollic acid.
Background
Thionocarbamate refers to a class of compounds having the general formula ROCSNHR, which are derivatives of xanthates (xanthates). The flotation agent is generally an oily liquid, has low solubility in water and special smell, and is an excellent sulfide ore flotation agent. The sulfur-urethane has strong collecting capability on copper sulfide ores, zinc blende activated by copper ions and gold, and has weak collecting capability on sulfide minerals such as iron sulfide and the like, so that the sulfur-urethane shows good selectivity in flotation separation of gold, sulfur, zinc and copper. It features less dosage and easy foaming, so it is widely used in the floatation of various copper ore, gold ore and lead-zinc ore. A large amount of tail liquid containing thioglycollic acid is generated in the production process of thiourethane, the tail liquid has high usable value, but environmental pollution is easily caused and difficult to treat, so that the stock in the production of thiourethane is overstocked, and the normal production of thiourethane is influenced.
In addition, because the thioglycolic acid molecules contain carboxyl and sulfhydryl groups, the thioglycolic acid molecules have the reaction characteristics of both carboxylic acid and sulfhydryl, can be used for aspects of depilatories, functional cosmetics, color developing agents, processing stabilizers, petroleum exploration corrosion inhibitors, metal surface treating agents, polyoxyethylene stabilizers, organic synthesis and the like, and is one of reagents necessary for industries such as chemical engineering, light industry, pharmacy, petroleum exploitation, mineral separation and the like. But the domestic market gap of thioglycolic acid is large at present, and high-purity thioglycolic acid is imported. The industrial methods for producing thioglycolic acid include a sodium hydrosulfide method, a sodium thiosulfate method, a sodium polysulfide method, and the like, and these methods all require separation and extraction of thioglycolic acid from an aqueous solution of thioglycolic acid, and although the purity of the obtained product is high, the process is complicated. The thioglycollic acid produced by the tail liquid of the thiourethane byproduct at home has relatively low purity and yellow color, so that the application of the thioglycollic acid is limited. Chinese patent CN 105254547 discloses a method for preparing high-quality thioglycollic acid from tail liquid of O-alkyl-N-alkyl thionocarbamate production, which comprises acidifying the tail liquid with inorganic acid, standing to separate organic matter in suspension, and extracting with organic solvent. The method has high recovery rate and high product purity, but the dosage of the organic extractant is too large (the volume ratio of the dosage of the organic solvent to the acidification liquid is 2.5:0.01-2.5: 0.1), the composition of the extractant is complex, and the energy consumption for recovering the extractant is high. Chinese patent CN 106167458 discloses a method for separating thioglycolic acid from a thioglycolic acid aqueous solution, which comprises the steps of concentrating the thioglycolic acid aqueous solution twice, carrying out filter pressing twice to obtain a secondary concentrated solution and solid sodium chloride, carrying out reduced pressure rectification on the secondary concentrated solution under the action of a stabilizer to separate a finished product, and washing and recovering the thioglycolic acid carried in the solid sodium chloride. The method avoids the problems caused by the use of an extracting agent, but has relatively complex process and high operating conditions. Xuqinghua [ Shandong chemical industry, 2015, 44 (12): 10-11; shandong chemical industry, 2015, 44 (21): 40-41] the ethyl acetate is used as an extracting agent to recover the thioglycollic acid from the tail liquid of the thiourethane, but the extraction frequency is too many, the process is complex and the energy consumption is high. Zhenghong et al [ nonferrous mining, 2006, 22 (6): 17-18] the mixed extractant of dichloromethane and ether is adopted to recover thioglycollic acid from the thiourethane tail liquid, the process is complex, and the purity is low.
According to the high-valued utilization method of the thiourethane tail liquid, after the thioglycollic acid in the tail liquid is enriched by a small amount of the extracting agent, the reaction liquid is used for separating out the intermediate sodium thioglycollate so as to reduce the content of impurities, and the high-purity thioglycollic acid product is obtained by carrying out reduced pressure distillation separation after re-acidification extraction.
Disclosure of Invention
The invention aims to provide a method for producing tail liquid by utilizing thiourethane with high value aiming at the problems in the separation of the tail liquid of thiourethane at present, and a high-purity thioglycollic acid product is obtained by separation.
The high-value utilization of the tail liquid in the production of thiourethane is realized by the following technical scheme: extracting mercaptoacetic acid in the tail solution by using a proper amount of extractant to extract and concentrate mercaptoacetic acid in the tail solution, removing impurities in the primary extraction liquid by adding reaction liquid to react in one step to separate out intermediate sodium mercaptoacetate, preparing the filtered sodium mercaptoacetate into solution to be acidified, extracting for the second time, and distilling to obtain a mercaptoacetic acid product with the purity of more than 99 wt%.
The method for separating thioglycollic acid from the thiourethane tail liquid comprises the following steps:
(1) adding a primary extracting agent into the thiourethane tail liquid, extracting at room temperature, standing and layering to obtain primary extraction liquid enriched with thioglycollic acid;
(2) adding equimolar reaction liquid into the primary extraction liquid obtained in the step (1), precipitating the obtained sodium thioglycolate, and washing solid sodium thioglycolate by using a detergent after filtering;
(3) preparing the sodium thioglycolate obtained in the step (2) into a solution with a fixed concentration, and acidifying the solution with inorganic acid to obtain an acidified solution;
(4) adding a secondary extracting agent into the acidized fluid obtained in the step (3), performing secondary extraction at room temperature, standing and layering to obtain secondary extraction liquid containing thioglycollic acid;
(5) and (4) carrying out reduced pressure distillation on the secondary extraction liquid obtained in the step (4) to obtain a mercaptoacetic acid product with the purity of more than 99 wt%.
In the above method, in the method of separating thioglycolic acid from the thiourethane tail solution, the reaction solution added to the primary extract is an alcoholic solution of sodium hydroxide, preferably an alcohol is any one of methanol and ethanol or a mixture of the two in any proportion.
In the above method, in the method of separating thioglycolic acid from the thiourethane tail solution, the washing agent used after filtration is an alcohol, ether or ketone, preferably methanol or ethanol.
In the above method, in the method of separating thioglycolic acid from thiourethane tail liquid, the thioglycolic acid content in the thiourethane tail liquid is 5-20 wt%.
In the above method, in the method for separating thioglycollic acid from thionocarbamate tail liquid, the primary and secondary extractants are toluene, diethyl ether, isobutyl acetate, butyl acetate or isopropyl acetate, and preferably ester extractants.
The method has the advantages of high recovery rate, high purity, good quality and simple process, and has good economic and environmental protection significance. Compared with the related art, the invention has the following advantages:
1. by utilizing the difference of the solubility of substances, the intermediate sodium thioglycolate is prepared by one-step reaction and is separated out, so that the loss and energy consumption caused by rectification separation after extraction in the traditional process are avoided, and the effective removal of impurity components is ensured;
2. the secondary extraction after the sodium thioglycolate solution is acidified ensures the purity of the thioglycolic acid.
The specific implementation mode is as follows:
the invention is further described with reference to specific examples, which employ a high-value method for producing tail liquid by utilizing thiourethane to separate high-purity thioglycollic acid products. However, the present invention is not limited to the following examples, and various examples are included in the technical scope of the present invention within the scope not departing from the gist of the present invention.
Example 1
The invention relates to a method for separating thioglycollic acid from thiourethane tail liquid, which removes impurities in primary extraction liquid by means of primary extraction and enrichment of thioglycollic acid in tail liquid, adding reaction liquid to react in one step to separate sodium thioglycollate, then prepares the filtered sodium thioglycollate into solution for acidification, and obtains a high-purity thioglycollic acid product through reduced pressure distillation after secondary extraction. Wherein, the content of thioglycollic acid in tail liquid is 10 wt%, and the treatment process comprises the following steps:
(1) and (3) carrying out first extraction on the tail liquid containing 10 wt% of thioglycollic acid by adopting a quantitative ester extractant, and extracting the enriched thioglycollic acid to obtain a first extraction liquid, wherein the content of the thioglycollic acid is 9.5 wt%. Wherein, the adopted extractant is isobutyl acetate, the volume ratio of the extractant to the tail liquid is 1:2, and the operation is carried out at room temperature;
(2) adding a reaction solution (sodium hydroxide methanol saturated solution) with the same molar weight as that of thioglycolic acid into the primary extraction liquid obtained in the step (1), reacting to generate intermediate sodium thioglycolate, precipitating and separating out, filtering, and washing solid sodium thioglycolate with methanol;
(3) preparing the sodium thioglycolate obtained in the step (2) into a solution with the mass concentration of 70%, and adding dilute hydrochloric acid for acidification until the pH value is =1 to obtain a thioglycolic acid solution;
(4) and (3) carrying out secondary extraction on the acidified liquid with the pH =1 obtained in the step (3), and carrying out reduced pressure distillation on the obtained extract liquid by adopting diethyl ether as an extracting agent to obtain a mercaptoacetic acid product with the purity of 99.6 wt%. Wherein, the volume ratio of the secondary extractant to the acidizing fluid is 1:2, and the operation is carried out at room temperature.
Example 2
The invention relates to a method for separating thioglycollic acid from thiourethane tail liquid, which removes impurities in primary extraction liquid by means of primary extraction and enrichment of thioglycollic acid in tail liquid, adding reaction liquid to react in one step to separate sodium thioglycollate, then prepares the filtered sodium thioglycollate into solution for acidification, and obtains a high-purity thioglycollic acid product through reduced pressure distillation after secondary extraction. Wherein, the content of thioglycollic acid in tail liquid is 5 wt%, and the treatment process comprises the following steps:
(1) and (3) carrying out first extraction on tail liquid containing 5 wt% of thioglycollic acid by adopting a quantitative ester extractant, and extracting and enriching the thioglycollic acid to obtain first extraction liquid, wherein the content of the thioglycollic acid is 4.9 wt%. Wherein, the adopted extractant is isopropyl acetate, the volume ratio of the extractant to tail liquid is 1:2, and the operation is carried out at room temperature;
(2) adding a reaction solution (sodium hydroxide ethanol saturated solution) with the same molar weight as that of thioglycolic acid into the primary extraction liquid obtained in the step (1), reacting to generate intermediate sodium thioglycolate, precipitating, filtering, and washing solid sodium thioglycolate with ethanol;
(3) preparing the sodium thioglycolate obtained in the step (2) into a solution with the mass concentration of 70%, and adding dilute hydrochloric acid for acidification until the pH value is =1 to obtain a thioglycolic acid solution;
(4) and (3) carrying out secondary extraction on the acidified liquid with the pH =1 obtained in the step (3), and carrying out reduced pressure distillation on the obtained extract liquid by using isopropyl acetate as an extracting agent to obtain a thioglycolic acid product with the purity of 99.8 wt%. Wherein, the volume ratio of the secondary extractant to the acidizing fluid is 1:2, and the operation is carried out at room temperature.
Example 3
The invention relates to a method for separating thioglycollic acid from thiourethane tail liquid, which removes impurities in primary extraction liquid by means of primary extraction and enrichment of thioglycollic acid in tail liquid, adding reaction liquid to react in one step to separate sodium thioglycollate, then prepares the filtered sodium thioglycollate into solution for acidification, and obtains a high-purity thioglycollic acid product through reduced pressure distillation after secondary extraction. Wherein, the content of thioglycollic acid in tail liquid is 15 wt%, and the treatment process comprises the following steps:
(1) and (3) carrying out first extraction on the tail liquid containing 15 wt% of thioglycollic acid by adopting a quantitative ester extractant, and extracting the enriched thioglycollic acid to obtain a first extraction liquid, wherein the content of the thioglycollic acid is 14.2 wt%. Wherein the adopted extractant is butyl acetate, the volume ratio of the extractant to tail liquid is 1:2, and the operation is carried out at room temperature;
(2) adding a reaction solution (a saturated solution of sodium hydroxide and methanol) with the same molar weight as that of thioglycolic acid into the primary extraction liquid obtained in the step (1), reacting to generate intermediate sodium thioglycolate, precipitating, filtering, and washing solid sodium thioglycolate with ethanol. Wherein the ratio of methanol to ethanol is 1:1 by volume;
(3) preparing the sodium thioglycolate obtained in the step (2) into a solution with the mass concentration of 70%, and adding dilute hydrochloric acid for acidification until the pH value is =1 to obtain a thioglycolic acid solution;
(4) and (3) carrying out secondary extraction on the acidified liquid with the pH =1 obtained in the step (3), and carrying out reduced pressure distillation on the obtained extract liquid by using isopropyl acetate as an extracting agent to obtain a mercaptoacetic acid product with the purity of 99.6 wt%. Wherein, the volume ratio of the secondary extractant to the acidizing fluid is 1:2, and the operation is carried out at room temperature.
Example 4
The invention relates to a method for separating thioglycollic acid from thiourethane tail liquid, which removes impurities in primary extraction liquid by means of primary extraction and enrichment of thioglycollic acid in tail liquid, adding reaction liquid to react in one step to separate sodium thioglycollate, then prepares the filtered sodium thioglycollate into solution for acidification, and obtains a high-purity thioglycollic acid product through reduced pressure distillation after secondary extraction. Wherein, the content of thioglycollic acid in tail liquid is 20 wt%, and the treatment process comprises the following steps:
(1) and (3) carrying out first extraction on tail liquid containing 20 wt% of thioglycollic acid by adopting a quantitative ester extractant, and extracting the enriched thioglycollic acid to obtain first extraction liquid, wherein the content of the thioglycollic acid is 18.9 wt%. Wherein, the adopted extractant is isobutyl acetate, the volume ratio of the extractant to the tail liquid is 1:2, and the operation is carried out at room temperature;
(2) adding a reaction solution (a saturated solution of sodium hydroxide and methanol) with the same molar weight as that of thioglycolic acid into the primary extraction liquid obtained in the step (1), reacting to generate an intermediate sodium thioglycolate, precipitating and separating out, filtering, and washing solid sodium thioglycolate with methanol;
(3) preparing the sodium thioglycolate obtained in the step (2) into a solution with the mass concentration of 70%, and adding dilute hydrochloric acid for acidification until the pH value is =1 to obtain a thioglycolic acid solution;
(4) and (3) carrying out secondary extraction on the acidified liquid with the pH =1 obtained in the step (3), and carrying out reduced pressure distillation on the obtained extract liquid by using isopropyl acetate as an extracting agent to obtain a mercaptoacetic acid product with the purity of 99.5 wt%. Wherein, the volume ratio of the secondary extractant to the acidizing fluid is 1:2, and the operation is carried out at room temperature.
Example 5
The invention relates to a method for separating thioglycollic acid from thiourethane tail liquid, which removes impurities in primary extraction liquid by means of primary extraction and enrichment of thioglycollic acid in tail liquid, adding reaction liquid to react in one step to separate sodium thioglycollate, then prepares the filtered sodium thioglycollate into solution for acidification, and obtains a high-purity thioglycollic acid product through reduced pressure distillation after secondary extraction. Wherein, the content of thioglycollic acid in tail liquid is 10 wt%, and the treatment process comprises the following steps:
(1) and (3) carrying out first extraction on the tail liquid containing 10 wt% of thioglycollic acid by adopting quantitative toluene, and extracting and enriching the thioglycollic acid to obtain a first extraction liquid, wherein the content of the thioglycollic acid is 8.9 wt%. Wherein the adopted extractant is toluene, the volume ratio of the extractant to the tail liquid is 1:2, and the operation is carried out at room temperature;
(2) adding a reaction solution (a saturated solution of sodium hydroxide and methanol) with the same molar weight as that of thioglycolic acid into the primary extraction liquid obtained in the step (1), reacting to generate an intermediate sodium thioglycolate, precipitating and separating out, filtering, and washing solid sodium thioglycolate with methanol;
(3) preparing the sodium thioglycolate obtained in the step (2) into a solution with the mass concentration of 70%, and adding dilute hydrochloric acid for acidification until the pH value is =1 to obtain a thioglycolic acid solution;
(4) and (3) carrying out secondary extraction on the acidified liquid with the pH =1 obtained in the step (3), and carrying out reduced pressure distillation on the obtained extract liquid by using toluene as an extracting agent to obtain a mercaptoacetic acid product with the purity of 99.6 wt%. Wherein, the volume ratio of the secondary extractant to the acidizing fluid is 1:2, and the operation is carried out at room temperature.
Example 6
The invention relates to a method for separating thioglycollic acid from thiourethane tail liquid, which removes impurities in primary extraction liquid by means of primary extraction and enrichment of thioglycollic acid in tail liquid, adding reaction liquid to react in one step to separate sodium thioglycollate, then prepares the filtered sodium thioglycollate into solution for acidification, and obtains a high-purity thioglycollic acid product through reduced pressure distillation after secondary extraction. Wherein, the content of thioglycollic acid in tail liquid is 10 wt%, and the treatment process comprises the following steps:
(1) and (3) carrying out first extraction on tail liquid containing 10 wt% of thioglycolic acid by adopting quantitative butyl acetate, and extracting and enriching the thioglycolic acid to obtain first extraction liquid, wherein the content of the thioglycolic acid is 9.5 wt%. Wherein, the adopted extractant is isobutyl acetate, the volume ratio of the extractant to the tail liquid is 1:2, and the operation is carried out at room temperature;
(2) adding reaction liquid (saturated solution of sodium hydroxide, methanol and ethanol mixture) with the same molar weight as that of the thioglycolic acid into the primary extraction liquid obtained in the step (1), generating intermediate sodium thioglycolate after reaction, precipitating, filtering, and washing solid sodium thioglycolate with ethanol. Wherein the ratio of methanol to ethanol is 1:1 by volume;
(3) preparing the sodium thioglycolate obtained in the step (2) into a solution with the mass concentration of 70%, and adding dilute hydrochloric acid for acidification until the pH value is =1 to obtain a thioglycolic acid solution;
(4) and (3) carrying out secondary extraction on the acidified liquid with the pH =1 obtained in the step (3), and carrying out reduced pressure distillation on the obtained extract liquid by adopting diethyl ether as an extracting agent to obtain a mercaptoacetic acid product with the purity of 99.6 wt%. Wherein, the volume ratio of the secondary extractant to the acidizing fluid is 1:2, and the operation is carried out at room temperature.
Claims (5)
1. A high-value utilization method of a thiourethane production tail liquid is characterized by comprising the following steps: the method comprises the following steps:
(1) adding a primary extracting agent into the thiourethane tail liquid, extracting at room temperature, standing and layering to obtain primary extraction liquid enriched with thioglycollic acid;
(2) adding equimolar reaction liquid into the primary extraction liquid obtained in the step (1), precipitating the obtained sodium thioglycolate, and washing solid sodium thioglycolate by using a detergent after filtering;
(3) preparing the sodium thioglycolate obtained in the step (2) into a solution with a fixed concentration, and acidifying the solution with inorganic acid to obtain an acidified solution;
(4) adding a secondary extracting agent into the acidized fluid obtained in the step (3), standing and layering after secondary extraction at room temperature to obtain secondary extraction liquid containing thioglycollic acid;
(5) and (4) carrying out reduced pressure distillation on the secondary extraction liquid obtained in the step (4) to obtain a mercaptoacetic acid product with the purity of more than 99 wt%.
2. The method for high-value utilization of the tail liquid in the thiourethane production according to claim 1, which is characterized in that: the reaction solution added to the primary extraction liquid is an alcoholic solution of sodium hydroxide (wherein the alcohol is methanol, ethanol or a mixture of the two in any proportion).
3. The method for high-value utilization of the tail liquid in the thiourethane production according to claim 1, which is characterized in that: the washing agent adopted after filtration is alcohol, ether or acetone.
4. The method for high-value utilization of the tail liquid in the thiourethane production according to claim 1, which is characterized in that: the mercaptoacetic acid content in the tail liquid of the thiourethane is 5-20 wt%.
5. The process of claim 1 for separating thioglycolic acid from thiourethane tail solutions, wherein: the primary and secondary extracting agents are toluene, diethyl ether, isobutyl acetate, butyl acetate or isopropyl acetate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111689884A (en) * | 2020-07-24 | 2020-09-22 | 青岛联拓化工有限公司 | Method for preparing critical saturated aqueous solution of sodium thioglycolate by utilizing thiourethane tail liquid |
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| CN111689884A (en) * | 2020-07-24 | 2020-09-22 | 青岛联拓化工有限公司 | Method for preparing critical saturated aqueous solution of sodium thioglycolate by utilizing thiourethane tail liquid |
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Application publication date: 20200313 |