CN103360291A - Method for preparing high-concentration mercaptoacetic acid from raffinate generated in production of O-alkyl-N-alkyl thinocarbamate - Google Patents
Method for preparing high-concentration mercaptoacetic acid from raffinate generated in production of O-alkyl-N-alkyl thinocarbamate Download PDFInfo
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- CN103360291A CN103360291A CN2013102490299A CN201310249029A CN103360291A CN 103360291 A CN103360291 A CN 103360291A CN 2013102490299 A CN2013102490299 A CN 2013102490299A CN 201310249029 A CN201310249029 A CN 201310249029A CN 103360291 A CN103360291 A CN 103360291A
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Abstract
The invention discloses a method for preparing high-concentration mercaptoacetic acid from raffinate generated in production of O-alkyl-N-alkyl thinocarbamate. The method comprises the following steps of: a, acidifying, purifying and decoloring the raffinate; b, extracting the acidizing fluid with an extraction agent to obtain an extract; c, removing solvent and water from the extract; and d, flashing the processed extract at the pressure of -0.01MPa and the temperature of 90-130 DEG C to obtain the mercaptoacetic acid product with the purity of over 99.5 percent by weight. The method is reasonable in production process, low in cost and high in product quality, can be used for changing the raffinate of the O-alkyl-N-alkyl thinocarbamate into wealth to realize reasonable and effective utilization of the raffinate, and has the effect of environment protection and excellent economical and social benefits.
Description
Technical field
The invention belongs to the organic chemical industry field, be specifically related to a kind of method with producing the tail washings of O-alkyl-N-alkyl sulfide by carbamate and prepare the high density Thiovanic acid.
Background technology
Thiourethane (O-alkyl-N-alkyl sulfide is by carbamate) is international a kind of high-efficient collecting agent, and it is widely used in the nonferrous metal mines such as copper, brill, nickel, gold.General in the world chloroactic acid method is adopted in the at present production of thiourethane, namely utilizes Mono Chloro Acetic Acid, soda ash (liquid caustic soda), alkyl xanthate (C
2~ C
6Alkyl xanthogenic acid potassium/sodium salt), C
1~ C
6Above amine, four kinds of industrial chemicals output thiourethanes, the while a large amount of waste liquids of output (1:5), the Thiovanic acid radical content is 5% ~ 18% in the waste liquid.Utilize the not only environmental protection of Thiovanic acid of the tail washings production of thiourethane, realize turning waste into wealth, and cost is low, but at present the domestic tail washings that the utilizes thiourethane Thiovanic acid color of producing is yellow, purity is lower, and high-quality product can only dependence on import, has limited the application of Thiovanic acid.
Summary of the invention
Deficiency for the prior art existence, technical problem to be solved by this invention is, provide a kind of and prepare the method for high density Thiovanic acid by the tail washings of carbamate with production O-alkyl-N-alkyl sulfide, in order to utilize the tail washings production high purity of thiourethane, high-quality Thiovanic acid, low cost turns waste into wealth, and is conducive to environmental protection.
For solving the problems of the technologies described above, the technical solution used in the present invention is, a kind of method with producing the tail washings of 0-alkyl-N-alkyl sulfide by carbamate and prepare high-quality Thiovanic acid, and it may further comprise the steps:
A, to described tail washings with the mineral acid acidification to PH be 0.5-2;
B, acidizing fluid was left standstill 0.5-3 days, the organism of removal of impurities separate out suspended, the then assorted decolouring of extraction removes impurity and coloring matter in the acidizing fluid with organic solvent extraction; Acidizing fluid after processing is extracted with extraction agent, be extracted liquid;
C, with extraction liquid desolvation and water, obtain thick acid;
D is under-0.01MPa vacuum tightness, and temperature is under 90-130 ℃ flash distillation to be carried out in thick acid, and obtaining purity is the above Thiovanic acid products of 99.5 wt %.
The volume ratio of extraction of the present invention its used organic solvent of assorted decolouring and acidizing fluid is 2.5:0. 1 ~ 1, used organic solvent is ester class organic solvent, is selected from one or more in ethyl acetate, propyl acetate, isopropyl acetate, butylacetate, the isobutyl acetate.
The volume ratio of the acidizing fluid after its used extraction agent of extraction described in the step b of the present invention and the processing is 2.0:0. 1 ~ 2, described extraction agent is ester class, ethers mixed extractant, and wherein: the ester class is one or more in ethyl acetate, propyl acetate, isopropyl acetate, butylacetate, the isobutyl acetate; Ethers is one or more in ether, isopropyl ether, sherwood oil, the methyl-isobutyl methyl ether.
The volume ratio of its used organic solvent of assorted decolouring of extraction described in the step b of the present invention and acidizing fluid is 2.5:0. 3, and the volume ratio of the acidizing fluid after its used extraction agent of described extraction step and the processing is 2.0:0. 8.Extraction described in the step b is multistage countercurrent continuous extraction.
The present invention extracts acidizing fluid and extracts assorted process and carries out respectively 2 ~ 7 times.
Mineral acid described in the step a of the present invention is dilute hydrochloric acid or dilute sulphuric acid.
Method with producing the tail washings of O-alkyl-N-alkyl sulfide by carbamate and prepare the high density Thiovanic acid of the present invention is utilized the tail washings production high purity of thiourethane, high-quality Thiovanic acid, and low cost turns waste into wealth, and is conducive to environmental protection.Have advantages of that production technique is reasonable and production cost is low, the Thiovanic acid purity of utilizing the present invention to prepare reaches more than the 99. 5 wt %, and quality reaches the imported product standard, alternative import.
Embodiment
Method with producing the tail washings of 0-alkyl-N-alkyl sulfide by carbamate and prepare high-quality Thiovanic acid of the present invention may further comprise the steps:
A, to described tail washings with the mineral acid acidification to PH be 0.5-2; B, acidizing fluid was left standstill 0.5-3 days, the organism of removal of impurities separate out suspended, the then assorted decolouring of extraction removes impurity and coloring matter in the acidizing fluid with organic solvent extraction; Acidizing fluid after processing is extracted with extraction agent, be extracted liquid; C, with extraction liquid desolvation and water, obtain thick acid; D is under-0.01MPa pressure, and temperature is under 90-130 ℃ flash distillation to be carried out in thick acid, and obtaining purity is the above Thiovanic acid products of 99.5 wt %.The present invention is described in more detail below in conjunction with embodiment, but be not limited to following approach.
Embodiment 1
In the present embodiment, prepare the method for high-quality Thiovanic acid by the tail washings of carbamate, comprise following content with production 0-alkyl-N-alkyl sulfide:
1) gets the tail washings 1L hcl acidifying that contains Thiovanic acid 10.5wt%, to PH=2, left standstill 24 hours, the organism of separate out suspended, then ether and the sherwood oil mixed solvent of quality such as use to carry out removal of impurities, decolouring to the tail washings after the acidifying, the volume ratio of organic solvent and acidizing fluid is 2.5:0. 1, and obtaining new acidizing fluid is colourless transparent solution, contains Thiovanic acid 9. 8wt%.
2) get the new acidizing fluid of 200m1 under 25 ℃ of temperature, ether, the ethyl acetate mixed solution of quality such as at first use to extract as extraction agent, the volume ratio of extraction agent and new acidizing fluid is 1:3, and the number of times of extraction is 6 times, obtains colourless extraction liquid after the extraction.
3) extraction liquid is carried out air distillation, remove extraction agent and water, obtain thick acid, content is 85 wt%.
4) under-0.01MPa vacuum tightness, carry out flash distillation under 130 ℃, obtaining purity is above, the colourless Thiovanic acid product of 99.5wt%.
Embodiment 2
In the present embodiment, prepare the method for high-quality Thiovanic acid by the tail washings of carbamate, comprise following content with production 0-alkyl-N-alkyl sulfide:
1) gets the tail washings 1L hcl acidifying that contains Thiovanic acid 10.5wt%, to PH=0.5, left standstill 12 hours, the organism of separate out suspended, then isopropyl ether and the methyl-isobutyl methyl ether mixed solvent of quality such as use to carry out removal of impurities, decolouring to the tail washings after the acidifying, the volume ratio of organic solvent and acidizing fluid is 2.5:1, and obtaining new acidizing fluid is colourless transparent solution, contains Thiovanic acid 9. 8wt%.
2) get the new acidizing fluid of 200m1 under 25 ℃ of temperature, isopropyl ether, the propyl acetate mixed solution of quality such as at first use to extract as extraction agent, the volume ratio of extraction agent and new acidizing fluid is 2:1, and the number of times of extraction is 2 times, obtains colourless extraction liquid after the extraction.
3) extraction liquid is carried out air distillation, remove extraction agent and water, obtain thick acid, content is 85 wt%.
4) under-0.01MPa vacuum tightness, carry out flash distillation under 90 ℃, obtaining purity is above, the colourless Thiovanic acid product of 99.5wt%.
Embodiment 3
In the present embodiment, prepare the method for high-quality Thiovanic acid by the tail washings of carbamate, comprise following content with production 0-alkyl-N-alkyl sulfide:
1) gets the tail washings 1L hcl acidifying that contains Thiovanic acid 10.5wt%, to PH=1, left standstill 72 hours, the organism of separate out suspended, then ether, the isopropyl ether mixed solvent of quality such as use to carry out removal of impurities, decolouring to the tail washings after the acidifying, the volume ratio of organic solvent and acidizing fluid is 2.5:0. 3, and obtaining new acidizing fluid is colourless transparent solution, contains Thiovanic acid 9. 8wt%.
2) get the new acidizing fluid of 200m1 under 25 ℃ of temperature, isopropyl ether, the propyl acetate mixed solution of quality such as at first use to extract as extraction agent, the volume ratio of extraction agent and new acidizing fluid is 2.0:0.8, the number of times of extraction is 7 times, obtains colourless extraction liquid after the extraction.
3) extraction liquid is carried out air distillation, remove extraction agent and water, obtain thick acid, content is 85 wt%.
4) under-0.01MPa vacuum tightness, carry out flash distillation under 110 ℃, obtaining purity is above, the colourless Thiovanic acid product of 99.5wt%.
The present invention has advantages of that production technique is reasonable and production cost is low.Utilize the present invention to prepare Thiovanic acid, make production O-alkyl-N-alkyl sulfide be fully utilized by the tail washings of carbamate, not only turn waste into wealth, and solved problem of environmental pollution.
The Thiovanic acid quality product of utilizing the present invention to prepare reaches the imported product standard, alternative import.The present invention can contain for the production of O-alkyl-N-alkyl sulfide the recycling of the tail washings of Thiovanic acid by amino formate.
Claims (7)
- Prepare the method for high-quality Thiovanic acid by the tail washings of carbamate, it is characterized in that: may further comprise the steps with production 0-alkyl-N-alkyl sulfide:A, to described tail washings with the mineral acid acidification to PH be 0.5-2; B, acidizing fluid was left standstill 0.5-3 days, the organism of removal of impurities separate out suspended, the then assorted decolouring of extraction removes impurity and coloring matter in the acidizing fluid with organic solvent extraction; Acidizing fluid after processing is extracted with extraction agent, be extracted liquid; C, with extraction liquid desolvation and water, obtain thick acid; D is under-0.01MPa vacuum tightness, and temperature is under 90-130 ℃ flash distillation to be carried out in thick acid, and obtaining purity is the above Thiovanic acid products of 99.5 wt %.
- Method with producing the tail washings of O-alkyl-N-alkyl sulfide by carbamate and prepare high-quality Thiovanic acid according to claim 1, it is characterized in that: the volume ratio of its used organic solvent of assorted decolouring of extraction described in the step b and acidizing fluid is 2.5:0. 1 ~ 1, used organic solvent is ester class organic solvent, is selected from one or more in ethyl acetate, propyl acetate, isopropyl acetate, butylacetate, the isobutyl acetate.
- Method with producing the tail washings of O-alkyl-N-alkyl sulfide by carbamate and prepare the high density Thiovanic acid according to claim 2, it is characterized in that: the volume ratio of the acidizing fluid after its used extraction agent of extraction described in the step b and the processing is 2.0:0. 1 ~ 2, described extraction agent is ester class, ethers mixed extractant, and wherein: the ester class is one or more in ethyl acetate, propyl acetate, isopropyl acetate, butylacetate, the isobutyl acetate; Ethers is one or more in ether, isopropyl ether, sherwood oil, the methyl-isobutyl methyl ether.
- Method with producing the tail washings of O-alkyl-N-alkyl sulfide by carbamate and prepare the high density Thiovanic acid according to claim 3, it is characterized in that: the volume ratio of its used organic solvent of assorted decolouring of extraction described in the step b and acidizing fluid is 2.5:0. 3, and the volume ratio of the acidizing fluid after its used extraction agent of described extraction and the processing is 2.0:0. 8.
- Method with producing the tail washings of O-alkyl-N-alkyl sulfide by carbamate and prepare high-quality Thiovanic acid according to claim 4 is characterized in that extraction is multistage countercurrent continuous extraction described in the step b.
- ：Method with producing the tail washings of O-alkyl-N-alkyl sulfide by carbamate and prepare high-quality Thiovanic acid according to claim 5 is characterized in that: acidizing fluid is extracted and extracts assorted process carry out respectively 2 ~ 7 times.
- Method with producing the tail washings of O-alkyl-N-alkyl sulfide by carbamate and prepare high-quality Thiovanic acid according to claim 1, it is characterized in that: mineral acid described in the step a is dilute hydrochloric acid or dilute sulphuric acid.
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|---|---|---|---|
| CN201310249029.9A CN103360291B (en) | 2013-06-21 | 2013-06-21 | With producing the method that high concentration TGA prepared by the O-alkyl-N-alkyl sulfide tail washings by carbamate |
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| CN201310249029.9A CN103360291B (en) | 2013-06-21 | 2013-06-21 | With producing the method that high concentration TGA prepared by the O-alkyl-N-alkyl sulfide tail washings by carbamate |
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| CN103360291B CN103360291B (en) | 2016-12-07 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237449A (en) * | 2015-11-09 | 2016-01-13 | 青岛联拓化工有限公司 | Method for preparing high-concentration mercaptoacetic acid from tail liquid of O-alkyl-N-alkyl thinocarbamate production |
| CN105254547A (en) * | 2015-11-05 | 2016-01-20 | 上海韬鸿化工科技有限公司 | Method for preparing high-quality mercaptoacetic acid from tail solution from O-alkyl-N-alkyl thinocarbamate production |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105664A (en) * | 1994-05-25 | 1995-07-26 | 沈阳矿冶研究所 | Preparation of isooctyl mercaptoacetate by using tailing liquor containing mercaptoacetic acid from production of thiourethane |
| CN1152569A (en) * | 1995-12-22 | 1997-06-25 | 陈忠平 | Method for recovering thioglycollic acid from waste liquid of producing thiamine ester |
| CN1408707A (en) * | 2001-09-20 | 2003-04-09 | 刘明友 | Process for recovering sodium mercaptoacetate from production of thia amino-ester waste liquid |
-
2013
- 2013-06-21 CN CN201310249029.9A patent/CN103360291B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105664A (en) * | 1994-05-25 | 1995-07-26 | 沈阳矿冶研究所 | Preparation of isooctyl mercaptoacetate by using tailing liquor containing mercaptoacetic acid from production of thiourethane |
| CN1152569A (en) * | 1995-12-22 | 1997-06-25 | 陈忠平 | Method for recovering thioglycollic acid from waste liquid of producing thiamine ester |
| CN1408707A (en) * | 2001-09-20 | 2003-04-09 | 刘明友 | Process for recovering sodium mercaptoacetate from production of thia amino-ester waste liquid |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254547A (en) * | 2015-11-05 | 2016-01-20 | 上海韬鸿化工科技有限公司 | Method for preparing high-quality mercaptoacetic acid from tail solution from O-alkyl-N-alkyl thinocarbamate production |
| CN105254547B (en) * | 2015-11-05 | 2019-01-01 | 青岛联拓化工有限公司 | With production O- alkyl-N- alkyl sulfide by the method for the tail washings preparation high-quality thioacetic acid of carbamate |
| CN105237449A (en) * | 2015-11-09 | 2016-01-13 | 青岛联拓化工有限公司 | Method for preparing high-concentration mercaptoacetic acid from tail liquid of O-alkyl-N-alkyl thinocarbamate production |
| 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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| CN103360291B (en) | 2016-12-07 |
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Inventor after: Li Xuan Inventor after: Li Fang Inventor after: Shen Wenbin Inventor before: Li Xuan |