CN103360291B - With producing the method that high concentration TGA prepared by the O-alkyl-N-alkyl sulfide tail washings by carbamate - Google Patents
With producing the method that high concentration TGA prepared by the O-alkyl-N-alkyl sulfide tail washings by carbamate Download PDFInfo
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- CN103360291B CN103360291B CN201310249029.9A CN201310249029A CN103360291B CN 103360291 B CN103360291 B CN 103360291B CN 201310249029 A CN201310249029 A CN 201310249029A CN 103360291 B CN103360291 B CN 103360291B
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Abstract
The invention discloses a kind of utilize O alkyl N alkyl sulfide by carbamate tail washings produce high concentration TGA method, comprise the following steps: a, tail washings is acidified, remove impurity, decolouring；B, by acidifying solution with extractant extract, be extracted liquid；C, by extract desolvation and water；D, under 0.01MPa, carry out flash distillation at 90 130 DEG C, obtain the TGA product that purity is 99.5 more than wt %.Production technology of the present invention is reasonable, low cost, and product quality is high, can be turned waste into wealth by the tail washings of carbamate by O alkyl N alkyl sulfide, the most efficient utilization, environmentally friendly, has good economic and social benefit.
Description
Technical field
The invention belongs to organic chemical industry field, be specifically related to a kind of method that production O-alkyl-N-alkyl sulfide prepares high concentration TGA by the tail washings of carbamate.
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.Producing of thiourethane uses the most general chloroactic acid method at present, i.e. utilizes monoxone, soda (liquid caustic soda), alkyl xanthate (C2~C6Alkyl xanthogenic acid potassium/sodium salt), C1~C6Above amine, four kinds of industrial chemicals output thiourethanes, the simultaneously a large amount of waste liquid of output (1:5), in waste liquid, TGA radical content is 5% ~ 18%.Utilize the TGA not only environmental protection that the tail washings of thiourethane produces, it is achieved turn waste into wealth, and low cost, but the TGA color that the most domestic tail washings utilizing thiourethane produces is more yellow, purity is relatively low, the product of high-quality can only dependence on import, limit the application of TGA.
Summary of the invention
The deficiency existed for prior art, the technical problem to be solved is, a kind of method that production O-alkyl-N-alkyl sulfide prepares high concentration TGA by the tail washings of carbamate is provided, so that the tail washings utilizing thiourethane produces high-purity, the TGA of high-quality, low cost turns waste into wealth, and beneficially environmental protection.
For solving above-mentioned technical problem, the technical solution used in the present invention is, a kind of method that production 0-alkyl-N-alkyl sulfide prepares high-quality TGA by the tail washings of carbamate, and it comprises the following steps:
A, it is 0.5-2 to described tail washings with mineral acid acidified process to PH；
B, acidifying solution standing 0.5-3 days, remove impurity separates the Organic substance suspended, and then extracts miscellaneous decolouring, with the impurity in organic solvent extraction removing acidifying solution and coloring matter；Acidifying solution extractant after processing extracts, and is extracted liquid；
C, by extract desolvation and water, obtain thick acid；
D is under-0.01MPa vacuum, and thick acid is carried out flash distillation at being 90-130 DEG C by temperature, obtains the TGA product that purity is 99.5 more than wt %.
The miscellaneous decolouring of extraction of the present invention organic solvent used by it is 2.5:0. 1 ~ 1 with the volume ratio of acidifying solution, and organic solvent used is based organic solvent, one or more in ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate.
The volume ratio of the acidifying solution after extracting extractant used by it described in step b of the present invention and processing is 2.0:0. 1 ~ 2, described extractant is esters, ethers mixed extractant, wherein: esters is one or more in ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate；Ethers is one or more in ether, diisopropyl ether, petroleum ether, methyl-isobutyl methyl ether.
The volume ratio extracting miscellaneous decolouring organic solvent used by it and acidifying solution described in step b of the present invention is 2.5:0. 3, described extraction step extractant used by it with process after the volume ratio of acidifying solution be 2.0:0. 8.Extraction described in step b is multistage countercurrent continuous extraction.
Acidifying solution is extracted and extracts miscellaneous process and carries out respectively 2 ~ 7 times by the present invention.
Mineral acid described in step a of the present invention is dilute hydrochloric acid or dilute sulfuric acid.
The present invention with producing the method that O-alkyl-N-alkyl sulfide prepares high concentration TGA by the tail washings of carbamate, utilize the tail washings of thiourethane to produce high-purity, the TGA of high-quality, low cost turns waste into wealth, beneficially environmental protection.Having the advantage that production technology is reasonable and production cost is low, the TGA purity utilizing the present invention to prepare reaches 99. 5 more than wt %, and quality reaches imported product standard, alternative import.
Detailed description of the invention
The present invention with producing the method that 0-alkyl-N-alkyl sulfide prepares high-quality TGA by the tail washings of carbamate, comprise the following steps:
A, it is 0.5-2 to described tail washings with mineral acid acidified process to PH；B, acidifying solution standing 0.5-3 days, remove impurity separates the Organic substance suspended, and then extracts miscellaneous decolouring, with the impurity in organic solvent extraction removing acidifying solution and coloring matter；Acidifying solution extractant after processing extracts, and is extracted liquid；C, by extract desolvation and water, obtain thick acid；D is under-0.01MPa pressure, and thick acid is carried out flash distillation at being 90-130 DEG C by temperature, obtains the TGA product that purity is 99.5 more than wt %.Below in conjunction with embodiment, the present invention is described in more detail, but is not limited to following approach.
Embodiment 1
In the present embodiment, with producing the method that high-quality TGA prepared by the 0-alkyl-N-alkyl sulfide tail washings by carbamate, including following content:
1) take the tail washings 1L hydrochloric acid containing TGA 10.5wt% to be acidified, to PH=2, stand 24 hours, separate the Organic substance suspended, then ether and petroleum ether mixed solvent to quality such as the tail washings use after acidifying carry out remove impurity, decolouring, organic solvent is 2.5:0. 1 with the volume ratio of acidifying solution, and obtaining new acidifying solution is colourless transparent solution, containing TGA 9. 8wt%.
2) taking the new acidifying solution of 200m1 at temperature 25 DEG C, the first ether of quality, the ethyl acetate mixtures such as use extracts as extractant, and extractant is 1 with the volume ratio of new acidifying solution:
3, the number of times of extraction is 6 times, obtains colourless extract after extraction.
3) extract carrying out air-distillation, remove extractant and water, obtain thick acid, content is 85 wt%.
4) under-0.01MPa vacuum, at 130 DEG C, carry out flash distillation, obtain purity be more than 99.5wt%, colourless TGA product.
Embodiment 2
In the present embodiment, with producing the method that high-quality TGA prepared by the 0-alkyl-N-alkyl sulfide tail washings by carbamate, including following content:
1) take the tail washings 1L hydrochloric acid containing TGA 10.5wt% to be acidified, to PH=0.5, stand 12 hours, separate the Organic substance suspended, then diisopropyl ether and methyl-isobutyl methyl ether mixed solvent to quality such as the tail washings use after acidifying carry out remove impurity, decolouring, organic solvent is 2.5:1 with the volume ratio of acidifying solution, and obtaining new acidifying solution is colourless transparent solution, containing TGA 9. 8wt%.
2) taking the new acidifying solution of 200m1 at temperature 25 DEG C, the first diisopropyl ether of quality, the propyl acetate mixed liquor such as use extracts as extractant, and extractant and the volume ratio of new acidifying solution are 2:1, and the number of times of extraction is 2 times, obtains colourless extract after extraction.
3) extract carrying out air-distillation, remove extractant and water, obtain thick acid, content is 85 wt%.
4) under-0.01MPa vacuum, at 90 DEG C, carry out flash distillation, obtain purity be more than 99.5wt%, colourless TGA product.
Embodiment 3
In the present embodiment, with producing the method that high-quality TGA prepared by the 0-alkyl-N-alkyl sulfide tail washings by carbamate, including following content:
1) take the tail washings 1L hydrochloric acid containing TGA 10.5wt% to be acidified, to PH=1, stand 72 hours, separate the Organic substance suspended, then the ether of quality, the diisopropyl ether mixed solvents such as the tail washings use after acidifying are carried out remove impurity, decolouring, organic solvent is 2.5:0. 3 with the volume ratio of acidifying solution, and obtaining new acidifying solution is colourless transparent solution, containing TGA 9. 8wt%.
2) the new acidifying solution of 200m1 is taken at temperature 25 DEG C, first the diisopropyl ether of quality such as use, propyl acetate mixed liquor extracts as extractant, and extractant and the volume ratio of new acidifying solution be, 2.0:0.8, the number of times of extraction is 7 times, obtains colourless extract after extraction.
3) extract carrying out air-distillation, remove extractant and water, obtain thick acid, content is 85 wt%.
4) under-0.01MPa vacuum, at 110 DEG C, carry out flash distillation, obtain purity be more than 99.5wt%, colourless TGA product.
The present invention has the advantage that production technology is reasonable and production cost is low.Utilize the present invention to prepare TGA, make production O-alkyl-N-alkyl sulfide be comprehensively utilized by the tail washings of carbamate, not only turn waste into wealth, and solve problem of environmental pollution.
The TGA product quality utilizing the present invention to prepare reaches imported product standard, alternative import.The present invention may be used for producing the recycling of the tail washings that O-alkyl-N-alkyl sulfide contains TGA by carbamates.
Claims (2)
1. with producing the method that TGA prepared by the 0-alkyl-N-alkyl sulfide tail washings by carbamate, it is characterised in that: comprise the following steps:
A, it is 0.5-2 to described tail washings with mineral acid acidified process to pH；
B, acidifying solution standing 0.5-3 days, remove impurity separates the Organic substance suspended, and then extracts miscellaneous decolouring 2～7 times, with organic solvent extraction removing acidifying
Impurity in liquid and coloring matter；Acidifying solution extractant after processing carries out extracting 2～7 times, is extracted liquid；
C, by extract desolvation and water, obtain thick acid；
D, under-0.01MPa vacuum, thick acid is carried out flash distillation at being 90-130 DEG C by temperature, obtains the TGA that purity is more than 99.5wt%
Product；
Mineral acid described in step a is dilute hydrochloric acid or dilute sulfuric acid；
The volume ratio extracting organic solvent used by miscellaneous decolouring and acidifying solution described in step b is 2.5: 0.1～1, and organic solvent used is that ether/petroleum ether mixes
Bonding solvent, diisopropyl ether/methyl-isobutyl methyl ether mixed solvent or ether/diisopropyl ether mixed solvent；
Extractant described in step b is esters, ethers mixed extractant, wherein: esters is ethyl acetate, propyl acetate, isopropyl acetate, second
One or more in acid butyl ester, isobutyl acetate；Ethers is one or more in ether, diisopropyl ether, petroleum ether, methyl-isobutyl methyl ether；
The volume ratio of the acidifying solution after extractant and process is 2.0: 0.1～2；
Extraction described in step b is multistage countercurrent continuous extraction.
The method that production 0-alkyl-N-alkyl sulfide the most according to claim 1 prepares TGA by the tail washings of carbamate, its feature
It is: the volume ratio extracting organic solvent used by miscellaneous decolouring and acidifying solution described in step b is 2.5: 0.3, after extractant used by described extraction and process
The volume ratio of acidifying solution be 2.0: 0.8.
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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 true CN103360291B (en) | 2016-12-07 |
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| 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 |
| CN111689884B (en) * | 2020-07-24 | 2021-12-17 | 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 |
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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 |
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Inventor after: Li Xuan Inventor after: Li Fang Inventor after: Shen Wenbin Inventor before: Li Xuan |
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