CN1105664A - Preparation of isooctyl mercaptoacetate by using tailing liquor containing mercaptoacetic acid from production of thiourethane - Google Patents
Preparation of isooctyl mercaptoacetate by using tailing liquor containing mercaptoacetic acid from production of thiourethane Download PDFInfo
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- CN1105664A CN1105664A CN 94110279 CN94110279A CN1105664A CN 1105664 A CN1105664 A CN 1105664A CN 94110279 CN94110279 CN 94110279 CN 94110279 A CN94110279 A CN 94110279A CN 1105664 A CN1105664 A CN 1105664A
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- thiovanic acid
- isooctyl
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Abstract
The present invention relates to a preparation method of isooctyl mercaptoacetate by using tail liquor containing mercaptoacetic acid used for producing thiourethane, including the following steps: it uses isooctyl alcohol and makes it pass through the process of counter-current extraction to extract mercapto-contained acetic acid solution; and esterifies its supporting organic phase to obtain a crude ester, and then it makes the crude ester pass through the processes of vacuum distillation and purification. It is characterized by that (1) the tail liquor containing mercaptoacetic acid used for producing thiourethane is used as raw material, in which the mercapto-contained acetic acid is 8-14%; (2) before counter-current extraction, the tail liquor is acidified by using sulfuric acid or chlorhydric acid, and its pH value is less than 3, and after having been acidified, it is stood for 1-3 days, and then its organic substances are separated out by using organic solvent.
Description
The present invention relates to the technology of preparing of isooctyl mercaptoacetate, particularly with the method that the Thiovanic acid tail washings is produced the different monooctyl ester of Thiovanic acid that contains of producing thiourethane.
Isooctyl mercaptoacetate is a raw material of producing nontoxic polyvinyl chloride thermo-stabilizer-ester group tin (or antimony), and this product development abroad is very fast, thereby the demand of isooctyl mercaptoacetate also increases thereupon.The technology of preparing of isooctyl mercaptoacetate is divided two big classes basically at present, a kind of is " sulfhydrylation after the first esterification " method, as at document Neth Appl 6500854(1965), Belg Pat 66843(1970), patent DD 214126(1984), DD270063(1989) carry.Another kind is " esterification behind the first sulfhydrylation " method, and the U.S. delivered patent US2832751(1958 in 1958), with the Thiovanic acid direct esterification of alcohol excess and 97%, this method needs the high Thiovanic acid of purity to make raw material, the cost height.The seventies East Germany proposes patent DD127117(1977), improved esterification equipment, adopt continuous processing, need be raw material with the Thiovanic acid of 80～90% purity, transformation efficiency can reach 98%.With the most approaching technology of the present invention be the patent DE2426399(1974 that West Germany Cibe company in 1971 delivers), primary process is the dilute solution (content 6.6%) of earlier synthetic Thiovanic acid, dewater in 110 ℃ of underpressure distillation esterifications with the isooctyl alcohol counter-current extraction, productive rate reaches about 85% again.This kind method is when the first step is produced Thiovanic acid, need with more expensive Mono Chloro Acetic Acid raw material, synthesize Thiovanic acid with Sodium sulfhydrate aqueous solution successive reaction in pressurised equipment, or Mono Chloro Acetic Acid and Sulfothiorine are reacted the special salt of generation group in water medium, add acid then, heating hydrolysis, add the zinc powder reduction after the hydrolysis again, make the Thiovanic acid dilute solution, this step needs more expensive raw material, complex process, synthesis cycle is long.
The object of the present invention is to provide a kind of method that the Thiovanic acid tail washings is produced isooctyl mercaptoacetate that contains, make production technique simple with the production thiourethane, with short production cycle, and the isooctyl mercaptoacetate product cost that synthesizes is low.
The invention provides a kind of method that the Thiovanic acid tail washings is produced isooctyl mercaptoacetate that contains, comprise the steps: with the production thiourethane
-contain Thiovanic acid solution with the isooctyl alcohol counter-current extraction;
-load organic phases is carried out esterification, obtain thick fat;
-thick fat underpressure distillation is purified;
It is characterized in that:
(1) adopts the Thiovanic acid tail washings that contains of producing thiourethane to make raw material, wherein contain Thiovanic acid 8～14%;
(2) tail washings needs through following processing before counter-current extraction:
-with sulfuric acid or hydrochloric acid to the tail washings acidification to PH＜3;
Left standstill after-the acidifying 1～3 day, and separated the come-up organism;
-extract organic substance in the tail washings with the hydro carbons of low carbon chain such as sherwood oil, ether or ether organic solvent, the amount of organic solvent is 1～5%(vol of acidizing fluid).
In general in the thiourethane tail washings, mainly contain the condenses of yellow soda ash, sodium hydroxide, sodium sulphite, trithiocarbonic acid sodium and a spot of thiourethane, Thiovanic acid of Thioglycolic acid sodium salt, sodium-chlor and trace or oxide compound etc.Thereby when producing the raw material of isooctyl mercaptoacetate with its conduct, must removal of impurities handle, this tail washings is an alkalescence, at first is acidified with acid, the acidifying tail washings is left standstill appropriate time, also the organic impurity of remnants such as thiourethane etc. can be extracted with the low carbon chain organic solvent again and remove.Then available isooctyl alcohol extraction Thiovanic acid, inorganics impurity will be stayed in the water collection tail and be separated.The concrete processing parameter of extraction and esterification is:
When (1) isooctyl alcohol extracts acidizing fluid,
Being in a ratio of of-acidizing fluid and isooctyl alcohol: 1: 0.3～1.2;
-adopt 3～5 stage countercurrents to extract;
-extraction temperature is 15～35 ℃.
When (2) esterification is carried out in underpressure distillation,
-make esterifying catalyst with tosic acid or sulfuric acid, catalyst levels is 0.02%～0.4%;
-under vacuum condition, esterification temperature is 50～140 ℃, 2～8 hours time.
Before esterification, can in the organic phase of load Thiovanic acid, add the Thiovanic acid of high density.
The present invention has following advantage:
1) make the Thiovanic acid tail washings that contains of producing thiourethane obtain comprehensive utilization, the protection environment.
2) make that the Thiovanic acid rate of recovery reaches 98% in the tail washings, turn waste into wealth.
3) isooctyl mercaptoacetate of producing reaches importer's series products standard, and cheap, alternative import.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
The removal of impurities of thiourethane tail washings is handled:
A. get tail washings 5000ml hcl acidifying, PH=2.5, contain Thiovanic acid 0.5% in the acidizing fluid, contain organic impurities 0.04%, acidizing fluid is filtered by secondary solid packing post, deviate from suspended substance, filtrate is clear solution, get 1000ml filtrate and use the 15ml petroleum ether extraction, stirred 10 minutes, left standstill 20 minutes, separating residual is micro organic impurity in filtrate, collection contains Thiovanic acid 10.1% in the tail, and as the raw material of producing ester, inorganics impurity such as sodium-chlor will be stayed the neutralization of water collection tail with separation after next step is with isooctyl alcohol extraction Thiovanic acid.
B. with A get tail washings 5000ml with hcl acidifying to PH=1.5, contain Thiovanic acid 9.43% in the acidizing fluid, filter, deviate from suspended substance by 2 grades of filled columns, filtrate is clear solution, get 1000ml filtrate, use the 15ml petroleum ether extraction, stirred 10 minutes, left standstill 20 minutes, the micro-content organism impurity of separating residual, the collection tail contains Thiovanic acid 9.08%, as the raw material of producing ester.
C. get tail washings 5000ml with A, to PH=1.5, contain Thiovanic acid 9.3% in the acidizing fluid with hcl acidifying, filter by 2 grades of filled columns, deviate from suspended substance, obtained transparent solution, got this solution of 2000ml, use the 50ml petroleum ether extraction, stirred 10 minutes, left standstill 20 minutes, the micro-content organism impurity of separating residual, the collection tail contains Thiovanic acid 8.9%, as the raw material of producing ester.
Embodiment 2
With industrial isooctyl alcohol extraction acidizing fluid, being in a ratio of of acidizing fluid and isooctyl alcohol: 1: 0.5; Acidizing fluid 250 with after the removal of impurities processing wherein contains Thiovanic acid 9.36%, after room temperature is with the isooctyl alcohol extraction, obtains load organic phases 197g, contains Thiovanic acid 11.64%, and raffinate contains Thiovanic acid 0.20%, and recovery of extraction is 98.10%.
Embodiment 3
With embodiment 2 extracting process, be in a ratio of: 1: 0.6, get load organic phases 490g, contain Thiovanic acid 12.55%, add 0.1g to a toluenesulphonic acids, material is put into the esterification bottle, under vacuum condition, in 80～140 ℃ of esterifications 6 hours, make thick ester 0.6258mole, transformation efficiency 93.63%.
Embodiment 4
With embodiment 2 extracting process, be in a ratio of 11: 0.9, get load organic phases 737g, contain Thiovanic acid 15.4%, add 2g to a toluenesulphonic acids, material is put into the esterification bottle, under vacuum condition, 80～140 ℃ of esterifications 6 hours make thick ester 1.2275mole, transformation efficiency 99.5%.
Embodiment 5
With embodiment 2 extracting process, be in a ratio of 1: 1.2, get load organic phases 426g, contain Thiovanic acid 17.7%, add vitriol oil 0.34g, material is put into the esterification bottle, under vacuum condition, in 70～130 ℃ of esterifications 6 hours, make the thick ester of 0.8121mole, transformation efficiency 99.06%.
Embodiment 6
With embodiment 2 extracting process, adding the denseer Thiovanic acid of a part in organic phase, to contain Thiovanic acid in organic phase be 22.6%, get this load organic phases 763g, add a toluenesulphonic acids 3g, material is put into the esterification bottle, under vacuum condition, in 80～140 ℃ of esterifications 6 hours, make thick ester 1.8593mole, transformation efficiency 99.2%.
Embodiment 7
Thick ester rectifying and rectifying: with the extracting process of embodiment 2, also add the denseer Thiovanic acid of a part, make load organic phases contain Thiovanic acid 21.14%, get this organic phase 846kg, adding is carried out underpressure distillation to a toluenesulphonic acids 1.6kg, steam water and mix ester in 80～100 ℃, water 20kg mixes ester 422kg, contains ester 19.76%, steam thick ester 345.7kg at 100 ℃～140 ℃, contain ester 88.87%, raffinate 43.2kg in the still contains ester 10.37%, promptly lose 1.11% in raffinate, total recovery is 98.5%.
Get the thick ester of 871kg (containing ester 88.79%), the heavy 773.36kg of pure ester, under vacuum condition, distill,, contain ester 65.83% in 80～115 ℃ of collection 225.5kg, account for 19.2% of total ester, steam 224.3kg at 115～125 ℃, contain ester 93.03%, account for 26.98% of total ester, obtain the smart ester of 419.6kg 125 ℃～145 ℃ distillations, purity is 99.19%, pure content 0.27%, acid number 0.5mgKOH/g, sulphur content＞15.3%, the yield of smart ester is 53.81%, and raffinate only is 1.6kg in the still, and total recovery is 99.99%, distillage is colourless transparent liquid, but preceding two cut redistillation are purified.
Claims (3)
1, a kind of with the method that the Thiovanic acid tail washings is produced isooctyl mercaptoacetate that contains of producing thiourethane, comprise the steps:
--contain Thiovanic acid solution with the isooctyl alcohol counter-current extraction;
--load organic phases is carried out esterification, obtain thick fat;
--thick fat underpressure distillation is purified;
It is characterized in that:
(1) adopts the Thiovanic acid tail washings that contains of producing thiourethane to make raw material, wherein contain Thiovanic acid 8～14%;
(2) tail washings needs through following processing before counter-current extraction:
--with sulfuric acid or hydrochloric acid to the tail washings acidification to pH＜3;
--left standstill after the acidifying 1～3 day, and separated the come-up organism;
--extract organic substance in the tail washings with the hydro carbons of low carbon chain such as sherwood oil, ether or ether organic solvent, the amount of organic solvent is 1～5% (a content percentage ratio) of acidizing fluid.
2, by the described method of producing isooctyl mercaptoacetate of claim 1, it is characterized in that
When (1) isooctyl alcohol extracts acidizing fluid,
Being in a ratio of of-acidizing fluid and isooctyl alcohol: 1: 0.3～1.2;
-adopt 3～5 stage countercurrents to extract;
-extraction temperature is 15～35 ℃.
When (2) esterification is carried out in underpressure distillation,
-make esterifying catalyst with tosic acid or sulfuric acid, catalyst levels is 0.02%～0.4%;
-under vacuum condition, esterification temperature is 50～140 ℃, 2～8 hours time.
3, by claim 1, the 2 described methods of producing isooctyl mercaptoacetate is characterized in that: before esterification, can add the Thiovanic acid of high density in the organic phase of load Thiovanic acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110279A CN1040978C (en) | 1994-05-25 | 1994-05-25 | Preparation of isooctyl mercaptoacetate by using tailing liquor containing mercaptoacetic acid from production of thiourethane |
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| CN94110279A CN1040978C (en) | 1994-05-25 | 1994-05-25 | Preparation of isooctyl mercaptoacetate by using tailing liquor containing mercaptoacetic acid from production of thiourethane |
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| CN1105664A true CN1105664A (en) | 1995-07-26 |
| CN1040978C CN1040978C (en) | 1998-12-02 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318750B (en) * | 2008-07-22 | 2010-06-09 | 湖北犇星化工有限责任公司 | Method for treating waste water from acetic acid mercapto- isooctyl ester |
| CN102229549A (en) * | 2011-05-16 | 2011-11-02 | 潍坊益华化工有限公司 | Method for preparing isooctyl mercaptoacetate |
| CN101665455B (en) * | 2009-09-27 | 2012-08-08 | 潍坊加华化工有限公司 | Method for preparing isooctyl thioglycolate by adopting tail liquid in the production process of O-alkyl-N-alkyl sulfide expelling carbamate |
| CN102775333A (en) * | 2012-07-31 | 2012-11-14 | 烟台恒邦化工助剂有限公司 | Method for preparing isooctyl thioglycolate by utilizing thionocarbamate tail liquid |
| CN103360291A (en) * | 2013-06-21 | 2013-10-23 | 青岛联拓化工有限公司 | Method for preparing high-concentration mercaptoacetic acid from raffinate generated in production of O-alkyl-N-alkyl thinocarbamate |
| 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 |
| CN105753649A (en) * | 2016-04-18 | 2016-07-13 | 南京师范大学 | Method of recycling isooctanol from waste solvent in production process of isooctyl thioglycolate |
| CN106518737A (en) * | 2016-08-31 | 2017-03-22 | 湖北犇星化工有限责任公司 | Quality control method for producing isooctyl mercaptoacetate used for tin mercaptan synthesis technology |
| CN110563621A (en) * | 2019-09-04 | 2019-12-13 | 中南大学 | Method for utilizing byproduct sodium 2-mercaptoacetate in thiourethane production process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2005375C3 (en) * | 1970-02-06 | 1978-06-29 | Ciba-Geigy Ag, Basel (Schweiz) | Process for the preparation of mercaptocarboxylic acid esters |
-
1994
- 1994-05-25 CN CN94110279A patent/CN1040978C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318750B (en) * | 2008-07-22 | 2010-06-09 | 湖北犇星化工有限责任公司 | Method for treating waste water from acetic acid mercapto- isooctyl ester |
| CN101665455B (en) * | 2009-09-27 | 2012-08-08 | 潍坊加华化工有限公司 | Method for preparing isooctyl thioglycolate by adopting tail liquid in the production process of O-alkyl-N-alkyl sulfide expelling carbamate |
| CN102229549A (en) * | 2011-05-16 | 2011-11-02 | 潍坊益华化工有限公司 | Method for preparing isooctyl mercaptoacetate |
| CN102775333A (en) * | 2012-07-31 | 2012-11-14 | 烟台恒邦化工助剂有限公司 | Method for preparing isooctyl thioglycolate by utilizing thionocarbamate tail liquid |
| CN103360291A (en) * | 2013-06-21 | 2013-10-23 | 青岛联拓化工有限公司 | Method for preparing high-concentration mercaptoacetic acid from raffinate generated in production of O-alkyl-N-alkyl thinocarbamate |
| CN103360291B (en) * | 2013-06-21 | 2016-12-07 | 青岛联拓化工有限公司 | With producing the method that high concentration TGA prepared by the O-alkyl-N-alkyl sulfide tail washings by carbamate |
| 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 |
| CN105753649A (en) * | 2016-04-18 | 2016-07-13 | 南京师范大学 | Method of recycling isooctanol from waste solvent in production process of isooctyl thioglycolate |
| CN105753649B (en) * | 2016-04-18 | 2018-01-05 | 南京师范大学 | A kind of method that isooctanol is reclaimed from the solvent slop of isooctyl thioglycolate production process |
| CN106518737A (en) * | 2016-08-31 | 2017-03-22 | 湖北犇星化工有限责任公司 | Quality control method for producing isooctyl mercaptoacetate used for tin mercaptan synthesis technology |
| CN110563621A (en) * | 2019-09-04 | 2019-12-13 | 中南大学 | Method for utilizing byproduct sodium 2-mercaptoacetate in thiourethane production process |
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| CN1040978C (en) | 1998-12-02 |
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