CN102775333B - Method for preparing isooctyl thioglycolate by utilizing thionocarbamate tail liquid - Google Patents
Method for preparing isooctyl thioglycolate by utilizing thionocarbamate tail liquid Download PDFInfo
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- CN102775333B CN102775333B CN201210267570.8A CN201210267570A CN102775333B CN 102775333 B CN102775333 B CN 102775333B CN 201210267570 A CN201210267570 A CN 201210267570A CN 102775333 B CN102775333 B CN 102775333B
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- thiourethane
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Abstract
The invention discloses a method for preparing isooctyl thioglycolate by utilizing thionocarbamate tail liquid, which is characterized by comprising the following process steps of: impurity removal and acidification, Zn powder decolorizing, extraction, crude distillation and rectification. The method has the beneficial effects that the impurity removal and the acidification are integrated, an efficient benzene extraction agent is adopted for replacing ethyl ether to reduce the risk and the pollution and the operation steps are also simplified, and meanwhile, the efficient benzene extraction agent can be recycled and is convenient to operate; a zinc powder decoloring process is increased, so that the he product quality stability is ensured; the esterification reaction is finished at the same time in the crude distillation process, and a qualified coarse ester semi-product is obtained at one time, so that the operation steps are reduced, and the efficiency is improved; and through direct rectification, a distillation kettle substrate is left in a crude distillation process, and no rectification kettle substrate is generated, so that the production capacity and the product yield are improved, and the cost is reduced.
Description
Technical field:
The present invention relates to chemical technique technical field, is a kind of method of utilizing thiourethane tail washings to manufacture isooctyl mercaptoacetate specifically.
Background technology:
At present, along with the continuous expansion in stabilizer for plastics market, as the demand of manufacturing the different monooctyl ester of stablizer raw material, also constantly increase.The technique of now adopting is: 1, tail washings acidifying; 2, ether removal of impurities; 3, isooctyl alcohol extraction; 4, esterification; 5, thick ester removal of impurities; 6, the technical process such as rectifying, its operation easier is large, long reaction time, cost is high, and unstable product quality exists ether to process the very dangerous problems such as environmental pollution that cause simultaneously.
Summary of the invention:
The object of the invention is to overcome the deficiency of above-mentioned prior art, and provide one to utilize thiourethane tail washings to manufacture the method for isooctyl mercaptoacetate, mainly solve that existing technological operation difficulty is large, long reaction time, cost are high, unstable product quality and ether are processed the dangerous problems such as environmental pollution that cause.
In order to achieve the above object, the present invention is achieved in that a kind of method of utilizing thiourethane tail washings to manufacture isooctyl mercaptoacetate, and its special character is to comprise following processing step:
A removal of impurities acidifying: by thiourethane tail washings and the efficient extraction agent of benzene class, evenly mix under normal pressure, tail washings is carried out to removal of impurities, add dilute hydrochloric acid to carry out acidifying in the time of removal of impurities, adjust pH value 4
~ 5;then stratification, separates bottom acidizing fluid, and the upper strata efficient extraction agent of benzene class stays former operation to recycle;
B Z
npowder decolouring: under acidizing fluid agitation condition, add zinc powder, make acidizing fluid reach colourless;
C extraction: acidizing fluid is adopted in extraction tank isooctyl alcohol carry out multi-stage continuous extraction, in extraction liquid, Thiovanic acid content, at 55%-60%, extracts Thiovanic acid content≤0.2% in tail washings;
D simple distillation: in extraction liquid, add Phenylsulfonic acid catalyzer, in perfect vacuum, it is-0.09 ~-0.1 MPa, temperature is under the condition of 80 ℃ ~ 140 ℃, in water distilling apparatus, and simple distillation 16-18 hours, gather each cut, obtain front-end volatiles alcohol water as the extraction agent recycle of extraction step, the thick ester of after cut isooctyl mercaptoacetate content >=85%, still kettle substrate;
E rectifying: thick ester is added to rectification process still, in perfect vacuum, it is-0.09 ~-0.1 MPa, temperature is under the condition of 110 ℃ ~ 140 ℃, distillation 16-18 hour is controlled in external reflux, gather each cut, obtain front-end volatiles isooctyl mercaptoacetate content < 90% for thick ester, content >=99.5%, colourity <'s 5 is isooctyl mercaptoacetate product.
Further, the efficient extraction agent of benzene class described in a step is toluene, dimethylbenzene or dinitrobenzene.
Further, the mol ratio of the thiourethane tail washings described in a step and the efficient extraction agent of benzene class is 1:6
~8.
Further, the zinc powder described in b step is the 1%-2% of acidizing fluid weight.
Further, the Phenylsulfonic acid catalyzer described in d step is 0.02% ~ 0.5% of extraction liquid weight.
A kind of method of utilizing thiourethane tail washings to manufacture isooctyl mercaptoacetate of the present invention is compared and is had outstanding substantive distinguishing features and marked improvement with the technology having, 1, removal of impurities acidifying unites two into one, with the efficient extraction agent of benzene class, replace ether to reduce dangerous and polluted, also simplified operation steps, while benzene kind of extractants reusable edible, convenient operation; 2, increase zinc powder decoloration process, guaranteed the stable of quality product; 3, in simple distillation process, complete esterification simultaneously, once obtain qualified thick ester half product, avoided existing technique repeatedly esterification repeatedly extract the process that just can obtain qualified thick ester product, reduced operation steps, improved efficiency; 4, reduced thick ester removal of impurities operation, directly rectifying, stays still kettle substrate slightly to heat up in a steamer operation, and rectifying produces without bottoms, has improved production capacity and product yield, has reduced cost.
Embodiment:
For Comprehension and Implementation better, below in conjunction with embodiment, describe the present invention in detail.
Embodiment 1, by thiourethane tail washings and xylene extraction agent, with the mol ratio of 1:7, under normal pressure, evenly mixes, and tail washings is carried out to removal of impurities; In removal of impurities, add dilute hydrochloric acid to carry out acidifying, adjust pH value 4
~ 5;stratification after acidifying completes, separates bottom acidizing fluid, and upper strata xylene extraction agent stays former operation to recycle; In acidizing fluid, under agitation condition, add the zinc powder of the 1%-2% of acidizing fluid weight, make acidizing fluid reach colourless; Esterifying liquid is adopted in extraction tank isooctyl alcohol carry out multi-stage continuous extraction, in extraction liquid, Thiovanic acid content, at 55%-60%, extracts Thiovanic acid content≤0.2% in tail washings; In extraction liquid, add 0.2% Phenylsulfonic acid catalyzer of extraction liquid weight, in perfect vacuum, be-0.09 ~-0.1 MPa, temperature is that under the condition of 110 ℃,, in water distilling apparatus, simple distillation 17 hours, gathers each cut; Obtain front-end volatiles alcohol water as the extraction agent recycle of extraction step, the thick ester of after cut isooctyl mercaptoacetate content>=85%, still kettle substrate; Thick ester is added to rectification process still, in perfect vacuum, it is-0.09 ~-0.1 MPa, temperature is under the condition of 125 ℃ ℃, distillation 17 hours are controlled in external reflux, gather each cut, obtain front-end volatiles isooctyl mercaptoacetate content < 90% for thick ester, content>=99.5%, colourity <'s 5 is isooctyl mercaptoacetate product.
Adopt the method for above-described embodiment 1 to test, statistics is as follows:
As seen from the above table, adopt method of the present invention, isooctyl mercaptoacetate Content >=99.5% of being manufactured by thiourethane tail washings, colourity < 5.
Embodiment 2, by thiourethane tail washings and toluene extraction agent, with the mol ratio of 1:6, under normal pressure, evenly mix, and tail washings is carried out to removal of impurities; In removal of impurities, add dilute hydrochloric acid to carry out acidifying, adjust pH value 4
~ 5;stratification after acidifying completes, separates bottom acidizing fluid, and upper toluene extraction agent stays former operation to recycle; In acidizing fluid, under agitation condition, add the zinc powder of the 1%-2% of acidizing fluid weight, make acidizing fluid reach colourless; Esterifying liquid is adopted in extraction tank isooctyl alcohol carry out multi-stage continuous extraction, in extraction liquid, Thiovanic acid content, at 55%-60%, extracts Thiovanic acid content≤0.2% in tail washings; In extraction liquid, add 0.02% Phenylsulfonic acid catalyzer of extraction liquid weight, in perfect vacuum, be-0.09 ~-0.1 MPa, temperature is that under the condition of 140 ℃,, in water distilling apparatus, simple distillation 16 hours, gathers each cut; Obtain front-end volatiles alcohol water as the extraction agent recycle of extraction step; The thick ester of after cut content>=85%, still kettle substrate; Thick ester is added to rectification process still, in perfect vacuum, it is-0.09 ~-0.1 MPa, temperature is under the condition of 110 ℃, distillation 18 hours are controlled in external reflux, gather each cut, obtain front-end volatiles isooctyl mercaptoacetate content < 90% for thick ester, content>=99.5%, colourity <'s 5 is isooctyl mercaptoacetate product.
Embodiment 3, by thiourethane tail washings and dinitrobenzene extraction agent, with the mol ratio of 1:8, under normal pressure, evenly mix, and tail washings is carried out to removal of impurities; In removal of impurities, add dilute hydrochloric acid to carry out acidifying, adjust pH value 4
~ 5;stratification after acidifying completes, separates bottom acidizing fluid, and upper strata dinitrobenzene extraction agent stays former operation to recycle; In acidizing fluid, under agitation condition, add the zinc powder of the 1%-2% of acidizing fluid weight, make acidizing fluid reach colourless; Esterifying liquid is adopted in extraction tank isooctyl alcohol carry out multi-stage continuous extraction, in extraction liquid, Thiovanic acid content, at 55%-60%, extracts Thiovanic acid content≤0.2% in tail washings; In extraction liquid, add 0.5% Phenylsulfonic acid catalyzer of extraction liquid weight, in perfect vacuum, be-0.09 ~-0.1 MPa, temperature is that under the condition of 80 ℃,, in water distilling apparatus, simple distillation 18 hours, gathers each cut; Obtain front-end volatiles alcohol water as the extraction agent recycle of extraction step; The thick ester of after cut content>=85%, still kettle substrate; Thick ester is added to rectification process still, in perfect vacuum, it is-0.09 ~-0.1 MPa, temperature is under the condition of 140 ℃ ℃, distillation 16 hours are controlled in external reflux, gather each cut, obtain front-end volatiles isooctyl mercaptoacetate content < 90% for thick ester, content>=99.5%, colourity <'s 5 is isooctyl mercaptoacetate product.
Claims (4)
1. utilize thiourethane tail washings to manufacture a method for isooctyl mercaptoacetate, it is characterized in that comprising following processing step:
A removal of impurities acidifying: by thiourethane tail washings and the efficient extraction agent of benzene class, evenly mix under normal pressure, tail washings is carried out to removal of impurities, add dilute hydrochloric acid to carry out acidifying in the time of removal of impurities, adjust pH value 4
~ 5;then stratification, separates bottom acidizing fluid, and the upper strata efficient extraction agent of benzene class stays former operation to recycle; The described efficient extraction agent of benzene class is toluene, dimethylbenzene or dinitrobenzene;
B Zn powder decolouring: under acidizing fluid agitation condition, add zinc powder, make acidizing fluid reach colourless;
C extraction: acidizing fluid is adopted in extraction tank isooctyl alcohol carry out multi-stage continuous extraction, in extraction liquid, Thiovanic acid content, at 55%-60%, extracts Thiovanic acid content≤0.2% in tail washings;
D simple distillation: in extraction liquid, add Phenylsulfonic acid catalyzer, in perfect vacuum, it is-0.09 ~-0.1 MPa, temperature is under the condition of 80 ℃ ~ 140 ℃, in water distilling apparatus, and simple distillation 16-18 hour, gather each cut, obtain front-end volatiles alcohol water as the extraction agent recycle of extraction step, the thick ester of after cut isooctyl mercaptoacetate content >=85%, still kettle substrate;
E rectifying: thick ester is added to rectification process still, in perfect vacuum, it is-0.09 ~-0.1 MPa, temperature is under the condition of 110 ℃ ~ 140 ℃, distillation 16-18 hour is controlled in external reflux, gather each cut, obtain front-end volatiles isooctyl mercaptoacetate content < 90% for thick ester, content >=99.5%, colourity <'s 5 is isooctyl mercaptoacetate product.
2. a kind of method of utilizing thiourethane tail washings to manufacture isooctyl mercaptoacetate according to claim 1, is characterized in that thiourethane tail washings described in a step and the mol ratio of the efficient extraction agent of benzene class are 1:6
~8.
3. a kind of method of utilizing thiourethane tail washings to manufacture isooctyl mercaptoacetate according to claim 1, is characterized in that the zinc powder described in b step is the 1%-2% of acidizing fluid weight.
4. a kind of method of utilizing thiourethane tail washings to manufacture isooctyl mercaptoacetate according to claim 1, is characterized in that the Phenylsulfonic acid catalyzer described in d step is 0.02% ~ 0.5% of extraction liquid weight.
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| 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 |
| 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 |
| 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 |
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| FR2652811B1 (en) * | 1989-10-06 | 1993-12-24 | Elf Aquitaine Ste Nale | CONTINUOUS SYNTHESIS OF MERCAPTOCARBOXYLIC ACID ESTERS. |
| CN1040978C (en) * | 1994-05-25 | 1998-12-02 | 沈阳矿冶研究所 | Preparation of isooctyl mercaptoacetate by using tailing liquor containing mercaptoacetic acid from production of thiourethane |
| 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 |
| CN102229549B (en) * | 2011-05-16 | 2013-11-06 | 潍坊益华化工有限公司 | Method for preparing isooctyl mercaptoacetate |
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Denomination of invention: A method for producing isooctyl mercaptoacetate from tail liquid of thiourethane Effective date of registration: 20211207 Granted publication date: 20140716 Pledgee: Yantai financing guarantee Group Co.,Ltd. Pledgor: YANTAI HUMON CHEMICAL AUXILIARY CO.,LTD. Registration number: Y2021980014207 |
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