CN104592070A - Preparation method of dimethyl disulfide - Google Patents
Preparation method of dimethyl disulfide Download PDFInfo
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- CN104592070A CN104592070A CN201510013890.4A CN201510013890A CN104592070A CN 104592070 A CN104592070 A CN 104592070A CN 201510013890 A CN201510013890 A CN 201510013890A CN 104592070 A CN104592070 A CN 104592070A
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Abstract
The invention provides a preparation method of dimethyl disulfide, which comprises the following steps: adding powder sulfur into a reactor under pressurized reaction conditions, and reacting the sulfur with a liquid catalyst sodium sulfide in the reactor to generate a sodium persulfide solution; introducing impure methyl mercaptan gas to react with sodium persulfate, wherein the reaction solution is divided into an organic layer dimethyl disulfide and byproducts (dimethyl trisulfide and dimethyl polysulfide); and rectifying the dimethyl disulfide and byproducts (dimethyl trisulfide and dimethyl polysulfide) to obtain dimethyl disulfide, wherein the mixed solution of the byproducts (dimethyl trisulfide and dimethyl polysulfide) returns to the reactor to complete the circular reaction. The reaction conditions are mild, the product is insoluble in the liquid catalyst and can be easily separated, and the catalyst can be circularly used for a long time.
Description
Technical field
The present invention relates to a kind of unpurified thiomethyl alcohol and sulphur adopts liquid catalyst to prepare the method for Methyl disulfide.
Background technology
The method of current domestic production Methyl disulfide generally all be dimethyl sulfate ester process, by dripping methyl-sulfate and its reaction generates Methyl disulfide in sodium sulfide solutions.The method production process produces with a large amount of waste water, and environmental pollution is more serious.Methyl-sulfate is originally as highly toxic substance simultaneously.In order to solve deficiency of the prior art, the present invention proposes a kind of new Methyl disulfide production method.
Summary of the invention
A kind of method adopting liquid catalyst system Methyl disulfide with unpurified thiomethyl alcohol (60%-99%) and sulfur reaction, specifically in reaction conditions downhill reaction device with pressure, add powder sulphur, sodium sulfide solution in itself and reactor is reacted and generates sodium sulfide solutions.The impure methyl mercaptan gas that reactor bottom passes into and sodium persulfide react and generate Methyl disulfide, dimethyltrisulfide and the many sulphur of dimethyl.In this reaction, sodium persulfide and thiomethyl alcohol react and generate Methyl disulfide and sodium sulphite, solution layering, and organic layer, from reactor top extraction, goes out purer Methyl disulfide through the rectifying of rectifying mode.Remaining by product sodium sulphite continues to generate sodium sulfide solutions by adding sulphur, passes into methyl mercaptan gas and repeat above-mentioned reaction in reactor.This reaction also can generate hydrogen sulfide simultaneously.Hydrogen Sulfide Tail Gas can be combined with solution and generate Sodium sulfhydrate, by making it decompose releasing hydrogen sulfide to reactor heating, and the gas desulfuration alcohol reactor of releasing and methanol-fueled CLC thiomethyl alcohol.This reactor pressure controls as 0.03MPa-0.4MPa, and reactor temperature controls, for 20-90 DEG C, to be alternately distributed the water at low temperature of the hot water passing into 60-90 DEG C and 6-8 DEG C in the coil pipe of reactor middle and upper part.
What adopt such scheme not only to improve sodium sulfide solution utilizes number of times, and makes Hydrogen Sulfide Tail Gas obtain second stage employ.Reaction equation is as follows:
Na
2S+S→Na
2S
2
Na
2S
2+2CH
3SH→CH
3S
2CH
3+Na
2S+H
2S
CH
3S
nCH
3+S→CH
3S
n+1CH
3n≥2
2CH
3SH+CH
3S
nCH
3→CH
3S
n-1CH
3+CH
3S
2CH
3+H
2S n>2
Na
2S+H
2S→2NaSH
Adopt technical scheme reaction conditions of the present invention gentle, product does not dissolve each other with liquid catalyst, be easy to be separated, catalyzer can recycle for a long time.
Embodiment
Embodiment 1
Liquid catalyst is loaded in reactor, catalyzer is sodium sulfide solution, reactor is built with multilayer coil pipe or chuck, reactor bottom coil pipe passes into hot water (20-90 DEG C), and reactor middle and upper part coil pipe passes into hot water (20-90 DEG C) respectively and water at low temperature (6-8 DEG C) is alternately distributed.In reactor, 1:2-1:5 adds powder sulphur and unpurified thiomethyl alcohol (60%-99%) in molar ratio.Control temperature of reactor is 20-90 DEG C, and pressure is 0.03MPa-0.4MPa, and first sulphur react with sodium sulphite and generate sodium persulfide, and sodium persulfide reacts with thiomethyl alcohol and generates Methyl disulfide, dimethyltrisulfide, dimethyl many sulphur mixture.After reacting completely, solution can divide organic layer and inorganic layer, and upper strata is organic layer, mainly Methyl disulfide, dimethyltrisulfide, dimethyl many sulphur mixture.Obtain purer Methyl disulfide by after organic layer extraction through rectifying mode, rectifying tower reactor is mainly returned reactor complete circulating reaction containing the mixing solutions of dimethyltrisulfide, the many sulphur of dimethyl.After completing one-period reaction, reactor lower part is without basic unit, be mainly sodium persulfide and thiomethyl alcohol reacts the sodium sulphite generated, in this reaction process, sodium sulphite and hydrogen sulfide can react generation Sodium sulfhydrate simultaneously, by regulating reactor bottom hot water to make Sodium sulfhydrate thermal degradation regeneration sodium sulphite, sodium sulphite continues to react with the sulphur added, thiomethyl alcohol execution cycle property again.The hydrogen sulfide produced after reaction returns thiomethyl alcohol reactor and methanol-fueled CLC thiomethyl alcohol by reactor head, and thiomethyl alcohol returns reactor cycles and utilizes.
Embodiment 2
Liquid catalyst is loaded in reactor, catalyzer is sodium sulfide solution, reactor is built with multilayer coil pipe or chuck, reactor bottom coil pipe passes into hot water (90 DEG C), and reactor middle and upper part coil pipe passes into hot water (65 DEG C) respectively and water at low temperature (8 DEG C) is alternately distributed.In reactor, 1:4.6 adds powder sulphur and unpurified thiomethyl alcohol (65%) in molar ratio.Controlling temperature of reactor is 58 DEG C, and pressure is 0.25MPa, and first sulphur react with sodium sulphite and generate sodium persulfide, and sodium persulfide reacts with thiomethyl alcohol and generates Methyl disulfide, dimethyltrisulfide, dimethyl many sulphur mixture.Other are with embodiment 1.
Embodiment 3
Liquid catalyst is loaded in reactor, catalyzer is sodium sulfide solution, reactor is built with multilayer coil pipe or chuck, reactor bottom coil pipe passes into hot water (45 DEG C), and reactor middle and upper part coil pipe passes into hot water (78 DEG C) respectively and water at low temperature (6 DEG C) is alternately distributed.In reactor, 1:2.2 adds powder sulphur and unpurified thiomethyl alcohol (78%) in molar ratio.Controlling temperature of reactor is 65 DEG C, and pressure is 0.15MPa, and first sulphur react with sodium sulphite and generate sodium persulfide, and sodium persulfide reacts with thiomethyl alcohol and generates Methyl disulfide, dimethyltrisulfide, dimethyl many sulphur mixture.Other are with embodiment 1.
Claims (5)
1. a preparation method for Methyl disulfide, is characterized in that, comprises the steps:
In reaction conditions downhill reaction device with pressure, add powder sulphur, the liquid catalyst sodium sulphite in itself and reactor is reacted and generates sodium sulfide solutions;
Pass into unpurified methyl mercaptan gas to above-mentioned reactor bottom, methyl mercaptan gas and sodium persulfide are reacted, after having reacted, reaction soln is divided into organic layer Methyl disulfide and by product methyl-sulfide trithio, the many sulphur of dimethyl, inorganic layer sodium sulphite and hydrogen sulfide;
Step 2) in organic layer Methyl disulfide and by product methyl-sulfide trithio, the many sulphur of dimethyl after rectifying, obtain methyl-sulfide two sulphur, the mixed solution of by product methyl-sulfide trithio, the many sulphur of dimethyl returns reactor and completes circulating reaction;
Step 2) in inorganic layer sodium sulphite and hydrogen sulfide can react generation Sodium sulfhydrate, Sodium sulfhydrate makes it be decomposed into sodium sulphite by regulating the hot water of reactor bottom, and sodium sulphite participates in the reaction of step 1) again, completes circulating reaction.
2. the preparation method of Methyl disulfide according to claim 1, is characterized in that, the mol ratio of sulphur, unpurified thiomethyl alcohol, sodium sulphite is 1:2-1:5.
3. the preparation method of Methyl disulfide according to claim 1 and 2, is characterized in that, unpurified methyl mercaptan gas refers to that concentration is the thiomethyl alcohol of 60-99%.
4. the preparation method of Methyl disulfide according to claim 1, is characterized in that, reactor pressure controls as 0.03MPa-0.4MPa.
5. the preparation method of Methyl disulfide according to claim 1, is characterized in that, reactor temperature controls, for 20-90 DEG C, to be alternately distributed the water at low temperature of the hot water passing into 60-90 DEG C and 6-8 DEG C in the coil pipe of reactor middle and upper part.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510013890.4A CN104592070A (en) | 2015-01-13 | 2015-01-13 | Preparation method of dimethyl disulfide |
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|---|---|---|---|
| CN201510013890.4A CN104592070A (en) | 2015-01-13 | 2015-01-13 | Preparation method of dimethyl disulfide |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107759501A (en) * | 2017-12-07 | 2018-03-06 | 查都（上海）科技有限公司 | A kind of device for producing DMDS coproduction dimethyltrisulfide |
| CN107827793A (en) * | 2017-12-07 | 2018-03-23 | 查都（上海）科技有限公司 | A kind of DMDS refining separation device |
| CN107827794A (en) * | 2017-12-07 | 2018-03-23 | 查都（上海）科技有限公司 | A kind of device of methyl mercaptan vulcanization method production DMDS |
| CN111440103A (en) * | 2020-04-28 | 2020-07-24 | 爱斯特（成都）生物制药股份有限公司 | Preparation method of tert-butyl disulfide |
| CN114478334A (en) * | 2022-02-25 | 2022-05-13 | 新疆广汇陆友硫化工有限公司 | Method for producing dimethyl disulfide by methyl mercaptan vulcanization method |
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| CN1031838A (en) * | 1987-05-06 | 1989-03-22 | 山东省农药氯碱协会 | Process for preparing dimethyl-disulfide |
| US6683221B1 (en) * | 1999-03-24 | 2004-01-27 | Lehigh University | Production of formaldehyde from CH4 and H2S |
| CN103864650A (en) * | 2014-03-20 | 2014-06-18 | 中国海洋石油总公司 | Method for continuously producing dimethyl disulfide |
| CN103910661A (en) * | 2013-02-26 | 2014-07-09 | 湖北兴发化工集团股份有限公司 | Method for producing dimethyl disulfide from methyl mercaptan and sulphur by employing sulfuration process |
-
2015
- 2015-01-13 CN CN201510013890.4A patent/CN104592070A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031838A (en) * | 1987-05-06 | 1989-03-22 | 山东省农药氯碱协会 | Process for preparing dimethyl-disulfide |
| US6683221B1 (en) * | 1999-03-24 | 2004-01-27 | Lehigh University | Production of formaldehyde from CH4 and H2S |
| CN103910661A (en) * | 2013-02-26 | 2014-07-09 | 湖北兴发化工集团股份有限公司 | Method for producing dimethyl disulfide from methyl mercaptan and sulphur by employing sulfuration process |
| CN103864650A (en) * | 2014-03-20 | 2014-06-18 | 中国海洋石油总公司 | Method for continuously producing dimethyl disulfide |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107759501A (en) * | 2017-12-07 | 2018-03-06 | 查都（上海）科技有限公司 | A kind of device for producing DMDS coproduction dimethyltrisulfide |
| CN107827793A (en) * | 2017-12-07 | 2018-03-23 | 查都（上海）科技有限公司 | A kind of DMDS refining separation device |
| CN107827794A (en) * | 2017-12-07 | 2018-03-23 | 查都（上海）科技有限公司 | A kind of device of methyl mercaptan vulcanization method production DMDS |
| CN111440103A (en) * | 2020-04-28 | 2020-07-24 | 爱斯特（成都）生物制药股份有限公司 | Preparation method of tert-butyl disulfide |
| CN114478334A (en) * | 2022-02-25 | 2022-05-13 | 新疆广汇陆友硫化工有限公司 | Method for producing dimethyl disulfide by methyl mercaptan vulcanization method |
| CN114478334B (en) * | 2022-02-25 | 2023-11-10 | 新疆广汇陆友硫化工有限公司 | Method for producing dimethyl disulfide by methyl mercaptan vulcanization |
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