CN1031838A - Process for preparing dimethyl-disulfide - Google Patents
Process for preparing dimethyl-disulfide Download PDFInfo
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- CN1031838A CN1031838A CN 87101332 CN87101332A CN1031838A CN 1031838 A CN1031838 A CN 1031838A CN 87101332 CN87101332 CN 87101332 CN 87101332 A CN87101332 A CN 87101332A CN 1031838 A CN1031838 A CN 1031838A
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- methyl
- disulfide
- dimethyltrisulfide
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Abstract
The present invention is a kind of manufacturing process of Methyl disulfide, be characterized in the methyl-sulfate being main raw material, at first make the mixing crude product that major ingredient is Methyl disulfide and dimethyltrisulfide through reaction, directly the dimethyltrisulfide in the crude product is converted into Methyl disulfide without separating then with sodium sulphite.The utilization ratio (in dimethyltrisulfide and Methyl disulfide) of preceding step reacting thiourea dimethyl phthalate is greater than 92%, back step transformation efficiency is greater than 96%, the content of Methyl disulfide is greater than 92% in the products obtained therefrom, the Methyl disulfide that makes with this technology can be used for producing content greater than important pesticide intermediate 3-methyl-4-methylthiophenol of 95%, also can obtain content greater than 99% Methyl disulfide after rectifying.
Description
The invention belongs to the organic synthesis field, include the manufacturing process of organic disulfide.
Methyl disulfide is used as the anticorrosion and scorch retarder of ethane cracking furnace in petroleum industry, the vulcanizing agent of gasoline hydrogenation catalyst, benzene nucleus takes off the inhibitor of hydrocracking in the alkyl reaction, is used in the synthesis material of making pesticide intermediate 3-methyl-4-methylthiophenol at present in a large number.
The process for preparing dimethyl-disulfide of foreign patent report, all be that employing thiomethyl alcohol or sodium methyl mercaptide are starting raw material, prepare through methods such as oxidation, sulfuration or replacements, therefore necessarily required the thiomethyl alcohol resource, China's thiomethyl alcohol generally all adopts methyl chloride and Sodium sulfhydrate to prepare sodium methyl mercaptide, cost is higher, and above-mentioned technological process and equipment more complicated all.
Shenyang Agricultural Chemicals Factory's " Tiguvon test production technology is summed up " confidential data had once been introduced the manufacture method of Methyl disulfide in domestic 1973, its technological process is to generate sodium disulfide with sodium sulphite and reaction of Salmon-Saxl earlier, drip methyl-sulfate again and prepare Methyl disulfide, practice through laboratory proofing and plant produced shows, adopt in the product of above-mentioned prepared through the stratographic analysis thiomethyl alcohol, the content of impurity such as dimethyl sulfide and dimethyltrisulfide is up to 30%, the content of Methyl disulfide about 60～70%, the utilization ratio of methyl-sulfate has only 60～70%, production process has malodorous in a large number " three wastes ", owing to administer not thorough, contaminate environment, the Methyl disulfide that the purity that makes with above-mentioned technology is lower can not make the 3-methyl-4-methylthiophenol of high-content and high yield.
The objective of the invention is to propose a kind of technology that can prepare high-load Methyl disulfide, product can be satisfied produce the requirement of content greater than 3-methyl-4-methylthiophenol of 95%, guarantee higher raw material availability simultaneously, thereby can reduce production costs, and solve the problem of complex utilization of " three wastes ".
The manufacturing process of Methyl disulfide of the present invention is a starting raw material with methyl-sulfate, sodium sulphite and sulphur, and it comprises the following steps and characteristics:
1, preparation is the mixing crude product (hereinafter to be referred as crude product) of major ingredient with Methyl disulfide and dimethyltrisulfide.
Press methyl-sulfate, sodium sulphite, the molecular ratio of sulphur is 1: (1.1～1.2): the ratio of components of (1.8～2.2), powdery sulphur joined in 18～22% the sodium sulfide solution, 60～90 ℃ of following stirring reactions one hour, be cooled to then below 35 ℃, and under this temperature, drip methyl-sulfate, drip the back and continue reaction 1-3 hour, carry out steam distillation, reaction product is distillated with water vapor, with condensed distillate standing demix, the oily mater of lower floor is Methyl disulfide and dimethyltrisulfide is the mixing crude product of major ingredient, and wherein dimethyltrisulfide content is greater than 30%.(must measure with the product composition and see embodiment table one for details).The water of condensation on upper strata can be used for next formulating vulcanization sodium solution and uses.Because this technology has improved the consumption of sulphur when selecting proportioning for use, thereby dimethyltrisulfide content significantly increases in the crude product that makes of reaction, can make low-boiling-point substance such as dimethyl sulfide like this, the amounts of minimizing such as thiomethyl alcohol (as less than 6%), thus improved the utilization ratio of methyl-sulfate.
2, adopt sodium sulfide solution, dimethyltrisulfide is converted into Methyl disulfide.
The crude product that above-mentioned steps makes, do not need in advance Methyl disulfide and dimethyltrisulfide to be separated, as long as crude product is accurately measured, and with the content of gas chromatography determination dimethyltrisulfide wherein, actual amount according to dimethyltrisulfide, molecular ratio by dimethyltrisulfide and sodium sulphite is 1: the ratio of components of (0.9～1.2), the aqueous solution of required sodium sulphite is joined in the crude product, can carry out conversion reaction, controlled temperature is 20～40 ℃, behind the stirring reaction 1～2 hour, carry out steam distillation, product after the conversion is distillated with water vapor, tell layer oily matter matter after the condensation, be the Methyl disulfide product, through stratographic analysis Methyl disulfide content greater than 92%, the transformation efficiency of dimethyltrisulfide is seen embodiment table two greater than 96%(), as product can be obtained content greater than 99% Methyl disulfide through rectifying again.Vinasse after the conversion mainly contains sodium polysulphide, can be used for batching next time after chemical examination.The water of steam distillation condensation can be used for next formulating vulcanization sodium solution and uses.
3, the processing of reacted steam distillation raffinate is reclaimed and utilization.
By step 1 remaining reacted vinasse behind the steam distillation crude product, mainly contain sodium sulphite, sodium polysulphide and sodium sulfate and a small amount of sodium methyl mercaptide etc. is arranged, after the chemical examination total alkalinity, under 80 ℃～100 ℃ temperature, drip dilute sulphuric acid, determine the sulfuric acid amount of needs according to total alkalinity, make solution be strongly-acid (about pH2), this moment sodium sulphite, sodium polysulphide and sodium methyl mercaptide etc. generate sodium sulfate with sulfuric acid reaction, the colloid sulphur that reaction process is separated out, be condensed into sulfur granules in heat-processed, filter, the recovery of washing back is used for next batching and uses.In the vitriolization process, the hydrogen sulfide of discharge, thiomethyl alcohol can absorb with caustic soda soln under little negative pressure, and the sodium sulphite of generation and sodium methyl mercaptide are used for batching use next time.Solution after vitriolization, be neutralized to pH=(6-7 with caustic soda soln after adding the small amounts agent), filtered while hot, to remove the oxyhydroxide of de-iron, (iron of bringing in the primary industry sodium sulphite) is cooled to room temperature with filtrate, promptly there is the sodium sulfate that contains crystal water to separate out, can be used as industrial raw material after the filtered and recycled, the mother liquor after the filtration is through concentrating under reduced pressure, all reclaim(ed) sulfuric acid sodium.This sodium sulfate quality product meets national relevant industrial sodium sulfate quality standard.
Process for preparing dimethyl-disulfide of the present invention, selected the at first mixing crude product of synthesization of dimethyl disulfide and dimethyltrisulfide for use, and then will mix the operational path that dimethyltrisulfide in the crude product is converted into Methyl disulfide, improved the utilization ratio of methyl-sulfate, thereby help reducing production costs and can obtain the higher Methyl disulfide of content, can satisfy the requirement of manufacturing 3-methyl-4-methylthiophenol.Waste gas in this technological process, waste liquid can all be recycled, and do not have " three wastes " emission pollution problem, simple, the control easily of this technological operation, and through pilot scale and practice of trial production examination proof, can commercial scale production.
Embodiment sees Table one, table two.
The compound experiment of table one, Methyl disulfide and dimethyltrisulfide mixing crude product
Name of material specification example 1 example 2 examples 3
1. methyl-sulfate is 98% 102.9 kilogram 102.9 kilograms 102.9 kilograms
2. sodium sulphite is analysed 100% 68.6 kilogram 74.9 kilograms 74.9 kilograms
3. sulphur is 99% 46.1 kilogram 51.7 kilograms 56.9 kilograms
4. the water tap water is 300.0 kilograms 300.0 kilograms 300.0 kilograms
Crude product must be measured 85.5 kilograms 80.5 kilograms 82.0 kilograms
Crude product composition Methyl disulfide 41.71% 60.13% 55.24%
Dimethyltrisulfide 54.63% 34.41% 39.80%
Thiomethyl alcohol 0.01% 1.64% 1.50%
Dimethyl sulfide 3.65 3.82% 3.46%
Methyl-sulfate: sodium sulphite: sulphur (molecular ratio)
1∶1.1∶1.8 1∶1.2∶2.0 1∶1.2∶2.2
Sodium sulphite: sulphur (molecular ratio) 1: 1.64 1: 1.66 1: 1.83
The utilization ratio % of methyl-sulfate 93.8% 92.0% 92.6%
(in Methyl disulfide and dimethyltrisulfide)
Table two, dimethyltrisulfide transformation experiment
Name of material specification example 1 example 2 examples 3
1, crude product is 85.5 kilograms 80.5 kilograms 82.0 kilograms
Wherein Methyl disulfide is 41.71 kilograms 48.4 kilograms 45.3 kilograms
54.63 kilograms 27.7 kilograms 32.6 kilograms of dimethyltrisulfides
2, sodium sulphite is rolled over 100% 26.0 kilogram 17.2 kilograms 24.5 kilograms
3, the water tap water is 190.0 kilograms 126.0 kilograms 180.0 kilograms
Product must be measured 78.0 kilograms 73.2 kilograms 75.0 kilograms
Product composition Methyl disulfide 92.34% 92.59% 93.2%
Dimethyltrisulfide 2.80% 1.11% 1.50%
Dimethyltrisulfide: sodium sulphite (molecular ratio)
1∶0.9 1∶1 1∶1.2
Dimethyltrisulfide transformation efficiency 96.0% 97.1% 96.6%
※ dimethyltrisulfide transformation efficiency %=(dimethyltrisulfide amount in the crude product-(product must measure * product in dimethyltrisulfide content %))/(dimethyltrisulfide amount in the crude product)
Claims (8)
1, a kind of process for preparing dimethyl-disulfide, it is a starting raw material with methyl-sulfate, sodium sulphite and sulphur, it is characterized in that:
11 sodium sulphite, sulphur and methyl-sulfate react at aqueous phase, and generating major ingredient is the mixing crude product (hereinafter to be referred as crude product) of Methyl disulfide and dimethyltrisulfide,
12 adopt sodium sulfide solution that dimethyltrisulfide is converted into Methyl disulfide,
Hydrogen sulfide, sulphur and sodium sulfate that 13 reacted vinasses are generated after vitriolization, can all recycle, the water of condensation of steam distillation, can all be used for the formulating vulcanization sodium solution, vinasse after the conversion, contain sodium polysulphide etc. and be used for batching next time, therefore whole process does not have trash discharge.
2, by the manufacturing process of the described Methyl disulfide of claim 1, carry the doctor positive consumption when it is characterized in that producing crude product, making and generating main component is the mixture of Methyl disulfide and dimethyltrisulfide, and wherein the content of dimethyltrisulfide is greater than 30%.
3, press the manufacturing process of claim 1 and 2 described Methyl disulfide, when it is characterized in that producing crude product, the ingredients molecular ratio of methyl-sulfate, sodium sulphite and sulphur is 1: (1.1～1.2): (1.8～2.2), the temperature that drips methyl-sulfate is less than 35 ℃.
4, by the manufacturing process of the described Methyl disulfide of claim 1, it is characterized in that said dimethyltrisulfide transforms, can directly react with crude product and sodium sulfide solution, Methyl disulfide contained in the crude product needn't be separated in advance.
5,, it is characterized in that method measures the wherein content of dimethyltrisulfide by claim 1 and 4 described process for preparing dimethyl-disulfide.
6,, it is characterized in that the ingredients molecular ratio of dimethyltrisulfide and sodium sulphite is 1: (0.9～1.2), invert point are 20～40 ℃ when carrying out the dimethyltrisulfide conversion by claim 1,4 and 5 described process for preparing dimethyl-disulfide.
7, by the described process for preparing dimethyl-disulfide of claim 1, it is characterized in that said reacted vinasse, can adopt the method for vitriolization to reclaim hydrogen sulfide, sulphur and sodium sulfate step by step.
8, by claim 1 and 7 described process for preparing dimethyl-disulfide, it is characterized in that before reclaim(ed) sulfuric acid sodium, removing iron contamination and handle, therefore can obtain to meet industrial sodium sulfate product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87101332.0A CN1004627B (en) | 1987-05-06 | 1987-05-06 | Process for preparing dimethyl disulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87101332.0A CN1004627B (en) | 1987-05-06 | 1987-05-06 | Process for preparing dimethyl disulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1031838A true CN1031838A (en) | 1989-03-22 |
| CN1004627B CN1004627B (en) | 1989-06-28 |
Family
ID=4813325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87101332.0A Expired CN1004627B (en) | 1987-05-06 | 1987-05-06 | Process for preparing dimethyl disulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1004627B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053891C (en) * | 1997-09-18 | 2000-06-28 | 廊坊三威化工有限公司 | Preparation method for dimethyl disulphide |
| CN104592070A (en) * | 2015-01-13 | 2015-05-06 | 湖北兴发化工集团股份有限公司 | Preparation method of dimethyl disulfide |
| CN114957061A (en) * | 2022-06-21 | 2022-08-30 | 金浦新材料股份有限公司 | Production method of dimethyl disulfide |
-
1987
- 1987-05-06 CN CN87101332.0A patent/CN1004627B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053891C (en) * | 1997-09-18 | 2000-06-28 | 廊坊三威化工有限公司 | Preparation method for dimethyl disulphide |
| CN104592070A (en) * | 2015-01-13 | 2015-05-06 | 湖北兴发化工集团股份有限公司 | Preparation method of dimethyl disulfide |
| CN114957061A (en) * | 2022-06-21 | 2022-08-30 | 金浦新材料股份有限公司 | Production method of dimethyl disulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1004627B (en) | 1989-06-28 |
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