CN103864650B - A kind of method of continuous production Methyl disulfide - Google Patents
A kind of method of continuous production Methyl disulfide Download PDFInfo
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- CN103864650B CN103864650B CN201410105544.4A CN201410105544A CN103864650B CN 103864650 B CN103864650 B CN 103864650B CN 201410105544 A CN201410105544 A CN 201410105544A CN 103864650 B CN103864650 B CN 103864650B
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- methyl disulfide
- dimethyltrisulfide
- sulfur
- methanthiol
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Abstract
The present invention is a kind of method of continuous production Methyl disulfide, it is characterised by: after raw material sulfur melts, dimethyltrisulfide reactor is sent into through feed pump, generation dimethyltrisulfide is reacted with the Methyl disulfide of circulation, dimethyltrisulfide enters Methyl disulfide reactor with methanthiol, reaction generates Methyl disulfide, the thick product of Methyl disulfide enters knockout drum, separate most hydrogen sulfide, liquid product enters rectifying column, overhead condensation reclaims Methyl disulfide product, hydrogen sulfide discharges as fixed gas, the Methyl disulfide of tower reactor and dimethyltrisulfide return and recycle.The method using dimethyltrisulfide excess so that methanthiol converts completely, reduces separation requirement, simplifies separating technology, not only the yield of Methyl disulfide improves to 90%, and product purity reaches 99wt%.
Description
Technical field:
The present invention relates to oil technical field of fine, for a kind of method of continuous production Methyl disulfide, tool
Say body and relate to a kind of method producing Methyl disulfide with methanthiol and sulfur for raw material continuously.
Background of invention:
Methyl disulfide is a kind of important Organic chemical products, can be widely used in the intermediate producing agricultural chemical insecticide；
In the oil industry, can be used as the vulcanizer in the anticorrosion of ethane cracking furnace and antiscorching agent, gasoline hydrogenation catalysis and phenyl ring
Decarboxylation reaction hydrogenates the inhibitor of cracking；In rubber industry, can be used as solvent, regenerative agent, softening agent and increasing
Mould agent etc.；Additionally, Methyl disulfide also acts as fuel and lubrication oil additive.
The Methyl disulfide production method great majority of current domestic report are to be former with dimethyl sulfate, sodium sulfide and sulfur
Material, including CN1075955, CN1031838 and CN1211568 etc., wherein dimethyl sulfate severe toxicity, to operative employee
People is in peril of one's life, and discharge a large amount of sulfur acid dimethyl ester and the sodium sulfate wastewater of sulfide, severe contamination environment.
The external method using methanthiol oxidation produces Methyl disulfide more, and oxidant includes oxygen, hydrogen peroxide, sulfur
With sodium nitrite etc., the method not only avoid the use of dimethyl sulfate, and production process is without the discharge of waste water.
CN102816093A discloses the method that the oxidation of a kind of methanthiol produces Methyl disulfide, and oxidant is oxygen or sulfur
Sulphur, catalyst is nitrogen dioxide, and emulsifying agent is acetone, dimethylformamide and dimethyl sulfoxide, at tower reactor
Middle successive reaction, product obtains Methyl disulfide finished product through Liquid liquid Separation, rectification.Methanthiol is very easy to blast, should
Method uses oxygen to be undoubtedly extremely hazardous as oxidant, and the emulsifying agent introduced significantly increases operation easier,
Improve production cost.
A kind of method that GB1094782A discloses methanthiol and sulfur produces Methyl disulfide continuously, sulfur and dimethyl
Two sulfur react generation dimethyltrisulfide in reactor A, react subsequently into reactor B and methanthiol and generate dimethyl
Two sulfur, the product of reactor B enters knockout tower I and takes off hydrogen sulfide and the methanthiol of excess, subsequently into knockout tower II
Reclaiming Methyl disulfide product, Methyl disulfide yield based on methanthiol is 85%, and product purity is 90wt%.Should
Hydrogen sulfide produced by method is discharged from reactor B, not only causes substantial amounts of methanthiol and loses, and dimethyl two
Sulfur also there occurs loss.
EP0202420 discloses a kind of method being raw material production Methyl disulfide with hydrogen sulfide, sulfur and methanol, sulfur
Sulphur and the reaction of part Methyl disulfide generate dimethyltrisulfide, methanol and hydrogen sulfide reaction and generate methanthiol, separate water
After the hydrogen sulfide of excess, methanthiol and dimethyltrisulfide reaction generate Methyl disulfide, and Methyl disulfide crude product is through 3
Individual knockout tower takes off hydrogen sulfide, methanthiol, thus obtains Methyl disulfide sterling, and Methyl disulfide based on methanol is produced
Product yield reaches 90%.The method using the methanthiol of excess, circulating load is big, and separating technology is complicated.
US4721813 discloses a kind of method that alkyl hydrosulfide dioxygen oxidation produces dialkyl disulfides, but methanthiol is easy
Blast, the method does not indicate and is applicable to Methyl disulfide.
On the basis of we study, it has been found that conventional method all uses the method for methanthiol excess produce diformazan
Base two sulfur, and Methyl disulfide removing methanthiol is an extremely complex job, the most not only yield is low, and produces
Product purity is the highest.We breach the thinking set of forefathers, the method using dimethyltrisulfide excess so that methanthiol
Converting completely, thus reduce separation requirement, simplify separating technology, not only the yield of Methyl disulfide improves to 90%,
And obtain purity and reach the Methyl disulfide product of 99wt%.
Summary of the invention:
Present invention mainly solves methanthiol present in prior art to reclaim difficult problem and provide and a kind of produce two continuously
The method of methyl two sulfur.
The present invention is a kind of method of continuous production Methyl disulfide, it is characterised in that:
A) sulfur reacts generation dimethyltrisulfide, dimethyl with the Methyl disulfide of excess in dimethyltrisulfide reactor
Two sulfur are 1～4 with the stoichiometric proportion of sulfur, and the Methyl disulfide of excess ensure that the conversion completely of sulfur, also subtracts simultaneously
Lack the generation of the many sulfur of dimethyl；Reaction temperature 0～80 DEG C；Reaction pressure 0～1MPaA；
B) dimethyltrisulfide of excess and methanthiol react generation Methyl disulfide, diformazan in Methyl disulfide reactor
Base trithio is 0.5～1 with the stoichiometric proportion of methanthiol, and the dimethyltrisulfide of excess ensure that the conversion completely of methanthiol,
Thus avoid methanthiol in follow-up workshop section and be difficult to the problem reclaimed；Reaction temperature 0～60 DEG C；Reaction pressure 0～1MPaA；
C) the thick product of Methyl disulfide after adiabatic flash uses single column rectification under vacuum to refine Methyl disulfide product, tower top
Pressure 10～500mmHg, a small amount of hydrogen sulfide discharges as fixed gas, the Methyl disulfide of tower reactor and dimethyltrisulfide warp
Circulating pump returns dimethyltrisulfide reactor cycles and uses, and tower top Methyl disulfide product purity reaches 99wt%, and yield is big
In 90%.
According to the method described in the present invention, it is characterised in that:
A) sulfur reacts generation dimethyltrisulfide, dimethyl with the Methyl disulfide of excess in dimethyltrisulfide reactor
Two sulfur are 2.1～3.4 with the stoichiometric proportion of sulfur, and the Methyl disulfide of excess ensure that the conversion completely of sulfur, simultaneously
Decrease the generation of the many sulfur of dimethyl；Reaction temperature 20～40 DEG C；Reaction pressure 0.2～0.6MPaA；
B) dimethyltrisulfide of excess and methanthiol react generation Methyl disulfide, diformazan in Methyl disulfide reactor
Base trithio is 0.6～0.8 with the stoichiometric proportion of methanthiol, and the dimethyltrisulfide of excess ensure that the conversion completely of methanthiol,
Thus avoid methanthiol in follow-up workshop section and be difficult to the problem reclaimed；Reaction temperature 10～30 DEG C, reaction pressure
0.2～0.5MPaA；
C) the thick product of Methyl disulfide after adiabatic flash uses single column rectification under vacuum to refine Methyl disulfide product, tower top
Pressure 50～200mmHg, a small amount of hydrogen sulfide discharges as fixed gas, the Methyl disulfide of tower reactor and dimethyltrisulfide warp
Circulating pump returns dimethyltrisulfide reactor cycles and uses, and tower top Methyl disulfide product purity reaches 99wt%, and yield is big
In 90%.
The concrete technology flow process of the present invention includes: after raw material sulfur melts, and sends into dimethyltrisulfide reactor through feed pump,
Generation dimethyltrisulfide (S+C2H6S2 → C2H6S3), dimethyltrisulfide and first sulfur is reacted with the Methyl disulfide of circulation
Alcohol enters Methyl disulfide reactor, reacts and generates Methyl disulfide (CH4S+C2H6S3 → 2C2H6S2+H2S), and two
The thick product of methyl two sulfur enters knockout drum, separates most hydrogen sulfide, and liquid product enters rectifying column, and tower top is cold
Solidifying recovery Methyl disulfide product, hydrogen sulfide discharges as fixed gas, and Methyl disulfide and the dimethyltrisulfide of tower reactor return
Return and recycle.
Sulfur and Methyl disulfide react generation dimethyltrisulfide, Methyl disulfide and sulfur in dimethyltrisulfide reactor
The stoichiometric proportion of sulphur is 1～4, preferably 2.1～3.4, and the Methyl disulfide of excess ensure that the conversion completely of sulfur, with
Time decrease the generation of the many sulfur of dimethyl；Reaction temperature 0～80 DEG C, preferably 20～40 DEG C；Reaction pressure 0～1MPaA,
Preferably 0.2～0.6MPaA；Those skilled in the art can the most skillfully select the type of reactor being suitable for.
Dimethyltrisulfide and methanthiol reacts generation Methyl disulfide in Methyl disulfide reactor, dimethyltrisulfide and
The stoichiometric proportion of methanthiol is 0.5～1, preferably 0.6～0.8, and the dimethyltrisulfide of excess ensure that turning completely of methanthiol
Change, thus avoid methanthiol in follow-up workshop section and be difficult to the problem reclaimed；Reaction temperature 0～60 DEG C, preferably 10～30 DEG C；
Reaction pressure 0～1MPaA, preferably 0.2～0.5MPaA；Those skilled in the art can the most skillfully select to use
Type of reactor.
Methyl disulfide thick product adiabatic flash in knockout drum, operates pressure 0.15MPaA, separates the sulfur of about 70%
Change hydrogen.
Liquid-phase product after flash distillation enters rectifying column, and rectification under vacuum refines Methyl disulfide product, tower top pressure
10～500mmHg, preferably 50～200mmHg, a small amount of hydrogen sulfide discharges as fixed gas, the Methyl disulfide of tower reactor
Returning dimethyltrisulfide reactor cycles with dimethyltrisulfide through circulating pump to use, tower top Methyl disulfide product purity reaches
99wt%, yield is more than 90%.
The hydrogen sulfide that system produces skillfully can be processed by those skilled in the art, and one is to use ripe Crouse's sulfur to return
Skill of knocking off is reclaimed, and two is to return methanthiol synthesis system by compressor cycle to recycle.
Accompanying drawing illustrates:
Fig. 1 is schematic flow sheet used in the present invention
1-sulfur melting tank；2-sulfur feed pump；3-dimethyltrisulfide reactor；4-Methyl disulfide reactor；5-divides
From tank；6-rectifying column；7-overhead condenser；8-tower reactor reboiler；9-Methyl disulfide circulating pump.
Detailed description of the invention:
According to the flow process of Fig. 1, with sulfur and methanthiol as raw material, produce Methyl disulfide continuously.
Embodiment 1
With being pumped to a tubular reactor, diameter 1m, long 10m after the thawing of 433.2kg/h sulfur, material 304 is stainless
Steel, with the 2999.9kg/h Methyl disulfide (composition Methyl disulfide 88.5wt%, dimethyltrisulfide 11.5wt%) of circulation
Mixing, is 20 DEG C by adjust the circular flow of Methyl disulfide controlling reactor inlet temperature, Methyl disulfide and sulfur
The stoichiometric proportion of sulphur (in terms of sulfur simple substance) is 2.1, reaction pressure 0.2MPaA, reactor outlet temperature 30 DEG C, mistake
The Methyl disulfide of amount makes sulfur convert completely, and does not the most produce the many sulfur of dimethyl in course of reaction.
The product of 3433.1kg/h (composition Methyl disulfide 40.3wt%, dimethyltrisulfide 59.7wt%) with
1298.9kg/h methanthiol mixes, and enters a tubular reactor, diameter 1.2m, long 12m, material 304 rustless steel,
Dimethyltrisulfide is 0.6 with the stoichiometric proportion of methanthiol, reaction inlet temperature 10 DEG C, reacts outlet temperature 23.1 DEG C,
Reaction pressure 0.2MPaA.
4732kg/h Methyl disulfide thick product (hydrogen sulfide 9.7wt%, Methyl disulfide 83wt%, dimethyltrisulfide
7.3wt%) enter knockout drum adiabatic flash, operation pressure 0.15MPaA, 354.5kg/h gas (hydrogen sulfide 94.63wt%,
Methyl disulfide 5.34wt%, dimethyltrisulfide 0.03wt%) discharge from gas phase, (the sulfuration of 4377.5kg/h liquid product
Hydrogen 2.8wt%, Methyl disulfide 89.2wt%, dimethyltrisulfide 7.9wt%) enter rectifying column.
Rectifying tower vacuum operates, tower top pressure 100mmHg, tower bottoms 3012.6kg/h(Methyl disulfide 88.5wt% altogether,
Dimethyltrisulfide 11.5%), wherein 2999.9kg/h recycles, and discharges to maintain system Compositional balance, tower top on a small quantity
Being cooled to 10 DEG C, the hydrogen sulfide (hydrogen sulfide 71.8wt%, Methyl disulfide 28.2wt%) of 168.3kg/h is as not coagulating
Gas discharges, and tower top obtains 1196.7kg/h Methyl disulfide product, and purity is 99.7wt%, and yield based on methanthiol reaches
93.8%。
Embodiment 2
With being pumped to a tubular reactor, diameter 1m, long 10m after the thawing of 434.2kg/h sulfur, material 304 is stainless
Steel, with the 4500.3kg/h Methyl disulfide (composition Methyl disulfide 75.9wt%, dimethyltrisulfide 24.1wt%) of circulation
Mixing, is 30 DEG C by adjust the circular flow of Methyl disulfide controlling reactor inlet temperature, Methyl disulfide and sulfur
The stoichiometric proportion of sulphur (in terms of sulfur simple substance) is 2.7, reaction pressure 0.4MPaA, reactor outlet temperature 35 DEG C, mistake
The Methyl disulfide of amount makes sulfur convert completely, and does not the most produce the many sulfur of dimethyl in course of reaction.
The product of 4934.5kg/h (composition Methyl disulfide 43.4wt%, dimethyltrisulfide 56.6wt%) with
1298.9kg/h methanthiol mixes, and enters a tubular reactor, diameter 1.2m, long 12m, material 304 rustless steel,
Dimethyltrisulfide is 0.8 with the stoichiometric proportion of methanthiol, reaction inlet temperature 20 DEG C, reacts outlet temperature 30 DEG C,
Reaction pressure 0.3MPaA.
6233.4kg/h Methyl disulfide thick product (hydrogen sulfide 7.4wt%, Methyl disulfide 75.1wt%, dimethyltrisulfide
17.5wt%) enter knockout drum adiabatic flash, operation pressure 0.15MPaA, 336.6kg/h gas (hydrogen sulfide 93.7wt%,
Methyl disulfide 6.2wt%, dimethyltrisulfide 0.1wt%) discharge from gas phase, 5896.8kg/h liquid product (hydrogen sulfide
2.5wt%, Methyl disulfide 79.1wt%, dimethyltrisulfide 18.5wt%) enter rectifying column.
Rectifying tower vacuum operates, tower top pressure 50mmHg, tower bottoms 4524.8kg/h(Methyl disulfide 75.9wt% altogether,
Dimethyltrisulfide 24.1%), wherein 4500.3kg/h recycles, and discharges to maintain system Compositional balance, tower top on a small quantity
Being cooled to 10 DEG C, the hydrogen sulfide (hydrogen sulfide 64wt%, Methyl disulfide 36wt%) of 223.7kg/h is arranged as fixed gas
Putting, tower top obtains 1148.2kg/h Methyl disulfide product, and purity is 99.9wt%, and yield based on methanthiol reaches 90%.
Embodiment 3
With being pumped to a tubular reactor, diameter 1m, long 10m after the thawing of 433.7kg/h sulfur, material 304 is stainless
Steel, with the 5000.3kg/h Methyl disulfide (composition Methyl disulfide 87.1wt%, dimethyltrisulfide 12.9wt%) of circulation
Mixing, is 35 DEG C by adjust the circular flow of Methyl disulfide controlling reactor inlet temperature, Methyl disulfide and sulfur
The stoichiometric proportion of sulphur (in terms of sulfur simple substance) is 3.4, reaction pressure 0.6MPaA, reactor outlet temperature 40 DEG C, mistake
The Methyl disulfide of amount makes sulfur convert completely, and does not the most produce the many sulfur of dimethyl in course of reaction.
The product of 5434kg/h (composition Methyl disulfide 56.7wt%, dimethyltrisulfide 43.3wt%) with
1298.9kg/h methanthiol mixes, and enters a tubular reactor, diameter 1.2m, long 12m, material 304 rustless steel,
Dimethyltrisulfide is 0.7 with the stoichiometric proportion of methanthiol, reaction inlet temperature 20 DEG C, reacts outlet temperature 28 DEG C,
Reaction pressure 0.5MPaA.
6732.9kg/h Methyl disulfide thick product (hydrogen sulfide 6.8wt%, Methyl disulfide 83.5wt%, dimethyltrisulfide
9.6wt%) enter knockout drum adiabatic flash, operation pressure 0.15MPaA, 329.5kg/h gas (hydrogen sulfide 92.8wt%,
Methyl disulfide 7.1wt%, dimethyltrisulfide 0.1wt%) discharge from gas phase, 6403.4kg/h liquid product (hydrogen sulfide
2.4wt%, Methyl disulfide 87.5wt%, dimethyltrisulfide 10.1wt%) enter rectifying column.
Rectifying tower vacuum operates, tower top pressure 200mmHg, tower bottoms 5026.4kg/h(Methyl disulfide 87.1wt% altogether,
Dimethyltrisulfide 12.9%), wherein 5000.3kg/h recycles, and discharges to maintain system Compositional balance, tower top on a small quantity
Being cooled to 10 DEG C, the hydrogen sulfide (hydrogen sulfide 84.7wt%, Methyl disulfide 15.3wt%) of 172.7kg/h is as not coagulating
Gas discharges, and tower top obtains 1204.3kg/h Methyl disulfide product, and purity is 99.3wt%, and yield based on methanthiol reaches
94%。
Claims (2)
1. the method for a continuous production Methyl disulfide, it is characterised in that:
A) sulfur reacts generation dimethyltrisulfide, diformazan with the Methyl disulfide of excess in dimethyltrisulfide reactor
The stoichiometric proportion of base two sulfur and sulfur is more than 1 less than 4, and the Methyl disulfide of excess ensure that the conversion completely of sulfur,
Decrease the generation of the many sulfur of dimethyl simultaneously；Reaction temperature 0～80 DEG C；Reaction pressure 0～1MPaA；
B) dimethyltrisulfide of excess and methanthiol react in Methyl disulfide reactor and generate Methyl disulfide, and two
Methyl trisulfide is 0.6-1 with the stoichiometric proportion of methanthiol, and the dimethyltrisulfide of excess ensure that turning completely of methanthiol
Change, thus avoid methanthiol in follow-up workshop section and be difficult to the problem reclaimed；Reaction temperature 0～60 DEG C；Reaction pressure
0～1MPaA；
C) the thick product of Methyl disulfide after adiabatic flash uses single column rectification under vacuum to refine Methyl disulfide product, tower
Pressure on top surface 10～500mmHg, a small amount of hydrogen sulfide discharges as fixed gas, the Methyl disulfide of tower reactor and dimethyl three
Sulfur returns dimethyltrisulfide reactor cycles through circulating pump and uses, and tower top Methyl disulfide product purity reaches 99wt%,
Yield is more than 90%.
The most in accordance with the method for claim 1, it is characterised in that:
A) sulfur reacts generation dimethyltrisulfide, diformazan with the Methyl disulfide of excess in dimethyltrisulfide reactor
Base two sulfur is 2.1～3.4 with the stoichiometric proportion of sulfur, and the Methyl disulfide of excess ensure that the conversion completely of sulfur,
Decrease the generation of the many sulfur of dimethyl simultaneously；Reaction temperature 20～40 DEG C；Reaction pressure 0.2～0.6MPaA；
B) dimethyltrisulfide of excess and methanthiol react in Methyl disulfide reactor and generate Methyl disulfide, and two
Methyl trisulfide is 0.6～0.8 with the stoichiometric proportion of methanthiol, and the dimethyltrisulfide of excess ensure that the complete of methanthiol
Convert, thus avoid methanthiol in follow-up workshop section and be difficult to the problem reclaimed；Reaction temperature 10～30 DEG C, reaction pressure
0.2～0.5MPaA；
C) the thick product of Methyl disulfide after adiabatic flash uses single column rectification under vacuum to refine Methyl disulfide product, tower
Pressure on top surface 50～200mmHg, a small amount of hydrogen sulfide discharges as fixed gas, the Methyl disulfide of tower reactor and dimethyl three
Sulfur returns dimethyltrisulfide reactor cycles through circulating pump and uses, and tower top Methyl disulfide product purity reaches 99wt%,
Yield is more than 90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410105544.4A CN103864650B (en) | 2014-03-20 | A kind of method of continuous production Methyl disulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410105544.4A CN103864650B (en) | 2014-03-20 | A kind of method of continuous production Methyl disulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103864650A CN103864650A (en) | 2014-06-18 |
| CN103864650B true CN103864650B (en) | 2016-11-30 |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant after: CNOOC Energy Development Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC Tianjin Chemical Research & Design Institute Applicant before: CNOOC Energy Development Co., Ltd. |
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Effective date of registration: 20161017 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant after: CNOOC Energy Development Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant before: CNOOC Energy Development Co., Ltd. |
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