CN114181125A - Process for the separation of methyl mercaptan - Google Patents
Process for the separation of methyl mercaptan Download PDFInfo
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- CN114181125A CN114181125A CN202111502521.3A CN202111502521A CN114181125A CN 114181125 A CN114181125 A CN 114181125A CN 202111502521 A CN202111502521 A CN 202111502521A CN 114181125 A CN114181125 A CN 114181125A
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- C07C319/28—Separation; Purification
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Abstract
The invention relates to a method for separating methyl mercaptan, which comprises the steps of carrying out two-stage condensation on methyl mercaptan product gas, arranging a water absorption process between the two-stage condensation process, distilling by using a water phase obtained by the first-stage condensation, and taking distillation residual liquid as a water absorption raw material; the product methyl mercaptan obtained by the method does not contain raw materials of hydrogen sulfide and methanol basically, and the exhaust gas does not contain hydrogen sulfide, methanol and methyl mercaptan basically, so that the reaction yield can be effectively increased, the side reaction can be reduced, and the loss can be reduced.
Description
Technical Field
The invention relates to the field of chemical production of methyl mercaptan, and particularly relates to a method for obtaining methyl mercaptan from methyl mercaptan reaction gas prepared from methanol and hydrogen sulfide after fractional condensation and refining.
Background
Methyl mercaptan is an important chemical intermediate, is widely used for synthesizing methomyl, bifenthrin, aldicarb, dimethyldisulfide, methanesulfonyl chloride and the like, and is more largely used for synthesizing a methionine intermediate 3-methylthiopropanal.
The synthetic method of methyl mercaptan is about three methods: the first method is obtained by nucleophilic substitution of hydrosulfide and methyl halide, wherein the methyl halide is expensive and only suitable for preparation of small dosage; the second method is nucleophilic substitution preparation of dimethyl sulfate and sulfide, theoretically with 0.5 equivalent of sulfate per 1 equivalent of methyl mercaptan produced, because of the incomplete and residual reaction, the cost of sulfate treatment is high, especially under the current increasingly strict environmental protection; the third method is also one of the main methods of industrial production, and the aluminum oxide supported transition metal is prepared by catalyzing hydrogen sulfide and methanol to react at 300-500 ℃ and 2-15 bar.
The method is characterized in that the methyl mercaptan is prepared from hydrogen sulfide and methanol, the reaction yield is generally 60-90%, and the reaction gas comprises dimethyl sulfide, dimethyl disulfide, dimethyl ether, carbon monoxide, methane, carbon dioxide and nitrogen besides the target product methyl mercaptan, the reaction raw material methanol, the reaction raw material hydrogen sulfide and the product water. Dimethyl ether and dimethyl sulfide can still continuously generate methyl mercaptan, other inert gases circularly extrude the reaction pressure, and the separation of mixed gas products, the return of raw materials to a system and the diversion of the inert gases are necessary operations. At standard atmospheric pressure, methyl mercaptan boiling point of 7.6 ℃, methanol boiling point of 64.7 ℃, dimethyl sulfide boiling point of 38 ℃, hydrogen sulfide boiling point of-60.4 ℃ and dimethyl ether boiling point of-24.8 ℃ mean that physical separation of the mixed gas is a difficult thing, and atmospheric pressure condensation is not desirable, which requires high cost preparation of condensing medium with proper temperature and larger equipment.
FR2477538 is that most of reaction gas is condensed at 20-30 deg.C and 8-10 bar, and is divided into water phase, organic phase and gas phase, and methyl mercaptan, methanol and hydrogen sulfide are obtained by separate treatment. The temperature of reaction gas at 300 ℃ is reduced to 20-30 ℃, the required energy consumption is large, the materials are not separated by phase separation, the solubility of methanol to water, methyl mercaptan, hydrogen sulfide, dimethyl sulfide and methyl sulfide is relatively high under high pressure, and a water phase, an organic phase and a gas phase all contain the components and respectively need to be refined to achieve the purpose of material fine separation.
CN1189487A uses two-stage condensation to respectively obtain water phase and organic phase, residual gas is absorbed by methanol and then returned to the system, and the discharged gas enables the methanol to absorb hydrogen sulfide so as to lead the hydrogen sulfide to be basically free of hydrogen sulfide. And (3) mixing and refining the water phase, the organic phase and the absorption methanol: separating hydrogen sulfide, methyl mercaptan, dimethyl sulfide and methanol separately, and introducing water into the system to prevent formation of methyl mercaptan/methanol azeotrope. The temperature of the aqueous phase condensate is 55-65 ℃, the contents of methyl mercaptan and hydrogen sulfide are very low, the mixture of the aqueous phase condensate and the organic phase and the absorbed methanol is not suitable for removing the hydrogen sulfide, and the methyl mercaptan and the dimethyl sulfide are proposed to be included in a system enriching the methanol, so that the separation efficiency is reduced, and the product purity is reduced.
In conclusion, the existing separation method has the disadvantages that the reaction gas is difficult to refine into high-purity substances, so that the operation is complicated, the refining energy consumption is high, the raw materials are wasted, the yield is reduced and the byproducts are increased due to the fact that the products return to the system and the reaction pressure is squeezed, the refined methyl mercaptan still contains methanol and hydrogen sulfide components, and the subsequent use yield is influenced by the ultra-strong reaction performance of the hydrogen sulfide.
Disclosure of Invention
In view of the above, the present invention aims to overcome the defects in the prior art and provide a method for separating methyl mercaptan, wherein the purity of the obtained methyl mercaptan is higher.
The separation method of methyl mercaptan comprises the steps of carrying out two-stage condensation on methyl mercaptan product gas to obtain a water phase containing methanol, an organic phase containing methyl mercaptan and hydrogen sulfide and condensing non-condensable gas, wherein the methyl mercaptan product gas is reaction gas obtained by catalytic reaction of methanol and hydrogen sulfide, and the separation method further comprises the following steps:
(A) the water phase is distilled separately, and condensed non-condensable gas is washed by using water phase distillation residual liquid before being discharged out of a system finally;
(B) a water absorption process is arranged between the two stages of condensation processes, and the absorption water used for absorption is water phase distillation residual liquid and/or washing liquid for condensing non-condensable gas;
(C) the organic phase is separately distilled to separate the methyl mercaptan.
Further, the condensed non-condensable gas is divided into a return part and a discharge part, methanol is used for primary washing before the division, the discharge part after the division is used for secondary washing by using the methanol to absorb hydrogen sulfide, the methanol after the secondary washing is used as washing liquid for the primary washing, and the methanol after the secondary washing is transferred to the primary condensation.
Further, the aqueous phase distillation residue washing is performed after the second washing.
Further, the method also comprises the step of carrying out water phase absorption on the methyl mercaptan product gas by utilizing the water phase countercurrent after the first-stage condensation.
Further, the distillation of the organic phase comprises:
(1) distilling at the tower top temperature of 30-40 ℃ under 10-14 bar to take out hydrogen sulfide, and merging the evaporated hydrogen sulfide into condensed noncondensable gas and/or a water absorption process between primary condensation and secondary condensation;
(2) and then, at 9-11 bar, controlling the temperature at the top of the tower to be 20-25 ℃, evaporating methyl mercaptan and condensing, and returning residual liquid in the tower kettle to the system to prepare methyl mercaptan again.
Further, condensing the methyl mercaptan in the step (2), extracting and purifying with water, wherein the mass ratio of the water to the methyl mercaptan is 0.1-3, concentrating hydrogen sulfide in the water, then distilling under reduced pressure to extract the hydrogen sulfide, and continuously using the water for extracting the methyl mercaptan; after methanol in water is enriched, the water is transferred out and is merged into an absorption process to be used as absorption liquid for water absorption.
Further, the methanol is extracted by water phase distillation, and the distillation is carried out in a distillation tower with the pressure of 8-11 bar and the temperature of 30-50 ℃ at the top of the tower, and the hydrogen sulfide and the methyl mercaptan are evaporated and transferred to an absorption process between primary condensation and secondary condensation.
Further, the pressure in the water absorption process, the primary washing process, the secondary washing process and the water phase distillation residual liquid washing process is 2-15 bar.
The invention has the beneficial effects that: the invention discloses a method for separating methyl mercaptan, which changes the traditional method of extracting low-content methyl mercaptan and hydrogen sulfide in a methanol-rich environment.
Drawings
The invention is further described below with reference to the following figures and examples:
FIG. 1 is a schematic flow diagram of the process of the present invention.
Description of reference numerals: the system comprises a first-stage condensation tower 11, a water absorption tower 12, a second-stage condensation tower 13, a first absorption tower 14, a second absorption tower 15, a water phase first distillation tower 21, a water phase second distillation tower 22, an organic phase first distillation tower 31, an organic phase second distillation tower 32, an auxiliary condensation tower 33, a liquid separator 34 and a low-pressure device 35.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, in the methyl mercaptan separation method in this embodiment, the reaction gas from the methyl mercaptan reactor exchanges heat, the temperature is reduced from 300-400 ℃ to 110-130 ℃, and the pressure is 8-10 bar. The mixed gas is primarily condensed into a water phase, a good condensation effect can be obtained by using the primary condensation tower 11, and the liquefaction rate of the methanol and the water reaches more than 85 percent. The condensing tower uses tower plates or fillers or tubes, the type of the tower plates, the filling mode and the tubes are not limited, desalted water is used for replacing condensate at the initial stage of starting, circulation and heat exchange are carried out from a tower kettle to the top of the tower, and the temperature of the top of the tower is controlled to be 50-70 ℃.
The primary condensation non-condensable gas still contains uncondensed methanol and water, the content of the uncondensed methanol and water changes according to the load of a primary condensation tower and a system, the primary condensation non-condensable gas is transferred to a water absorption tower 12 to absorb residual methanol again, the temperature of the tower top is controlled to be 50-60 ℃, the water absorption can reduce the content of the non-condensable gas methanol to be below 1 v/v%, when the content of the non-condensable gas methanol is increased to 1 v/v%, absorbed water is transferred to primary condensation, and at the moment, the absorbed water methanol is enriched.
The non-condensable gas after water absorption is mainly hydrogen sulfide and methyl mercaptan, the ratio of the non-condensable gas to the methyl mercaptan is more than 90 v/v%, the non-condensable gas enters a second-stage condensation tower 13 at the temperature of 10-30 ℃ to be subjected to secondary condensation, more than 90% of methyl mercaptan and 5-15% of hydrogen sulfide are condensed into an organic phase, and the condensed gas also comprises dimethyl sulfide, water and methanol.
And (3) absorbing the secondary condensed non-condensable gas at 10-30 ℃ by using methanol in a first absorption tower 14 and discharging residual gas, wherein the content of hydrogen sulfide in the residual gas is more than 95 v/v%, the residual gas is returned to the system after compression to prepare methyl mercaptan again, in the reaction process or the inert gas introduced by the methanol or the hydrogen sulfide is accumulated in the system, 5-20% of the raw material methanol needs to be shunted and discharged out of the system after being absorbed in a second absorption tower 15, the absorption temperature is 10-15 ℃, and when the content of the hydrogen sulfide in the discharged gas is more than 0.8 v/v%, the methanol is transferred into the methanol of the secondary condensed non-condensable gas for absorption.
Transferring the water phase into a first water phase distillation tower 21, merging residual hydrogen sulfide and methyl mercaptan evaporated at the pressure of 8-10 bar and the tower top temperature of 30-50 ℃ into water between primary condensation and secondary condensation for absorption, transferring the methanol water solution into a second water phase distillation tower 22, controlling the tower top temperature of 60-70 ℃ and 0bar to evaporate methanol, transferring the residual liquid which is the water solution with the methanol content of not more than 3 wt% into water absorption of exhaust gas, controlling the temperature of the exhaust gas to be 10-15 ℃, and fully transferring heat and mass without pre-cooling the transferred residual liquid.
And transferring the organic phase into an organic phase first distillation tower 31, controlling the tower top temperature at 11-14 bar and 30-40 ℃ to evaporate hydrogen sulfide into secondary condensed noncondensable gas, transferring the tower bottom liquid into an organic phase second distillation tower 32, controlling the tower top temperature at 32 at 9-11 bar and 20-25 ℃ to take out methyl mercaptan, and returning the tower bottom liquid which is dimethyl sulfide to the system.
The methyl mercaptan evaporated from the top of the organic phase second distillation tower 32 is condensed into liquid in the auxiliary condensation tower 33, the condensed methyl mercaptan is mixed with water, the condensed methyl mercaptan is kept stand and layered in the liquid separator 34, the upper layer of methyl mercaptan is taken out, the purity of the upper layer of methyl mercaptan can reach more than 99.7 wt%, the lower layer of water is continuously mixed with the methyl mercaptan after hydrogen sulfide is removed in the low-pressure device 35 to extract hydrogen sulfide and methanol of the methyl mercaptan, and when the quality of the methyl mercaptan is influenced by water-methanol enrichment, water absorption between primary condensation and secondary condensation is carried out. The water extraction can change the content of methyl mercaptan hydrogen sulfide from 0.01-0.05 wt% to 0.001-0.005 wt%, the content of methanol from 0.01-0.05 wt% to 0.001-0.01 wt%, and the circulation frequency of water can reach 20-50 times.
Example 2
The temperature of the reaction gas is above 300 ℃, the reaction gas is quenched and cooled to 110-130 ℃, then the reaction gas is separated into water phase condensate and primary condensed noncondensable gas through primary condensation at 50-70 ℃, the water phase condensate (also called water phase) is in countercurrent flow to absorb the reaction gas, methanol, water and dimethyl disulfide are condensed in the temperature range, the respective liquefaction rate of the methanol and the water can reach above 85%, the dimethyl disulfide is basically completely liquefied, and the methyl mercaptan and the hydrogen sulfide basically exist in a gas phase.
And (3) carrying out secondary condensation and separation on the primary condensed non-condensable gas at the temperature of 10-30 ℃ to obtain an organic phase condensate (also called an organic phase) and a secondary condensed non-condensable gas, condensing more than 90% of methyl mercaptan, substantially all dimethyl sulfide, and condensing methanol and 5-15% of hydrogen sulfide.
And (3) absorbing methyl mercaptan by using methanol at the temperature of 10-30 ℃ in the secondary condensation noncondensable gas, and converting the methyl mercaptan into residual gas after absorbing the methyl mercaptan. The residual gas is divided according to the content of the inert gas, generally speaking, the system stability can be ensured by 5-20% of division ratio, the conversion rate of the methyl mercaptan and the generation rate of byproducts have no obvious fluctuation, and the residual gas is hydrogen sulfide for circulation.
The split-flow residual gas absorbs hydrogen sulfide at 0-15 ℃ by using methanol, so that the loss of the hydrogen sulfide is reduced as much as possible. The content of hydrogen sulfide in the exhaust gas is preferably below 1 v/v%, and the content of hydrogen sulfide is transferred out by 2-5 wt% after the methanol is absorbed.
In order to further reduce hydrogen sulfide and methanol in the exhaust gas, the exhaust gas is preferably subjected to absorption washing again by using water, the water is preferably aqueous phase distillation raffinate, the proportion of the aqueous phase distillation raffinate is returned to 10-50%, and the rest is discharged out of the system.
The raw material methanol is preferably used for absorbing the split residual gas, the temperature is low, the sulfur is not contained, the cooling cost is low, and the efficiency of absorbing the hydrogen sulfide is high.
The methanol absorbed by the secondary condensed non-condensable gas is preferably the methanol absorbed by the split-flow residual gas, the methanol absorbed by the secondary condensed non-condensable gas is mainly used for absorbing methyl mercaptan to release hydrogen sulfide, and the methanol absorbed by the split-flow residual gas is used for saving the use amount of methanol and reducing the distillation energy.
The usage amount of the methanol absorbed by the secondary condensed non-condensable gas is related to the content of methyl mercaptan in the secondary condensed non-condensable gas, the methyl mercaptan saturated methanol is transferred out when the content of the methyl mercaptan in the residual gas is higher than 0.8 v/v%, the methyl mercaptan unsaturated methanol is supplemented, the methanol absorbed by the transferred out secondary condensed non-condensable gas is preferably transferred into primary condensation, and the methyl mercaptan in the primary condensation is evaporated again.
In order to further reduce the content of the methanol in the condensed organic phase, water absorption is increased in primary condensation and secondary condensation, the temperature is preferably 50-60 ℃, and the water is preferably the absorption water of the discharged gas and the distillation residual liquid of the water phase. When the methanol content of the non-condensable gas absorbed by the water exceeds 3 v/v%, the absorbed water is transferred to primary condensation.
All the above operating pressures are carried out at 2-15 bar, the preferable pressure is 7-12 bar, the further preferable pressure is 9-11 bar, the pressure of the patent is not specially stated and is relative pressure, and heating and cooling energy can be effectively saved in the pressure interval.
The main component of the organic phase is methyl mercaptan, and the other components are hydrogen sulfide, methanol and water, and need to be transferred out for refining. And (3) distilling at the tower top temperature of 30-40 ℃ under the condition of 10-14 bar to take out hydrogen sulfide, and merging the distilled hydrogen sulfide into secondary condensation noncondensable gas or water absorption between primary condensation and secondary condensation. And then, controlling the temperature at the top of the tower at 9-11 bar and 20-25 ℃ to evaporate methyl mercaptan and condense the methyl mercaptan, returning the residual liquid in the tower kettle to the system to prepare methyl mercaptan again, wherein the dimethyl sulfide is dimethyl sulfide.
The reaction activity of hydrogen sulfide contained in the condensed methyl mercaptan is stronger, the methanol can also cause the purification operation of subsequent reaction, in order to further improve the purity of the methyl mercaptan, the condensed methyl mercaptan can be mixed with water, and the upper layer after layering is the high-purity methyl mercaptan, and the purity of the high-purity methyl mercaptan can reach more than 99.7 wt%. Methyl mercaptan is mixed with water, which extracts the methanol and hydrogen sulfide from the organic phase using static vortexing or mixing or circulating. The mass ratio of water to methyl mercaptan is 0.1-3, and no clear requirement exists. The mixing temperature is preferably the condensation temperature of methyl mercaptan.
When the hydrogen sulfide in the water tends to be enriched and shows that the concentration of the hydrogen sulfide in the methyl mercaptan begins to increase, the water is transferred out and is pumped out under reduced pressure, the water is continuously used for extracting the methyl mercaptan, the pressure is preferably-0.1-5 bar, the pumped hydrogen sulfide is transferred into secondary condensed non-condensable gas after being compressed, more preferably, raw material methanol is used for absorption, and the partial raw material methanol is used for absorbing the secondary condensed non-condensable gas.
When the methanol in the water tends to be enriched, which is indicated by the beginning of the increase in methanol concentration in methyl mercaptan, the water is diverted and fed to a quantitative water, the extraction can be operated batchwise or in a continuous manner, preferably continuously, preferably with the diverted water being incorporated into the water absorption between the primary and secondary condensation.
And (3) transferring the primary condensed water phase out to extract methanol, preferably selecting the pressure to be 8-11 bar after transferring out, preferably selecting the temperature at the top of the tower to be 30-50 ℃, evaporating the hydrogen sulfide and the methyl mercaptan in the residual system, and transferring the hydrogen sulfide and the methyl mercaptan into water absorption between primary condensation and secondary condensation. Collecting the main component of the fraction of 60-70 ℃ in the methanol aqueous solution under the atmospheric pressure, and returning the fraction to the system.
The mixed gas is separated into the product methyl mercaptan, the product methyl mercaptan basically does not contain raw materials of hydrogen sulfide and methanol, the methyl mercaptan returns to a system, the discharged gas basically does not contain hydrogen sulfide, methanol and methyl mercaptan, the reaction yield can be effectively increased, the side reaction is reduced, and the loss is reduced.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (8)
1. The separation method of methyl mercaptan comprises the steps of carrying out two-stage condensation on methyl mercaptan product gas to obtain a water phase containing methanol, an organic phase containing methyl mercaptan and hydrogen sulfide and condensing non-condensable gas, wherein the methyl mercaptan product gas is reaction gas obtained by catalytic reaction of methanol and hydrogen sulfide, and the separation method is characterized by further comprising the following steps of:
(A) the water phase is distilled separately, and condensed non-condensable gas is washed by using water phase distillation residual liquid before being discharged out of a system finally;
(B) a water absorption process is arranged between the two stages of condensation processes, and the absorption water used for absorption is water phase distillation residual liquid and/or washing liquid for condensing non-condensable gas;
(C) the organic phase is separately distilled to separate the methyl mercaptan.
2. The process according to claim 1, characterized in that: the condensed noncondensable gas is divided into a return part and a discharge part, methanol is used for primary washing before the division, the discharge part after the division is used for secondary washing by the methanol to absorb hydrogen sulfide, the methanol after the secondary washing is used as washing liquid of the primary washing, and the methanol after the secondary washing is used for transferring the methanol after the secondary washing into the primary condensation.
3. A process according to claim 2, characterized in that: the aqueous phase distillation residue wash was performed after the second wash.
4. The process according to claim 1, characterized in that: and the method also comprises the step of carrying out water phase absorption on the methyl mercaptan product gas by utilizing the water phase countercurrent after the first-stage condensation.
5. The process according to claim 1, characterized in that: the distillation of the organic phase comprises:
(1) distilling at the tower top temperature of 30-40 ℃ under 10-14 bar to take out hydrogen sulfide, and merging the evaporated hydrogen sulfide into condensed noncondensable gas and/or a water absorption process between primary condensation and secondary condensation;
(2) and then, at 9-11 bar, controlling the temperature at the top of the tower to be 20-25 ℃, evaporating methyl mercaptan and condensing, and returning residual liquid in the tower kettle to the system to prepare methyl mercaptan again.
6. A process according to claim 5, characterized in that: extracting and purifying the condensed methyl mercaptan with water in a mass ratio of the water to the methyl mercaptan of 0.1-3 in the step (2), concentrating hydrogen sulfide in the water, then distilling under reduced pressure to extract the hydrogen sulfide, and continuously using the water for extracting the methyl mercaptan; after methanol in water is enriched, the water is transferred out and is merged into a water absorption process to be used as absorption liquid for water absorption.
7. The process according to claim 1, characterized in that: and distilling the water phase to extract the methanol, and distilling the hydrogen sulfide and the methyl mercaptan out in a distillation tower with the pressure of 8-11 bar and the temperature of the tower top of 30-50 ℃ to transfer the hydrogen sulfide and the methyl mercaptan into a water absorption process between primary condensation and secondary condensation.
8. A process according to any one of claims 2 to 7, characterized in that: the pressure in the water absorption process, the primary washing process, the secondary washing process and the water phase distillation residual liquid washing process is 2-15 bar.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB830932A (en) * | 1955-06-22 | 1960-03-23 | American Oil Co | Improved method of making methyl mercaptan |
| FR2477538A2 (en) * | 1980-03-06 | 1981-09-11 | Rhone Poulenc Ind | Vapour phase prepn. of methyl-mercaptan - from methanol and hydrogen sulphide using activated alumina catalyst |
| CN1189487A (en) * | 1996-12-27 | 1998-08-05 | 底古萨股份公司 | Separation method of product gas mixture for catalytic synthesis of methyl mercaptan |
| CN1894207A (en) * | 2003-12-18 | 2007-01-10 | 德古萨股份公司 | Method for the separation of methyl mercaptan from reaction gas mixtures |
-
2021
- 2021-12-10 CN CN202111502521.3A patent/CN114181125A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB830932A (en) * | 1955-06-22 | 1960-03-23 | American Oil Co | Improved method of making methyl mercaptan |
| FR2477538A2 (en) * | 1980-03-06 | 1981-09-11 | Rhone Poulenc Ind | Vapour phase prepn. of methyl-mercaptan - from methanol and hydrogen sulphide using activated alumina catalyst |
| CN1189487A (en) * | 1996-12-27 | 1998-08-05 | 底古萨股份公司 | Separation method of product gas mixture for catalytic synthesis of methyl mercaptan |
| CN1894207A (en) * | 2003-12-18 | 2007-01-10 | 德古萨股份公司 | Method for the separation of methyl mercaptan from reaction gas mixtures |
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Application publication date: 20220315 |