CN107473992B - Method for preparing methanesulfonyl chloride by using waste generated in dimethyl sulfone production - Google Patents
Method for preparing methanesulfonyl chloride by using waste generated in dimethyl sulfone production Download PDFInfo
- Publication number
- CN107473992B CN107473992B CN201710745419.3A CN201710745419A CN107473992B CN 107473992 B CN107473992 B CN 107473992B CN 201710745419 A CN201710745419 A CN 201710745419A CN 107473992 B CN107473992 B CN 107473992B
- Authority
- CN
- China
- Prior art keywords
- reaction
- solid
- sodium methanesulfonate
- sodium
- methanesulfonyl chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a method for preparing methanesulfonyl chloride by using waste generated in the production of dimethyl sulfone, which comprises the following steps: a. uniformly mixing solid waste generated in the production of dimethyl sulfone with acetone, and removing organic sulfur components in the solid waste by condensation and reflux; b. uniformly mixing the solid waste from which the organic sulfur component is removed with water, separating sodium methanesulfonate and sodium nitrate by using a strong acid cation exchange resin, and performing rotary evaporation on the sodium methanesulfonate aqueous solution obtained by separation to obtain sodium methanesulfonate solid; c. and dissolving the obtained sodium methanesulfonate solid in chloroform, adding a proper amount of DMF (dimethyl formamide), slowly adding thionyl chloride, heating the mixed solution in an oil bath to react, cooling the reaction solution after the reaction is finished, filtering in vacuum, and carrying out rotary evaporation on the filtrate to obtain methanesulfonyl chloride. The invention utilizes the solid waste generated in the production of the dimethyl sulfone to prepare the methanesulfonyl chloride, fully utilizes waste resources, not only reduces the cost, but also avoids the environmental pollution caused by the waste.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method for preparing methanesulfonyl chloride by using waste generated in dimethyl sulfone production.
Background
Dimethyl sulfone, as an organic sulfide, has the ability to enhance insulin production in the human body, plays a role in promoting the metabolism of saccharides, is also an essential substance for the synthesis of collagen in the human body, can also promote wound healing, and also plays a role in the synthesis and activation of vitamin B, vitamin C and biotin, which are required for metabolism and nerve health, and is called as a "natural beautifying carbon substance".
At present, the domestic industrial production method of dimethyl sulfone is mainly obtained by oxidizing dimethyl sulfoxide by nitric acid, and the method not only has the problems of high reaction temperature, high energy consumption, long process flow, more byproducts and the like, but also can generate a large amount of waste materials containing sodium nitrate, sodium nitrite, sodium methanesulfonate and the like, has low utilization rate of the waste materials, and most of the waste materials are discarded, thereby not only polluting the environment, but also being a waste for available substances in the waste materials.
Methanesulfonyl chloride has high reaction activity, is an important organic synthesis intermediate, and can be used as a catalyst for esterification and polymerization; in chemical industry, it is used as wool dyeing assistant, color regulator for color photograph, fast solidifying agent for oil film of drying oil and paint, and raw material for medicine and agricultural chemicals. The raw materials of the two methods are expensive, the methanethiol, dimethyl disulfide, methyl thiocyanate and the like are used as substrates, and the methane sulfonyl chloride is produced by directly oxidizing or electrolyzing chlorine gas, so that the side reactions are more, the yield is low, and the product is not easy to separate.
Disclosure of Invention
The invention provides a method for preparing methanesulfonyl chloride by using waste generated by dimethyl sulfone production, aiming at the problem of low utilization rate of waste generated by dimethyl sulfone production in the existing method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing methanesulfonyl chloride by using waste generated in the production of dimethyl sulfone comprises the following steps:
a. uniformly mixing solid waste generated in the production of dimethyl sulfone with acetone, and removing organic sulfur components in the solid waste by condensation and reflux;
b. uniformly mixing the solid waste from which the organic sulfur component is removed with water, separating sodium methanesulfonate and sodium nitrate by using a strong acid cation exchange resin, and performing rotary evaporation on the sodium methanesulfonate aqueous solution obtained by separation to obtain sodium methanesulfonate solid;
c. and dissolving the obtained sodium methanesulfonate solid in chloroform, adding a proper amount of DMF (dimethyl formamide), then adding thionyl chloride, heating the mixed solution in an oil bath to react, cooling the reaction solution after the reaction is finished, filtering in vacuum, and carrying out rotary evaporation on the filtrate to obtain methanesulfonyl chloride. In the step, thionyl chloride and sodium methanesulfonate are subjected to exothermic reaction, the thionyl chloride needs to be slowly added, and DMF is used as a catalyst; and washing the filtered filter residue with ethanol and drying to obtain sodium chloride.
Preferably, the step a specifically comprises the following steps:
a1, uniformly mixing solid waste generated in the production of dimethyl sulfone with acetone according to the mass-volume ratio of 1g: 1.2-1.8 mL, stirring in a water bath at the temperature of 65-70 ℃, condensing and refluxing for 1-1.5 h, and then cooling to 20-25 ℃;
a2, filtering the cooled mixture in vacuum, and drying the filter residue at 60 ℃.
Step a is mainly to remove organic sulfur components in the solid waste, wherein the filter residue filtered in step a2 can be added with acetone with the mass volume ratio of 1g: 0.6-0.7 mL according to needs to be mixed and stirred for 30min so as to further remove the organic sulfur components, and the obtained filter residue mainly contains sodium methanesulfonate and sodium nitrate; the resulting filtrate was collected by filtration and acetone was removed by rotary evaporation to give dimethyl sulfone and dimethyl sulfoxide.
Preferably, the step b specifically comprises the following steps:
b1, uniformly mixing the filter residue dried in the step a2 with water in equal mass, adjusting the pH to 5-6 with dilute nitric acid, heating to 55-65 ℃, stirring for 1.5-3 h, and cooling to 20-25 ℃; the dried filter residue contains a small amount of sodium nitrite, a small amount of dilute nitric acid is added, heating and stirring are matched, the added dilute nitric acid can react with the sodium nitrite to generate nitrous acid, and the generated nitrous acid can be further decomposed into nitrogen dioxide, so that the sodium nitrite is removed;
b2, adding the reaction liquid cooled in the step b1 and strong acid cation resin into a separating funnel according to the volume ratio of 1: 3.5-4.5, standing for 1-2 hours, and collecting an aqueous solution at the lower part of the separating funnel; in the step, the flow rate of the aqueous solution at the lower part of the separating funnel is controlled to discharge the aqueous solution for 4-4.5 hours, and a proper amount of deionized water can be added to flush the cation exchange resin for several times according to needs, wherein the control of the flow rate of the aqueous solution is particularly critical, the flow rate is too high, sodium ions in the solution can be incompletely adsorbed, so that the problems of excessive sodium nitrate content in the final product and incomplete flushing of sodium methanesulfonate can be caused if the flow rate is too low;
b3, rotationally evaporating the water solution collected in the step b2 to obtain a yellow-white solid, mixing the yellow-white solid with absolute ethyl alcohol, stirring in a water bath for 5-6 hours, then carrying out vacuum filtration on the mixed solution, and drying filter residues at 90 ℃ to obtain a sodium methanesulfonate solid. In the step, water is removed by rotary evaporation and concentration until no water drips from the condenser, and most of nitric acid is removed along with the evaporation of the water; the anhydrous ethanol can react with the residual nitric acid in the solid, and has the exothermic phenomenon, so that acetaldehyde is generated and bubbles are emitted.
Preferably, the oil bath heating reaction step described in step c is as follows:
the oil temperature is increased to 35 ℃, the stirring reaction is carried out for 30-35 min, the temperature is increased to 60 ℃, the reaction is carried out for 50-60 min, the temperature is increased to 80 ℃, the reaction is carried out for 10-15 min, the temperature is increased to 100 ℃, the reaction is carried out for 6-7 h, then the temperature is reduced to 60 ℃, and the chloroform is supplemented, wherein the mass volume ratio of the sodium methanesulfonate to the supplemented chloroform is 1g: 2-3 mL, and the mixture is stirred uniformly and cooled to 20-25 ℃. The influence of the temperature rise and reduction processes of the reaction in the step on the yield of the methanesulfonyl chloride is particularly critical and needs to be strictly controlled.
Preferably, when the sodium methanesulfonate solid is dissolved in chloroform in the step c, the mass volume ratio of the sodium methanesulfonate to the chloroform is 1g: 0.4-0.5 mL.
Preferably, the molar ratio of the sodium methanesulfonate to the thionyl chloride in step c is 1: 1.1-1.5.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention utilizes the waste generated in the production of dimethyl sulfone to prepare methanesulfonyl chloride, fully utilizes waste resources, not only reduces the cost, but also avoids the waste from polluting the environment, and improves the utilization value of industrial byproducts.
2. The method adopts chloroform as a solvent, DMF as a catalyst and thionyl chloride as a chlorinating agent, and combines the control of temperature rise and temperature reduction in the reaction process, so that the yield of reaction products is greatly improved, wherein the influence of the temperature rise and temperature reduction process on the yield of methanesulfonyl chloride in the reaction is particularly critical and needs to be strictly controlled.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
1. Extraction of organic sulphur components from solid waste
A. 300g of a sample (the pH value is not more than 8, and the main components are waste materials such as sodium nitrate, sodium nitrite, sodium methanesulfonate and the like) of the Hengjie chemical waste brought back from the Tanjiang in 3 months in 2014 is added into a 1L single-neck flask, 450mL of acetone is weighed by using a measuring cylinder and added into the flask, and stirring seeds are added. The flask was placed in a magnetic stirring water bath, a spherical condenser tube with cooling water was installed, and magnetic stirring was started. Heating the water bath to 65 ℃, gradually starting acetone to reflux, stirring and refluxing the acetone for 1 hour after the acetone is stably refluxed, and then cooling the mixture to room temperature.
B. After cooling, the mixture obtained is filtered by a glass sand funnel in a vacuum pumping way, the solid is returned to the flask after being pumped to be dry, 200ml of acetone is added into the flask, the mixture is magnetically stirred for 30 minutes at room temperature, then the mixture is filtered in a vacuum pumping way, and finally the solid is washed by 50ml of acetone and pumped to be dry. The obtained solid was dried in a drying oven at 60 ℃ for 3 hours to obtain 224g of a solid mainly containing sodium methanesulfonate and sodium nitrate.
C. All the acetone filtrates are collected and combined, vacuum-pumped and decompressed, and concentrated by a rotary evaporator to remove acetone, and finally 68.8g of yellow oily matter is obtained, and the yellow oily matter is cooled to room temperature and partially solidified to separate out solid, mainly comprising dimethyl sulfone and dimethyl sulfoxide.
2. Separation of sodium methanesulfonate and sodium nitrate using a strongly acidic cation exchange resin
A. And B, putting 200g of the solid dried in the step B into a 1L beaker, adding 200ml of deionized water (equal to the mass of the dried solid), putting the stirred seeds into the beaker, putting the beaker into a magnetic stirring water bath, starting stirring, uniformly mixing, adjusting the pH value to 5-6 by using a small amount of dilute nitric acid, and decomposing nitrous acid generated by the reaction of sodium nitrite and nitric acid to generate nitrogen dioxide. Then the water bath is heated to 60 ℃ and stirred for 2 hours to remove nitrous acid, and the reaction liquid is cooled to room temperature to obtain a mixed water solution with the main components of sodium methanesulfonate and sodium nitrate, wherein the volume of the mixed water solution is 330 ml.
B. Adding 1.2L of regenerated strong acid cation resin into a separating funnel, discharging water until the water is level with the resin, wherein the pH value of the discharged water is close to 7, adding 330ml of cooled mixed aqueous solution into the separating funnel, and standing for 1 hour.
C. The lower switch of the separating funnel is opened, the aqueous solution is discharged, the pH value of the aqueous solution is 1, the aqueous solution is discharged after 4 hours, and the flow rate is about 100 ml/hour. When the added mixed aqueous solution is discharged, deionized water is added to continuously wash the ion exchange resin, 100ml of deionized water (half of the deionized water added in the step A) is added each time, the total amount is 800ml, the flow rate is about 114 ml/hour, and the discharge is finished in 7 hours. The whole process yielded 1100ml of aqueous solution, which took 11 hours.
And (3) judging the end point: burning the water sample with clean fine iron wire in alcohol lamp, soaking the water from the lower port of separating funnel, burning in alcohol lamp, and gradually generating carbonized matter and yellow flame (flame reaction) if the water sample contains sodium methanesulfonate along with the evaporation of water; if sodium methanesulfonate is not present, no carbide is produced on ignition, and the pH value of the aqueous solution is about 4.
D. Adding the collected sodium methanesulfonate and nitric acid aqueous solution into a 1L single-neck flask, vacuumizing, reducing pressure, and concentrating by using a rotary evaporator to remove water until no water drips from a condenser, and removing most of nitric acid along with the evaporation of water to finally obtain a yellow-white solid.
E. Putting the obtained yellowish white sodium methanesulfonate crude product into a 1L single-neck flask, adding 200ml of absolute ethyl alcohol, reacting residual nitric acid in the solid with the absolute ethyl alcohol, generating heat and acetaldehyde, and bubbling. The flask is placed in a magnetic stirring water bath, and magnetic stirring seeds are added to stir for 5 hours.
F. And (2) performing vacuum filtration on the mixture of the sodium methanesulfonate and the anhydrous ethanol by using a glass sand funnel, washing the obtained sodium methanesulfonate by using 50ml of anhydrous ethanol, performing suction drying, collecting the sodium methanesulfonate, drying at 90 ℃ in an oven, and obtaining 138.1g of the sodium methanesulfonate, wherein the yield is 69%, and no characteristic peak of sodium nitrate is detected by infrared. Distilling the filtered ethanol at normal pressure to recover ethanol, and treating the residual liquid with sodium hydroxide.
G. Regeneration of strong acid cation resin:
about 62g of sodium nitrate in sodium ion resin, 62 ÷ 85 ═ 0.729mol of sodium ions, corresponding to the need for 0.729mol of hydrogen ion replacement.
The resin was removed from the separatory funnel and added to a 2L beaker. The resin contained about 0.3L of water, 0.3L of deionized water was added, concentrated hydrochloric acid (12mol/L)0.06L × 12 ═ 0.72mol was added to a beaker, the resin was stirred and soaked for 24 hours, with a hydrogen ion concentration of about 1.1 mol/L. The soaked resin is added into a separating funnel, acid solution is discharged, and 240ml of 1mol/L hydrochloric acid solution is used for washing the resin at the flow rate of 120 ml/h.
The resin was rinsed with deionized water to a pH test of approximately 7 using 1200ml of deionized water for 7.6 hours at a flow rate of 157 ml/hour. At this point, the resin is regenerated and can be reused.
Except that deionized water is required to be used for regenerating resin, other samples are pretreated, tap water with low hardness can be used for replacing the deionized water in the process of separating the sodium methanesulfonate and the sodium nitrate from the resin, cations in the tap water can occupy a part of resin exchange capacity, and the quality of the finally obtained sodium methanesulfonate is close to the effect of using the deionized water.
3. Preparation of methanesulfonyl chloride using sodium methanesulfonate
The chloroform used in this step should be free of alcohols such as methanol and ethanol, and if alcohols are present, the chloroform should be washed with water, separated for 5 times to remove the alcohols, and dried over sodium sulfate for use. The glassware used must be dry and water free and the glassware must have a good seal at each interface.
The reaction formula is as follows:
CH3SO3Na+SOCl2→CH3SO2Cl+NaCl+SO2
A. and F, adding 50g (0.49mol) of the sodium methanesulfonate obtained in the step F, 1.2g of DMF1 and 20ml of chloroform into a 500ml three-neck flask, placing the flask into a magnetic oil bath pan, installing a thermometer and a spherical condenser pipe, connecting an upper opening of the condenser pipe with a tail gas absorption device, and absorbing the tail gas by using a sodium hydroxide aqueous solution. Then 75.6g (0.64mol) of thionyl chloride is slowly added, the exothermic phenomenon occurs, the temperature of the reaction solution rises to 35 ℃, the reaction solution is slowly stirred for reaction for 30min, and the reaction raw materials gradually turn yellow.
B. Heating by stages, heating the oil to 60 ℃, starting condensed water, refluxing liquid and emitting bubbles, and reacting for 50 minutes at the temperature.
C. The temperature of the oil is continuously increased to 80 ℃, reaction bubbles are increased to react for 10 minutes, then the temperature is increased to 100 ℃, the temperature of the reaction liquid is gradually increased to 87 ℃ due to the generation of methanesulfonyl chloride, the reactant is gradually changed from yellow to white, and the reaction time is 6 hours at 100 ℃.
D. After the reaction, the heating is stopped, the temperature is reduced to 60 ℃, 130ml of chloroform is added, and the mixture is stirred uniformly.
E. Cooling the reaction liquid to room temperature, vacuumizing and rapidly filtering the reaction liquid by using a glass sand funnel, washing and drying the solid by using 100ml of chloroform, collecting the solid, putting the collected solid in a 250ml single-neck flask, adding 100ml of ethanol, stirring and washing the mixture, filtering the mixture by using the glass sand funnel, and drying the mixture in an oven at 80 ℃ to obtain 25g of the mixture. Infrared test shows no sodium methanesulfonate peak, and the solid is mainly sodium chloride.
G. The resulting chloroform solution was filtered, and the chloroform was removed by vacuum evaporation and concentration using a rotary evaporator to obtain 44.7g of methanesulfonyl chloride. The main content is 98.1% by gas phase detection (normalization method).
Purification of methanesulfonyl chloride by distillation under reduced pressure:
44.7g of the methanesulfonyl chloride obtained above was added to a 250ml single-neck flask, the flask was placed in a magnetic stirring oil bath pan, a distillation head, a thermometer, a straight condenser tube, a dovetail tube, and a collection bottle were mounted, and a small amount of vacuum grease was applied to each port for sealing. Decompressing a water circulation vacuum pump, starting magnetic stirring, gradually increasing the oil temperature, finally increasing the oil temperature to 110 ℃, ensuring that the temperature of stable distillate is 90 ℃, and totally collecting 41.8g of methanesulfonyl chloride, wherein the total yield of the reaction is 83.6%.
Examples 2 to 3
Example 2 the same procedure as in example 1, except that in example 2 the molar ratio of sodium methanesulfonate to thionyl chloride was 1:1.5, the results of the reaction are shown in Table 1.
Example 3 the same procedure as in example 1, except that in example 3 the molar ratio of sodium methanesulfonate to thionyl chloride was 1:1.1, the reaction results are shown in Table 1.
TABLE 1 test results of reaction products of examples 1-3
| Examples | Methanesulfonic acidSodium inventory | Yield of the product | Yield of | Purity after distillation |
| 1 | 50g | 41.8g | 83.6％ | 99.7％ |
| 2 | 75.8g | 63.7g | 84.0％ | 99.7％ |
| 3 | 50g | 41.3g | 82.6％ | 99.7％ |
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 (5)
1. A method for preparing methanesulfonyl chloride by using waste generated in the production of dimethyl sulfone is characterized by comprising the following steps:
a. uniformly mixing solid waste generated in the production of dimethyl sulfone with acetone, and removing organic sulfur components in the solid waste by condensation and reflux;
b. uniformly mixing the solid waste from which the organic sulfur component is removed with water in equal mass, adjusting the pH value to 5 ~ 6 by using dilute nitric acid, heating to 55 ~ 65 ℃, stirring for 1.5 ~ 3h, cooling to 20 ~ 25 ℃, adding the reaction solution and strong-acid cation resin into a separating funnel according to the volume ratio of 1:3.5 ~ 4.5.5, standing for 1 ~ 2h, collecting the aqueous solution at the lower part of the separating funnel, carrying out rotary evaporation on the collected aqueous solution to obtain a yellow-white solid, mixing the yellow-white solid with absolute ethyl alcohol, stirring for 5 ~ 6h in a water bath, carrying out vacuum filtration on the mixed solution, and drying filter residues at 90 ℃ to obtain a sodium methanesulfonate solid;
c. and dissolving the obtained sodium methanesulfonate solid in chloroform, adding a proper amount of DMF (dimethyl formamide), slowly adding thionyl chloride, heating the mixed solution in an oil bath to react, cooling the reaction solution after the reaction is finished, filtering in vacuum, and carrying out rotary evaporation on the filtrate to obtain methanesulfonyl chloride.
2. The method according to claim 1, wherein the step a specifically comprises the steps of:
a1, uniformly mixing the solid waste generated in the production of dimethyl sulfone with acetone according to the mass-volume ratio of 1g:1.2 ~ 1.8.8 mL, stirring in a water bath at 65 ~ 70 ℃, condensing and refluxing for 1 ~ 1.5.5 h, and then cooling to 20 ~ 25 ℃;
a2, filtering the cooled mixture in vacuum, and drying the filter residue at 60 ℃.
3. The process of claim 1, wherein the oil bath heating reaction step in step c is as follows:
the oil temperature is firstly increased to 35 ℃, the stirring reaction is carried out for 30 ~ 35min, the temperature is increased to 60 ℃, the reaction is carried out for 50 ~ 60min, the temperature is increased to 80 ℃, the reaction is carried out for 10 ~ 15min, the temperature is increased to 100 ℃, the reaction is carried out for 6 ~ 7h, the temperature is reduced to 60 ℃, chloroform is added, the mass-volume ratio of the sodium methanesulfonate to the added chloroform is 1g:2 ~ 3mL, and the mixture is stirred uniformly and cooled to 20 ~ 25 ℃.
4. The method as claimed in claim 3, wherein when the sodium methanesulfonate solid is dissolved in chloroform in step c, the mass-to-volume ratio of sodium methanesulfonate to chloroform is 1g:0.4 ~ 0.5.5 mL.
5. The process according to claim 3, wherein the molar ratio of sodium methanesulfonate to thionyl chloride in step c is 1:1.1 ~ 1.5.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710745419.3A CN107473992B (en) | 2017-08-26 | 2017-08-26 | Method for preparing methanesulfonyl chloride by using waste generated in dimethyl sulfone production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710745419.3A CN107473992B (en) | 2017-08-26 | 2017-08-26 | Method for preparing methanesulfonyl chloride by using waste generated in dimethyl sulfone production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107473992A CN107473992A (en) | 2017-12-15 |
| CN107473992B true CN107473992B (en) | 2020-01-10 |
Family
ID=60602909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710745419.3A Active CN107473992B (en) | 2017-08-26 | 2017-08-26 | Method for preparing methanesulfonyl chloride by using waste generated in dimethyl sulfone production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107473992B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111138841A (en) * | 2019-12-30 | 2020-05-12 | 江苏利宏科技发展有限公司 | Environment-friendly polyurethane grouting material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311460A (en) * | 2014-09-15 | 2015-01-28 | 夏瑜 | Waste dimethyl sulfoxide recovery and treatment method |
| CN104592067A (en) * | 2015-01-30 | 2015-05-06 | 湖北大学 | Method for recycling dimethyl sulfoxide waste residue through multi-stage extraction |
| CN106117094A (en) * | 2016-08-31 | 2016-11-16 | 湖北兴发化工集团股份有限公司 | A kind of recovery dimethyl sulfoxide organic method of DMSO abraum salt |
-
2017
- 2017-08-26 CN CN201710745419.3A patent/CN107473992B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311460A (en) * | 2014-09-15 | 2015-01-28 | 夏瑜 | Waste dimethyl sulfoxide recovery and treatment method |
| CN104592067A (en) * | 2015-01-30 | 2015-05-06 | 湖北大学 | Method for recycling dimethyl sulfoxide waste residue through multi-stage extraction |
| CN106117094A (en) * | 2016-08-31 | 2016-11-16 | 湖北兴发化工集团股份有限公司 | A kind of recovery dimethyl sulfoxide organic method of DMSO abraum salt |
Non-Patent Citations (1)
| Title |
|---|
| Dimethyl 2-（Tosylmethyl）fumarate: An Allyl Sulfone as Electrophilic Reagent for the Synthesis of Itaconate Ester Derivatives;Rafael Chinchilla et al.;《Tetrahedron》;19961231;第52卷(第3期);第1035-1046页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107473992A (en) | 2017-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105693559B (en) | A kind of method for preparing taurine and coproduction bicarbonate | |
| US10683264B2 (en) | Process for producing taurine | |
| CN100434416C (en) | Production technique of N,N'-dicyclo hexylcar bodiimide | |
| US20210114978A1 (en) | Method and production system for fully recovering and treating taurine mother liquor | |
| CN101804330A (en) | Heavy metal ion adsorbent and preparation and application method thereof | |
| CN111646881B (en) | Synthetic method of m-trifluoromethyl phenol | |
| CN108821308B (en) | Method and device for preparing high-concentration ammonia water by using coking residual ammonia water | |
| CN104710483A (en) | Preparation method for glucosamine sulfate | |
| CN111330412B (en) | System and process for absorbing and purifying byproduct hydrogen chloride gas in chlorination section into acid | |
| CN107473992B (en) | Method for preparing methanesulfonyl chloride by using waste generated in dimethyl sulfone production | |
| CN210736624U (en) | Production system for recycling taurine mother liquor completely | |
| CN114620692A (en) | Process for preparing sulfuric acid by carrying out salt extraction and co-firing on coking desulfurization foam sulfur melting and desulfurization waste liquid melting method | |
| CN104877042A (en) | Preparation method of heparinoid | |
| CN107445870B (en) | Method for preparing sodium methanesulfonate by using waste generated in dimethyl sulfone production | |
| CN110818569B (en) | Treatment method of RT base production waste gas | |
| CN1762991A (en) | Adsorption treating method for resinifying sulfonated waste acid in DSD acid production | |
| CN1775718A (en) | Production process for recovering methanol and sul furic acid from dimethyl sulfate slag | |
| CN106977362A (en) | 1.1.1 the recoverying and utilizing method of the high-boiling components produced in chlorodifluoroethane production process | |
| WO2023245633A1 (en) | Process for producing chloroethane | |
| CN113896614B (en) | Method for continuously synthesizing chlorobutane in non-aqueous system | |
| CN114130428B (en) | Preparation method and application of novel polyacid-based ionic liquid oxidation desulfurization catalyst | |
| CN109651072B (en) | Method for preparing chloroethane from hydrochloric acid containing sulfur dioxide | |
| CN109803747A (en) | For cleaning the method for viscose glue production exhaust gas and for the catalyst of this method | |
| CN114470827B (en) | Production method and production system of clean thiocarbazide | |
| CN101343230B (en) | 2,4-dinitrophenol inhibitor purification process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20191217 Address after: 408325 Tong Ji village, Chengxi Town, Dianjiang County, Chongqing City, 1 Applicant after: Chongqing Kai Kai Environmental Protection Technology Co., Ltd. Address before: 408325 Tong Ji village, Chengxi Town, Dianjiang County, Chongqing City, 1 Applicant before: Chongqing Heng Jie Chemical Co., Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |