CN103570591A - Method for removing residues out of dimethyl sulfate - Google Patents
Method for removing residues out of dimethyl sulfate Download PDFInfo
- Publication number
- CN103570591A CN103570591A CN201310550096.4A CN201310550096A CN103570591A CN 103570591 A CN103570591 A CN 103570591A CN 201310550096 A CN201310550096 A CN 201310550096A CN 103570591 A CN103570591 A CN 103570591A
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- China
- Prior art keywords
- sulfate
- methyl
- catalyzer
- hydrogen peroxide
- molecular sieve
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Abstract
The embodiment of the invention provides a method for removing residues out of dimethyl sulfate, belonging to the technical field of chemical purification. The method comprises the steps: adding a catalyst and a hydrogen peroxide solution with the mass concentration of 30-70%, reacting at the temperature of 35-55 DEG C, removing residues, and separating the catalyst and water to obtain high-purity dimethyl sulfate after the reaction is finished, wherein the usage amount of the hydrogen peroxide solution is 0.15-0.35% of that of the dimethyl sulfate, the usage amount of the catalyst is 0.05-0.2% of weight of the dimethyl sulfate, and the catalyst comprises manganese dioxide, calcium oxide, cobalt sulfate or copper sulfate. The method for removing residues, provided by the invention, can be used for effectively removing the residues such as CHOSO3H, SO2 and (CH3O)2SO out of the dimethyl sulfate, and a treated dimethyl sulfate product contains more than or equal to 99.5% of DMS, less than or equal to 20ppm of SO2 and less than or equal to 30ppm of (CH3O)2SO, so that the removing effect is very remarkable.
Description
Technical field
The invention belongs to chemical purification technical field, particularly a kind of method of removing the residue in methyl-sulfate.
Background technology
Methyl-sulfate, the methylating agent for the manufacture of dye well as amine and alcohols.Can do reaction raw materials, solvent, analytical reagent and methylating reagent.Its steam strong toxicity, once as war gas.Specifically can be used as measuring the reagent of coal tar oils, in organic synthesis, be used as methyl substituted agent.
In the methyl-sulfate that prior art is produced, contain a small amount of CHOSO
3h, SO
2, (CH
3o)
2the residues such as SO.The existence of residue can affect the result of use of methyl-sulfate, as when preparing ester quat, under comparatively high temps, formed some by product, thereby the smell to methyl-sulfate quaternized products has a negative impact, these problems relevant with smell can be traced back to the SO in methyl-sulfate
2, (CH
3o)
2the residues such as SO, common by adding oxygenant to remove SO wherein in prior art
2.
Granted publication is number for the patent of CN101142171B discloses a kind of method of removing residual sulfur dioxide from methyl-sulfate, and the method adopts and in methyl-sulfate, adds the mode of oxygenant to remove SO
2, the method can only effectively be removed the sulfur dioxide residue in methyl-sulfate, not good to the removal effect of residues such as dimethyl sulfite wherein, and dimethyl sulfite can cause that ester quat produces stink equally.In addition, this treatment process can not effectively improve the purity of methyl-sulfate, do not relate to reaction rear oxidation agent Transformatin yet, especially take hydrogen peroxide during as oxygenant, the water long-term existence of introducing can cause hydrolysis, the muddiness of methyl-sulfate in methyl-sulfate, reduces the content of methyl-sulfate and improves its acidity.
Summary of the invention
In order to address the above problem, the embodiment of the present invention provides a kind of method of removing the residue in methyl-sulfate, and the principal reaction principle of method provided by the invention is as shown in reaction formula (1) and (2):
Wherein, method provided by the invention is mainly to utilize H
2o
2make oxygenant and add catalyzer to remove the SO in methyl-sulfate simultaneously
2, (CH
3o)
2the residues such as SO, the H that added not only catalysis of catalyzer
2o
2to SO
2and (CH
3o)
2the oxidation of the residues such as SO, can also promote the decomposition of hydrogen peroxide, and when finish to reaction on historical facts or anecdotes border, the dioxygen water yield residual in system is very low, has avoided the introducing of allogenic material, and H
2o
2moisture (the H introducing
2o
2the moisture that moisture in solution and oxidizing reaction generate) can adopt siccative to absorb.Described scheme is as follows:
The embodiment of the present invention provides a kind of method of removing the residue in methyl-sulfate, and the method comprises:
In common dimethyl phthalate, adding catalyzer and mass concentration is the hydrogen peroxide solution of 30%-70%, in 35-55 ℃ of reaction, remove residue, after having reacted rear Separation of Water and catalyzer, obtain highly purified methyl-sulfate, wherein, in aforementioned sepn process mainly by removing by filter catalyzer, use siccative to remove moisture, and siccative can together remove by filter with catalyzer, also can remove by filter separately.
Wherein, the usage quantity of hydrogen peroxide solution is the 1.5-3.5 ‰ of methyl-sulfate weight, and the usage quantity of catalyzer is the 0.5-2.0 ‰ of methyl-sulfate weight, and catalyzer comprises Manganse Dioxide, calcium oxide, rose vitriol or copper sulfate etc.
Wherein, the concentration of the hydrogen peroxide of participation oxidizing reaction is more high better, because the hydrogen peroxide of high density can effectively reduce moisture (H
2o) introducing, avoids water long-term existence to cause hydrolysis, the muddiness of methyl-sulfate, and can reduce the consumption of siccative in aftertreatment.But current industrial hydrogen peroxide maximum concentration is also with regard to 70% left and right, so the hydrogen peroxide solution that functional quality concentration of the present invention is 30%-70%, in concrete actual production, can adopt mass concentration is 30% and the hydrogen peroxide solution of 50% two kind of specification.
Preferably, catalyzer is Manganse Dioxide or calcium oxide.Through experiment, find, while making catalyzer with Manganse Dioxide or calcium oxide, after reaction finishes, reducing comparatively significantly has also appearred in the acidity of methyl-sulfate, can effectively improve the content of methyl-sulfate.By analysis, this may be that the cause of acid-base reaction has occurred due to the methyl-hydrogen-sulfate monomethyl-sulfate in methyl-sulfate acidity source and Manganse Dioxide or calcium oxide.
Wherein, in the present invention, for removing the reaction times of the oxidizing reaction of residue, be 2.5-4.0 hour.
Particularly, in the present invention, reacted and obtained highly purified methyl-sulfate process after rear Separation of Water and catalyzer and specifically comprise:
After having reacted, add desiccant dryness 36-48 hour, remove by filter siccative and catalyzer and obtain highly purified methyl-sulfate.Wherein, siccative specifically comprises molecular sieve, silica gel or Calcium Chloride Powder Anhydrous etc.When being applicable to process a small amount of methyl-sulfate, this treatment process uses.
Or, in the present invention, reacted and obtained highly purified methyl-sulfate process after rear Separation of Water and catalyzer and specifically comprise:
After having reacted, through 800-1000 object strainer, remove by filter after catalyzer, add desiccant dryness 36-48 hour, refilter and remove siccative and obtain highly purified methyl-sulfate.Wherein, siccative comprises molecular sieve, silica gel or Calcium Chloride Powder Anhydrous etc.When being applicable to process a large amount of methyl-sulfate, this treatment process uses.
In aforesaid two kinds of sepn processes, for silica gel, molecular sieve and calcium chloride, water and hydrogen peroxide can be removed.Particularly, silica gel both can absorb moisture and partially absorb hydrogen peroxide, can promote again the decomposition of hydrogen peroxide; Molecular sieve can absorb hydrogen peroxide and water; Calcium chloride can absorb water and can promote the decomposition of hydrogen peroxide; Meanwhile, due to the unstable of hydrogen peroxide, after water is absorbed, hydrogen peroxide also can decompose.In fact, owing to having added catalyzer in reaction process, these catalyzer can promote the decomposition of hydrogen peroxide, simultaneously also catalysis to SO
2and (CH
3o)
2the oxidation of SO, when finish to reaction on historical facts or anecdotes border, the dioxygen water yield residual in system is very low.
Preferably, in the present invention, siccative is molecular sieve, can be specifically 4A molecular sieve.
Preferably, the method for the residue in the removal methyl-sulfate that the embodiment of the present invention provides, specifically comprises:
In common dimethyl phthalate, adding catalyst manganese dioxide or calcium oxide and mass concentration is the hydrogen peroxide solution of 30%-70%, in 35-55 ℃, react after 2.5-4.0 hour, add desiccant dryness 36-48 hour, obtain highly purified methyl-sulfate after removing by filter siccative and catalyzer.Wherein, the usage quantity of hydrogen peroxide solution is the 1.5-3.5 ‰ of methyl-sulfate weight, and the usage quantity of catalyzer is the 0.5-2.0 ‰ of methyl-sulfate weight.
Or, specifically comprise:
In common dimethyl phthalate, adding catalyst manganese dioxide or calcium oxide and mass concentration is the hydrogen peroxide solution of 30%-70%, in 35-55 ℃, react after 2.5-4.0 hour, through 800-1000 object strainer, remove by filter after Manganse Dioxide or calcium oxide, add molecular sieve drying 36-48 hour, refilter and remove molecular sieve and obtain highly purified methyl-sulfate.Wherein, the usage quantity of hydrogen peroxide solution is the 1.5-3.5 ‰ of methyl-sulfate weight, and the usage quantity of catalyzer is the 0.5-2.0 ‰ of methyl-sulfate weight.
After testing, our company produces methyl-sulfate (acidity≤0.4%, SO
2content is at 200PPM left and right, (CH
3o)
2sO content more than 450PPM, DMS(methyl-sulfate) content is in 99% left and right), in the dimethyl sulfate product after present method is processed, DMS content>=99.5%, SO
2content≤20ppm, (CH
3o)
2sO content≤30ppm, the removal effect of residue is very obvious, and can also improve the content of methyl-sulfate.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below embodiment of the present invention is described further in detail.
Embodiment 1
Take acidity and be 0.32%, SO
2content is 207ppm, (CH
3o)
2sO content is in the 500ml there-necked flask that stirs in band of the methyl-sulfate 400g of 462ppm, then adds the H of 0.9g mass concentration 30%
2o
2.Start to stir, then to the MnO that drops into 0.4g in system
2, heat temperature raising, when system temperature rises to 35
0during C, start timing, and at this temperature (35 ± 2
0c) insulation reaction 3.5h.Finish reaction, and in system, add 10g molecular sieve, filtering molecular sieve and MnO after standing 36h
2, gained methyl-sulfate acidity 0.25%, SO
28.9ppm, (CH
3o)
2sO 18.7ppm, product appearance is colourless, clear.
Embodiment 2
Take acidity and be 0.32%, SO
2content is 207ppm, (CH
3o)
2sO content is in the 500ml there-necked flask that stirs in band of the methyl-sulfate 400g of 462ppm, then adds the H of 0.5g mass concentration 50%
2o
2.Start to stir, then to the MnO that drops into 0.4g in system
2, heat temperature raising, when system temperature rises to 35
0during C, start timing, and at this temperature (35 ± 2
0c) insulation reaction 3.5h.Finish reaction, and in system, add 6g silica gel, filtering silica gel and MnO after standing 40h
2, gained methyl-sulfate acidity 0.24%, SO
29.8ppm, (CH
3o)
2sO 20.6ppm, product appearance is colourless, clear.
Embodiment 3
Take acidity and be 0.32%, SO
2content is 207ppm, (CH
3o)
2sO content is in the 500ml there-necked flask that stirs in band of the methyl-sulfate 400g of 462ppm, then adds the H of 0.9g mass concentration 30%
2o
2, start and stir.To the CaO that drops into 0.35g in system, heat temperature raising, when system temperature rises to 48 again
0during C, start timing, and at this temperature (48 ± 2
0c) insulation reaction 4.0h.Finish reaction, and in system, add 10g calcium chloride, filtering calcium chloride and CaO after standing 38h, gained methyl-sulfate acidity 0.22%, SO
211.5ppm, (CH
3o)
2sO 17.9ppm, product appearance is colourless, clear.
Embodiment 4
Take acidity and be 0.28%, SO
2content is 193ppm, (CH
3o)
2sO content is in the 500ml there-necked flask that stirs in band of the methyl-sulfate 400g of 524ppm, then adds the H of 0.9g mass concentration 30%
2o
2.Start to stir, then to the MnO that drops into 0.4g in system
2, heat temperature raising, when system temperature rises to 35
0during C, start timing, and at this temperature (35 ± 2
0c) insulation reaction 3.5h.Finish reaction, and in system, add 10g molecular sieve, filtering molecular sieve and MnO after standing 36h
2, gained methyl-sulfate acidity 0.21%, SO
212.7ppm, (CH
3o)
2sO 22.1ppm, product appearance is colourless, clear.
Embodiment 5
By 3.5t through the acidity of accurate-metering be 0.34%, SO
2content is 201ppm, (CH
3o)
2sO content is that dimethyl sulfate product that 493ppm, DMS content are 99.2% is put to the enamel reaction still that is 3000L of the nominal volume with grid agitator, then adds that to pour wherein 7.0kg mass concentration into be 30% H
2o
2.Start and stir, then add 3.5kg MnO in system
2.Heat temperature raising, when temperature rises to 36
0during C, start timing, maintenance system temperature 36 ± 2
0c continues reaction 3.5h.Finish reaction, reaction gained methyl-sulfate is filtered with filtering MnO with 800 object strainers
2solid.In filtrate, add 70kg molecular sieve again, after standing 38h, shift out molecular sieve, sampling analysis.Analytical results is acidity 0.26%, SO
213.7ppm, (CH
3o)
2sO 23.5ppm, DMS 99.53%.
Embodiment 6
Acidity 0.34%, SO by 3.5t through accurate-metering
2content is 201ppm, (CH
3o)
2sO content is that dimethyl sulfate product that 493ppm, DMS content are 99.2% is put to the enamel reaction still that is 3000L of the nominal volume with grid agitator, then adds that to pour wherein 4.0kg mass concentration into be 50% H
2o
2.Start and stir, then add 2.5kgCaO in system.Heat temperature raising, when temperature rises to 53
0during C, start timing, maintenance system temperature 53 ± 2
0c continues reaction 4h and finishes reaction.Reaction gained methyl-sulfate is filtered to the solid with filtering CaO with 1000 object strainers.To more than adding the standing 36h of 40kg molecular sieve in filtrate, shift out molecular sieve, sampling analysis again.Analytical results is acidity 0.27%, SO
214.1ppm, (CH
3o)
2sO 22.6ppm, DMS 99.57%.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. a method of removing the residue in methyl-sulfate, is characterized in that, described method comprises:
Adding catalyzer and mass concentration is the hydrogen peroxide solution of 30%-70%, in 35-55 ℃ of reaction, removes residue, obtains highly purified methyl-sulfate after having reacted rear separating catalyst and water; The usage quantity of hydrogen peroxide solution is the 1.5-3.5 ‰ of methyl-sulfate weight, and the usage quantity of catalyzer is the 0.5-2.0 ‰ of methyl-sulfate weight, and catalyzer comprises Manganse Dioxide, calcium oxide, rose vitriol or copper sulfate.
2. method according to claim 1, is characterized in that, described catalyzer is Manganse Dioxide or calcium oxide.
3. method according to claim 1, is characterized in that, the reaction times is 2.5-4.0 hour.
4. method according to claim 1, is characterized in that, after described reaction completes, after separating catalyst and water, obtains highly purified methyl-sulfate, specifically comprises:
After having reacted, add desiccant dryness 36-48 hour, obtain highly purified methyl-sulfate after removing by filter siccative and catalyzer, described siccative comprises molecular sieve, silica gel or Calcium Chloride Powder Anhydrous.
5. method according to claim 1, is characterized in that, after described reaction completes, after separating catalyst and water, obtains highly purified methyl-sulfate, specifically comprises:
After having reacted, through 800-1000 object strainer, remove by filter after catalyzer, add desiccant dryness 36-48 hour, refilter and remove siccative and obtain highly purified methyl-sulfate, described siccative comprises molecular sieve, silica gel or Calcium Chloride Powder Anhydrous.
6. according to the method described in claim 4 or 5, it is characterized in that, described siccative is molecular sieve.
7. according to the method described in claim 1 or 4, it is characterized in that, described method specifically comprises:
Adding catalyzer and mass concentration is the hydrogen peroxide solution of 30%-70%, in 35-55 ℃, react after 2.5-4.0 hour, add desiccant dryness 36-48 hour, after removing by filter siccative and catalyzer, obtain highly purified methyl-sulfate, described siccative comprises molecular sieve, silica gel or Calcium Chloride Powder Anhydrous.
8. method according to claim 1 or 5, is characterized in that, described method specifically comprises:
Adding catalyzer and mass concentration is the hydrogen peroxide solution of 30%-70%, in 35-55 ℃, react after 2.5-4.0 hour, through 800-1000 object strainer, remove by filter after catalyzer, add molecular sieve drying 36-48 hour, refilter and remove molecular sieve and obtain highly purified methyl-sulfate, described catalyzer is Manganse Dioxide or calcium oxide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130850A (en) * | 2015-09-17 | 2015-12-09 | 湖北远大富驰医药化工股份有限公司 | Method for purifying dimethyl sulfate |
| CN105712903A (en) * | 2016-01-20 | 2016-06-29 | 山东兴辉化工有限公司 | Dimethyl sulfate residue treatment method |
| CN106518731A (en) * | 2016-08-31 | 2017-03-22 | 湖北远大富驰医药化工股份有限公司 | Automatic separator for refining products of dimethyl sulfate |
| CN107501133A (en) * | 2017-09-14 | 2017-12-22 | 湖北远大富驰医药化工股份有限公司 | A kind of preparation method of high-purity dimethyl sulfate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101142171A (en) * | 2005-03-14 | 2008-03-12 | 阿克佐诺贝尔股份有限公司 | Removal of residual sulfur dioxide from dimethyl sulfate |
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2013
- 2013-11-08 CN CN201310550096.4A patent/CN103570591B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101142171A (en) * | 2005-03-14 | 2008-03-12 | 阿克佐诺贝尔股份有限公司 | Removal of residual sulfur dioxide from dimethyl sulfate |
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| JAHIR UDDIN AHMAD，ET AL: "Copper catalyzed oxidation of benzylic alcohols in water with H2O2", 《APPLIED CATALYSIS A:GENERAL》, vol. 411412, 3 November 2011 (2011-11-03) * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130850A (en) * | 2015-09-17 | 2015-12-09 | 湖北远大富驰医药化工股份有限公司 | Method for purifying dimethyl sulfate |
| CN105712903A (en) * | 2016-01-20 | 2016-06-29 | 山东兴辉化工有限公司 | Dimethyl sulfate residue treatment method |
| CN106518731A (en) * | 2016-08-31 | 2017-03-22 | 湖北远大富驰医药化工股份有限公司 | Automatic separator for refining products of dimethyl sulfate |
| CN106518731B (en) * | 2016-08-31 | 2018-02-16 | 湖北远大富驰医药化工股份有限公司 | Dimethyl suflfate purified product automates separator |
| CN107501133A (en) * | 2017-09-14 | 2017-12-22 | 湖北远大富驰医药化工股份有限公司 | A kind of preparation method of high-purity dimethyl sulfate |
| CN107501133B (en) * | 2017-09-14 | 2020-02-04 | 湖北远大富驰医药化工股份有限公司 | Preparation method of high-purity dimethyl sulfate |
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