CN112079751B - Preparation method of high-purity methane sulfonic acid - Google Patents
Preparation method of high-purity methane sulfonic acid Download PDFInfo
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- CN112079751B CN112079751B CN202011013717.1A CN202011013717A CN112079751B CN 112079751 B CN112079751 B CN 112079751B CN 202011013717 A CN202011013717 A CN 202011013717A CN 112079751 B CN112079751 B CN 112079751B
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- organic solvent
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- sodium sulfite
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- 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
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- 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
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Abstract
The invention relates to a preparation method of high-purity methane sulfonic acid. The method comprises the following steps: adding sodium sulfite, an organic solvent and a catalyst into a mixing reactor, adding a pH regulator to regulate the pH =3-6, stirring uniformly, and slowly dropwise adding a methylating agent; after the methylating agent is added dropwise, reacting for 5-8 hours at 10-40 ℃, and stopping the reaction; extracting organic solvent under reduced pressure, adding small amount of water, stirring for 5-10min, and performing ion exchange via an exchange column filled with strong acid cation resin to obtain crude product; removing water from the obtained crude product at-0.098 MPa, and taking 180-200 ℃ fraction to obtain high-purity methane sulfonic acid. The preparation method provided by the invention is carried out under anhydrous condition, and avoids the decomposition of a methylating agent or incompatibility with a reaction system. Simple process, high yield and low cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical industry organic synthesis, and particularly relates to a preparation method of high-purity methane sulfonic acid.
Background
Methane sulfonic acid is an important organic synthesis and medical intermediate, and is often used as a solvent, an alkylation reagent and an esterification reagent in organic synthesis; in addition, it is also an ideal leveling agent and brightener. Methanesulfonic acid has many uses, and is used not only as a raw material for medicines and agricultural chemicals but also as a dehydrating agent, a coating curing accelerator, and a fiber treating agent, and has been widely used as an additive for plating solutions in recent years. In recent years, methane sulfonate electroplating baths have been applied to tin and tin-lead alloy electroplating, and the performance of many new electroplating baths depends greatly on the quality of methane sulfonic acid used, and the methane sulfonic acid has wide application prospects in the field of electroplating, and has been proved to be a good substitute for fluoboric acid or phenolsulfonic acid.
In the prior art, the method for preparing methane sulfonic acid by adopting a dimethyl sulfate method is mature, but still has more defects, such as the problems that a sulfite aqueous solution takes water as a system, dimethyl sulfate is easy to decompose in the reaction process, the use amount is large, impurity ions are introduced after acidification, and the rectification and purification are hindered due to the existence of a large amount of salt in the post-treatment.
Disclosure of Invention
The invention aims to avoid the defects in the prior art and provide an improved preparation method of high-purity methane sulfonic acid, wherein an organic solvent is used for replacing water as a solvent, the product yield reduction or material waste caused by the decomposition of a methylating agent or the incompatibility with a reaction system is avoided, the organic solvent can be repeatedly utilized, the cost is saved, and the ion exchange is carried out through a strong-acid cation exchange resin, so that the difficulty in post-treatment caused by the introduction of impurity ions is avoided.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows: a preparation method of high-purity methane sulfonic acid comprises the following steps:
1) Adding sodium sulfite, an organic solvent and a catalyst into a mixing reactor, adding a pH regulator to regulate the pH =3-6, stirring uniformly, and slowly dropwise adding a methylating agent;
2) After the methylating agent is dripped, reacting for 5-8 hours at 10-40 ℃, and stopping the reaction; extracting organic solvent under reduced pressure, adding small amount of water, stirring for 5-10min, and performing ion exchange via an exchange column filled with strong acid cation resin to obtain crude product;
3) Removing water from the obtained crude product at-0.098 MPa, and taking 180-200 ℃ fraction to obtain high-purity methane sulfonic acid.
Further, in the above preparation method, the organic solvent is diethylene glycol dimethyl ether or diethylene glycol diethyl ether.
Further, in the preparation method, the adding amount of the organic solvent is 70-120% of the mass of the sodium sulfite.
Further, in the preparation method, the strong acid cation resin is DT-010 macroporous strong acid special type adsorption resin.
Further, in the above preparation method, the catalyst is aluminum chloride, ferric chloride, zinc chloride, lanthanum chloride or boron trifluoride.
Further, in the preparation method, the adding amount of the catalyst is 1-5% of the mass of the sodium sulfite.
Further, in the above preparation method, the pH adjusting agent is perchloric acid.
Further, in the preparation method, the pH of the system is adjusted to be 4-5.
Further, in the above preparation method, the methylating agent is dimethyl sulfate, dimethyl carbonate, methyl p-toluenesulfonate or methyl trifluoromethanesulfonate.
Further, in the above preparation method, the molar ratio of the methylating agent sodium sulfite = 1.3-2.5.
The beneficial effects of the invention are: the preparation method provided by the invention is carried out under an anhydrous condition, thereby avoiding the product yield reduction or material waste caused by the decomposition of a methylating reagent or incompatibility with a reaction system, and the difficulty in post-treatment caused by introducing impurity ions after acidification. The preparation method has the advantages of simple process, high yield and low cost, and is suitable for industrial mass production.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described in more detail by way of preferred embodiments, but the scope of the invention is not limited to the following specific embodiments.
A preparation method of high-purity methane sulfonic acid comprises the following steps:
1) Adding sodium sulfite, an organic solvent and a catalyst into a mixing reactor, adding a pH regulator to regulate the pH =3-6, stirring uniformly, and slowly dropwise adding a methylating agent.
Preferably, the organic solvent is diethylene glycol dimethyl ether or diethylene glycol diethyl ether. More preferably, the organic solvent is diethylene glycol dimethyl ether.
Preferably, the amount of the organic solvent added is 70 to 120% by mass of sodium sulfite, and more preferably, the amount of the organic solvent added is 100% by mass of sodium sulfite.
Preferably, the catalyst is aluminum chloride, ferric chloride, zinc chloride, lanthanum chloride or boron trifluoride. More preferably, the catalyst is aluminum chloride.
Preferably, the amount of the catalyst added is 1 to 5% by mass of sodium sulfite, and more preferably, the amount of the catalyst added is 3% by mass of sodium sulfite.
Preferably, the pH adjusting agent is perchloric acid.
Preferably, a pH regulator is added to adjust the system pH =4-5.
Preferably, the methylating agent is dimethyl carbonate, dimethyl sulfate, methyl p-toluenesulfonate or methyl trifluoromethanesulfonate, and more preferably, the methylating agent is dimethyl carbonate.
Preferably, the molar ratio of methylating agent to sodium sulfite =1.3-2.5, more preferably, the molar ratio of methylating agent to sodium sulfite =1.7-2:1.
2) After the methylating agent is added dropwise, reacting for 5-8 hours at 10-40 ℃, and stopping the reaction; extracting organic solvent under reduced pressure, adding small amount of water, stirring for 5-10min, and performing ion exchange via exchange column filled with strong acid cation resin to obtain crude product;
preferably, the reaction temperature is kept at 25 ℃ and the reaction time is kept at 6h.
Preferably, the strong acid cation resin is DT-010 macroporous strong acid special adsorption resin.
3) Removing water from the obtained crude product at-0.098 MPa, and taking 180-200 ℃ fraction to obtain high-purity methane sulfonic acid.
Example 1
A preparation method of high-purity methane sulfonic acid comprises the following steps:
1) Adding 10g of sodium sulfite, 10g of diethylene glycol dimethyl ether and 0.3g of aluminum chloride into a mixing reactor, uniformly stirring, adjusting the pH value of the system to 3-4 by using perchloric acid, keeping the temperature at 25 ℃, uniformly stirring, and slowly dropwise adding 13g of dimethyl carbonate.
2) After the addition of the dimethyl carbonate, the reaction was stopped at 25 ℃ for 6 hours. After the diethylene glycol dimethyl ether is pumped out under reduced pressure, 10g of water is added, and after stirring for 8min, ion exchange is carried out through an exchange column filled with DT-010 macroporous strong acid special adsorption resin, so as to obtain a crude product.
3) Removing water from the obtained crude product at-0.098 MPa, and taking 180-200 ℃ fractions to obtain the high-purity methane sulfonic acid. The acid value was determined at 579mgKOH/g (theoretical 582 mgKOH/g).
Example 2
A preparation method of high-purity methane sulfonic acid comprises the following steps:
1) Adding 10g of sodium sulfite, 12g of diethylene glycol dimethyl ether and 0.25g of ferric chloride into a mixing reactor, uniformly stirring, adjusting the pH value of the system to 3-4 by using perchloric acid, keeping the temperature at 30 ℃, uniformly stirring, and slowly dropwise adding 15g of dimethyl sulfate.
2) After the dimethyl sulfate was added dropwise, the reaction was stopped at 30 ℃ for 7 hours. After the diethylene glycol dimethyl ether is pumped out under reduced pressure, 10g of water is added, and after stirring for 7min, ion exchange is carried out through an exchange column filled with DT-010 macroporous strong acid special adsorption resin, so as to obtain a crude product.
3) Removing water from the obtained crude product at-0.098 MPa, and taking 180-200 ℃ fraction to obtain high-purity methane sulfonic acid. The acid value was measured to be 581mgKOH/g.
Example 3
1) Adding 10g of sodium sulfite, 8g of diethylene glycol diethyl ether and 0.4g of zinc chloride into a mixing reactor, uniformly stirring, adjusting the pH value of the system to 4-5 by using perchloric acid, keeping the temperature at 20 ℃, uniformly stirring, and slowly dropwise adding 13g of dimethyl carbonate.
2) After the addition of the dimethyl carbonate, the reaction was stopped at 20 ℃ for 6 hours. After the diethylene glycol diethyl ether is extracted under reduced pressure, 10g of water is added, and after stirring for 9min, ion exchange is carried out through an exchange column filled with DT-010 macroporous strong acid special adsorption resin, so as to obtain a crude product.
3) Removing water from the obtained crude product at-0.098 MPa, and taking 180-200 ℃ fractions to obtain the high-purity methane sulfonic acid. The acid value was measured to be 578mgKOH/g.
Example 4
A preparation method of high-purity methane sulfonic acid comprises the following steps:
1) Adding 10g of sodium sulfite, 12g of diethylene glycol dimethyl ether and 0.4g of boron trifluoride into a mixing reactor, uniformly stirring, adjusting the pH value of the system to 5-6 by using perchloric acid, keeping the temperature at 25 ℃, uniformly stirring, and slowly dropwise adding 30g of methyl p-toluenesulfonate.
2) After the dropwise addition of methyl p-toluenesulfonate, the reaction was stopped at 25 ℃ for 5 hours. And (3) after the diethylene glycol dimethyl ether is extracted under reduced pressure, adding 10g of water, stirring for 10min, and carrying out ion exchange through an exchange column filled with DT-010 macroporous strong acid special adsorption resin to obtain a crude product.
3) Removing water from the obtained crude product at-0.098 MPa, and taking 180-200 ℃ fractions to obtain the high-purity methane sulfonic acid. The acid value was measured to be 581mgKOH/g.
Example 5
A preparation method of high-purity methane sulfonic acid comprises the following steps:
1) Adding 10g of sodium sulfite, 10g of diethylene glycol diethyl ether and 0.2g of lanthanum chloride into a mixing reactor, uniformly stirring, adjusting the pH value of the system to 4-5 by using perchloric acid, keeping the temperature at 15 ℃, uniformly stirring, and slowly dropwise adding 26g of methyl trifluoromethanesulfonate.
2) After the addition of methyl trifluoromethanesulfonate, the reaction was stopped at 15 ℃ for 5 hours. After the diethylene glycol diethyl ether is extracted under reduced pressure, 10g of water is added, and after stirring for 5min, ion exchange is carried out through an exchange column filled with DT-010 macroporous strong acid special adsorption resin, so as to obtain a crude product.
3) Removing water from the obtained crude product at-0.098 MPa, and taking 180-200 ℃ fraction to obtain high-purity methane sulfonic acid. The acid value was measured at 580mgKOH/g.
Claims (5)
1. The preparation method of the high-purity methanesulfonic acid is characterized by comprising the following steps:
1) Adding sodium sulfite, an organic solvent and a catalyst into a mixing reactor, adding a pH regulator to regulate the pH =3-6, stirring uniformly, and slowly dropwise adding a methylating agent; the organic solvent is diethylene glycol dimethyl ether or diethylene glycol diethyl ether; the catalyst is aluminum chloride, ferric chloride, zinc chloride, lanthanum chloride or boron trifluoride; according to the mol ratio, the methylating agent sodium sulfite =1.3-2.5: 1; the methylating agent is dimethyl sulfate, dimethyl carbonate, methyl p-toluenesulfonate or methyl trifluoromethanesulfonate;
2) After the methylating agent is added dropwise, reacting for 5-8 hours at 10-40 ℃, and stopping the reaction; extracting organic solvent under reduced pressure, adding small amount of water, stirring for 5-10min, and performing ion exchange via exchange column filled with DT-010 macroporous strong acid special adsorption resin to obtain crude product;
3) Removing water from the obtained crude product at-0.098 MPa, and taking 180-200 ℃ fraction to obtain high-purity methane sulfonic acid.
2. The process according to claim 1, wherein the amount of the organic solvent added is 70 to 120% by mass based on the sodium sulfite.
3. The process according to claim 1, wherein the amount of the catalyst added is 1 to 5% by mass based on the sodium sulfite.
4. The method according to claim 1, wherein the pH adjusting agent is perchloric acid.
5. The method according to claim 1, wherein the system pH is adjusted to be 4 to 5.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991000268A1 (en) * | 1989-06-28 | 1991-01-10 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of light-coloured lower alkane sulphonic acids, especially methane sulphonic acid |
| CN1218040A (en) * | 1997-10-04 | 1999-06-02 | 格里罗工厂股份公司 | Process for preparation of methanesulfonic acid |
| CN1343200A (en) * | 1999-02-03 | 2002-04-03 | Basf公司 | Method for producing alkanesulfonic acids |
| CN1810780A (en) * | 2005-01-26 | 2006-08-02 | 河北亚诺化工有限公司 | Methylsulfonic acid preparing process |
| CN101219975A (en) * | 2007-01-10 | 2008-07-16 | 河北亚诺化工有限公司 | Process for producing methanesulfonic acid |
-
2020
- 2020-09-24 CN CN202011013717.1A patent/CN112079751B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991000268A1 (en) * | 1989-06-28 | 1991-01-10 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of light-coloured lower alkane sulphonic acids, especially methane sulphonic acid |
| CN1218040A (en) * | 1997-10-04 | 1999-06-02 | 格里罗工厂股份公司 | Process for preparation of methanesulfonic acid |
| CN1343200A (en) * | 1999-02-03 | 2002-04-03 | Basf公司 | Method for producing alkanesulfonic acids |
| CN1810780A (en) * | 2005-01-26 | 2006-08-02 | 河北亚诺化工有限公司 | Methylsulfonic acid preparing process |
| CN101219975A (en) * | 2007-01-10 | 2008-07-16 | 河北亚诺化工有限公司 | Process for producing methanesulfonic acid |
Non-Patent Citations (1)
| Title |
|---|
| "甲烷磺酸制备工艺改进";胥波;《四川化工与腐蚀控制》;19981231;第1卷(第4期);第12-13页 * |
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