CN100348579C - Methylsulfonic acid preparing process - Google Patents
Methylsulfonic acid preparing process Download PDFInfo
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- CN100348579C CN100348579C CNB200510002684XA CN200510002684A CN100348579C CN 100348579 C CN100348579 C CN 100348579C CN B200510002684X A CNB200510002684X A CN B200510002684XA CN 200510002684 A CN200510002684 A CN 200510002684A CN 100348579 C CN100348579 C CN 100348579C
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- ammonium
- reaction
- sulfate
- methylsulphonic acid
- methyl
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Abstract
The present invention discloses an environmentally friendly and novel method for the industrialization preparation of methanesulfonic acid. Under high temperature, aqueous solution of ammonium sulphite, or aqueous solution of the mixture of ammonium sulphite and ammonium bisulfite, or solid mixture reacts with dimethyl sulfate so as to generate methanesulfonic acid ammonium. Reaction liquid containing the methanesulfonic acid ammonium and the ammonium sulfate is processed by compounds, such as calcium hydroxide which can form deposition with sulfate ions so as to generate methanesulfonic acid which is easy to dissolve in water, calcium sulfate dihydrate which is difficult to dissolve in water, and ammonium hydroxide. The obtained methanesulfonic acid calcium is then processed by strong acid which can form deposition with calcium ions. Finally, methanesulfonic acid is obtained via vacuum distillation. The present invention has the advantages of available raw material, simple manufacturing process, superior production quality, low cost and no pollution to the environment, and is suitable for industrialization application.
Description
Technical field
The present invention relates to a kind of method for preparing methylsulphonic acid, belong to the chemical industry technical field of organic synthesis.
Background technology
In the chemical industry technical field of organic synthesis, methylsulphonic acid is a kind of intermediate that is used to prepare agricultural chemicals, medicine etc., is widely used in electroplating industry simultaneously.The operational path of preparation methylsulphonic acid has a lot, as Methanesulfonyl chloride hydrolysis method (US4,859,373), methane and Sulphurex process (US2,493,038), methylthiocyanide methylthiocyanate oxidation style (SU1,313,853), thiomethyl alcohol oxidation style (US3,392,095; US4,239,696; GB1,350,328), Methyl disulfide oxidation style (US2,697,722; US3,509,206; US3,948,922; GB1,350,328), halomethane method (US5,312,974), method of acetic acid (US6,207,025) and electrochemical process (EP0,331,864) etc.These method ubiquities problems such as Production Flow Chart length, complex procedures, operational condition harshness, environmental pollution are serious, poor product quality, production cost height.It is industrial that to prepare methylsulphonic acid method commonly used be Methanesulfonyl chloride hydrolysis method (US4,859,373), this method is that Methanesulfonyl chloride hydrolysis is at high temperature prepared methylsulphonic acid, by-product hydrochloric acid, the deficiency that this method exists is that Production Flow Chart is long, complex procedures, operational condition harshness, the production cost height, and have the hydrochloric acid of severe corrosive to generate, therefore, exist the serious environmental pollution problem.At present, the more advanced method for preparing methylsulphonic acid is: methyl-sulfate method (US6,060,621), this method is under comparatively high temps, and in aqueous solution system Central Asia vitriol and methyl-sulfate reaction, reaction mixture disengages methylsulphonic acid with excessive sulfuric acid acidation, obtain the mixture of methylsulphonic acid, sulfuric acid and a large amount of vitriol this moment, after underpressure distillation obtains the methylsulphonic acid product.This method raw material is simple, single step reaction only, and environmental pollution is little, has the suitability for industrialized production potentiality.But, owing to generate a large amount of vitriol in this method reaction, the extraction of methylsulphonic acid becomes a maximum difficult problem, this is because if adopt the distillatory method, be equivalent in solid, methylsulphonic acid be distilled, the existence of a large amount of vitriol will seriously hinder the heat transfer of Distallation systm, industrially implement very difficult; In addition, because existing, a large amount of vitriol solid cause wall temperature too high in the still-process, form coking easily at the wall place, side reaction increases, and influences reaction yield and product quality, and, this method adopts much larger than the sulfuric acid of theoretical consumption in industrial production and displaces methylsulphonic acid, and sulfuric acid and methylsulphonic acid are difficult to fractionation by distillation together, therefore, sulfuric acid content is very high in the resulting methylsulphonic acid, has a strong impact on quality product.
Summary of the invention
The purpose of this invention is to provide that a kind of environmental friendliness, technology are simple, the novel method of good quality of product, preparation of industrialization methylsulphonic acid with low cost.
In order to realize purpose of the present invention, the inventor has conscientiously studied the method for the different synthesizing methyl sulfonic acid of forefathers, particularly at methyl-sulfate method (US6,060,621) prepare the defective that the method for methylsulphonic acid exists, put forth effort to solve in this method by the product that occurs in methyl-sulfate and the sulphite prepared in reaction methylsulphonic acid process and extract and the problem of poor product quality, proposed a kind of novel method of preparation of industrialization methylsulphonic acid through concentrating on studies for many years.Particularly, design of the present invention is such: the aqueous solution of the mixture of ammonium salt such as ammonium sulphite, ammonium sulphite and ammonium bisulfite or solid mixture and methyl-sulfate reaction generate the methylsulphonic acid ammonium, and reaction equation is as follows:
2(NH
4)
2SO
3+(CH
3O)
2SO
2＝2CH
3SO
3NH
4+(NH
4)
2SO
4
4NH
4HSO
3+(CH
3O)
2SO
2＝2CH
3SO
3NH
4+(NH
4)
2SO
4+2H
2O+2SO
2↑
The reaction solution that contains methylsulphonic acid ammonium and ammonium sulfate forms the compound that sedimentary compound is a periodic table of elements IIA family element, preferably calcium oxide or calcium hydroxide with sulfuric acid herein again with forming sedimentary compound treatment with sulfate ion.Generate methylsulphonic acid calcium soluble in water and the calcium sulfate and the ammonium hydroxide that are insoluble in water, adopt method in common such as distillation, rare gas element or air in autoreaction liquid such as the following stripping that heats up, to isolate ammonia, resulting ammonia through water absorb back and sulfurous gas react produce ammonium sulphite after recycle, calcium sulfate is removed in centrifuging.Reaction equation is as follows:
2CH
3SO
3NH
4+(NH
4)
2SO
4+2Ca(OH)
2＝(CH
3SO
3)
2Ca+CaSO
4↓+4NH
3↑
With resulting metilsulfate be methylsulphonic acid calcium with stoichiometry can be that calcium ion forms sedimentary strong acid treatment with metallic cation in the metilsulfate, be preferably sulfuric acid here, obtain methylsulphonic acid crude product and calcium sulfate precipitation.Reaction equation is as follows:
(CH
3SO
3)
2Ca+H
2SO
4＝2CH
3SO
3H+CaSO
4↓
After filtering and the washing precipitation, filtrate is concentrated, after underpressure distillation obtains methylsulphonic acid.Because in the method for the invention, the salt that reaction is generated is converted into the form of gaseous compound and precipitation compound respectively and separates from reaction solution, methylsulphonic acid just can extract at an easy rate by the distillatory method, and method of the present invention adopts the sulfuric acid displacement methylsulphonic acid of stoichiometry, so, the excellent product quality that obtains, adopt this technology, the productive rate 70-86% of methylsulphonic acid (pressing methyl-sulfate calculates), product is a colourless transparent liquid, Cl
-Ion content equals 0ppm, SO
4 2-Ion content is less than 10ppm.
The present invention is described in detail as follows:
The reaction of the aqueous solution of the mixture of ammonium salt such as ammonium sulphite, ammonium sulphite and ammonium bisulfite or solid mixture and methyl-sulfate obtains methylsulphonic acid ammonium and ammonium sulfate, and the feed way of employing is that methyl-sulfate is added drop-wise in the aqueous solution or solid mixture of mixture of ammonium sulphite, ammonium sulphite and ammonium bisulfite.The feed way here is not a key factor, can conveniently taking once the slow intensification in reinforced back or ammonium sulphite is joined the medium feed way of methyl-sulfate according to industrial implementation yet.
Reaction mass can be the aqueous solution or the solid mixture of the mixture of ammonium sulphite, ammonium sulphite and ammonium bisulfite, but ammonium sulfite solution preferably.When selecting the solid ammonium salt, react restive as raw material.From reaction equation as can be seen the mol ratio of ammonium sulphite and methyl-sulfate reaction be 2: 1, the mol ratio of ammonium bisulfite and methyl-sulfate reaction is 4: 1, and have in a large amount of sulfur dioxide gas autoreaction systems and overflow, the utilization ratio of sulfurous gas is very low in the ammonium bisulfite.
When being raw material with the ammonium sulphite, the concentration of the ammonium sulphite aqueous solution is generally 10～50% (wt%), is preferably 30～40% (wt%), excessive concentration, the easy crystallization of the ammonium sulphite aqueous solution, industrial operation inconvenience; Concentration is low excessively, and the production unit utilization ratio reduces, and the burden of aftertreatment has increased production cost.The mol ratio that ammonium sulphite and methyl-sulfate feed intake is generally 1.5～5: 1, be preferably 2～3: and 1, feed ratio reduces, and will cause the methyl-sulfate reaction not exclusively, and feed ratio is too high, can cause the waste of ammonium sulphite.Temperature of reaction is generally 50～150 ℃, is preferably 80～110 ℃, and temperature is too high, and ammonium sulphite decomposes violent, and temperature is low excessively, and speed of reaction reduces, and the reaction times is long, and side reaction increases, and causes yield to descend.The material dropping time was generally 1～10 hour, was preferably 2～5 hours, and the time is too short, and exothermic heat of reaction is restive; Time is oversize, and ammonium sulphite decomposes gradually, causes the material waste, can come control reaction temperature by regulating rate of addition during industrial implementation.Reaction times was generally 0.5～10 hour, was preferably 2～5 hours, and the time is too short, and the methyl-sulfate reaction not exclusively causes material waste and potential safety hazard, and the time is oversize, has reduced throughput, causes cost to improve.In the method, reaction pressure is not a key factor, is generally 0.01～1.0MPa, is preferably normal pressure, and hypertonia then has higher requirement to equipment, has also strengthened operation easier, hypotony, and the inaccessible requirement of temperature of reaction, ammonium sulphite decomposes easily.
In the present invention, with the compound of the sedimentable compound preferred elements of sulfuric acid periodictable IIA family element, preferably calcium oxide or calcium hydroxide here.The calcium oxide or the calcium hydroxide that add in the reaction solution with the stoichiometry such as ammonium salt that generate carry out deamination, and the pH value by detection reaction liquid and distillate and add modes such as calcium oxide or calcium hydroxide as one feels fit and guarantee the deamination effect.
The acid of handling metilsulfate should be and can form sedimentary strong acid with calcium ion, is preferably sulfuric acid here.Reaction solution is after obtain the methylsulphonic acid crude product, stoichiometry such as the methylsulphonic acid calcium of vitriolic consumption and generation after the vitriolization.
The methylsulphonic acid crude product obtains methylsulphonic acid through underpressure distillation.
The present invention compares with conventional art has following progress: raw material is easy to get, and technology is simple, and ammonia does not consume in theory only as a kind of carrier and recycle in the reaction, and in fact this law is equivalent to the reaction of methyl-sulfate and sulfurous gas.The salt that reaction is generated is converted into the form of gaseous compound and precipitation compound respectively and separates from reaction solution, and methylsulphonic acid just can extract at an easy rate by the distillatory method.The small amount of methanol that generates in the reaction process can be recycled, and the calcium sulfate that contains a small amount of acidic substance can together use as material of construction with the calcium sulfate filter cake that contains a small amount of alkaline matter after calcium oxide or calcium hydroxide processing.This law is with low cost, because this law adopts the sulfuric acid of stoichiometry to carry out acidifying, so products obtained therefrom is best in quality, Cl
-Ion content equals 0ppm, SO
4 2-Ion content is less than 10ppm.The most important thing is that this law does not fundamentally adopt thiomethyl alcohol or Methyl disulfide as raw material, therefore to environment without any pollution.This method not only Production Flow Chart is simple, and industrial production is workable, and low production cost is fit to industrial applications.
Embodiment
The following examples are in order to explanation the present invention.
It may be noted that following examples are not construed as limiting the invention.
Example 1: with the pump ammonium sulfite solution that to squeeze into 1.9 tons of concentration in 3000 liters of reactors be 35% (wt%), open stirring and be warming up to 90 ± 2 ℃, keep this temperature and in 3 hours, drip 330 kilograms of methyl-sulfates, after dripping off methyl-sulfate, isothermal reaction is 2 hours under said temperature, reaction finishes the back intensification distillation methyl alcohol that water outlet and side reaction generated, and reaction solution is slowly joined contain 370 kilograms of Ca (OH) then
2Emulsion (moisture about 1 ton) in, have this moment a large amount of ammonias to generate, stir to distill down and be blown into air and remove ammonia, ammonia reclaims also and SO by the ammonia absorber water
2Prepared in reaction ammonium sulphite aqueous solution recycled, with the centrifuging of still kettle raffinate cooling back, and with 100 kg of water with filter cake washing 2 times, filtrate and washing lotion merging, to wherein slowly dripping 220 kilograms of vitriol oils and stirring 0.5 hour, reaction solution centrifuging, with filter cake washing 2 times, filtrate and washing lotion merge with 60 kg of water, underpressure distillation goes out most water, the concentration kettle raffinate obtains methylsulphonic acid through underpressure distillation again, and product is a colourless transparent liquid, Cl
-Ion content equals 0ppm, SO
4 2-Ion content is less than 10ppm, and the still kettle raffinate is circulated to together distillation in the next batch acid adjustment liquid, and the average yield of methylsulphonic acid product is 84% (pressing methyl-sulfate calculates).
Example 2: with the pump ammonium sulfite solution that to squeeze into 1.97 tons of concentration in 3000 liters of reactors be 20% (wt%), open stirring and be warming up to 95 ± 2 ℃, keep this temperature and in 2 hours, drip 300 kilograms of methyl-sulfates, after dripping off methyl-sulfate, isothermal reaction is 2 hours under said temperature, reaction finishes the back intensification distillation methyl alcohol that water outlet and side reaction generated, and reaction solution is slowly joined contain 340 kilograms of Ca (OH) then
2Emulsion (moisture about 1 ton) in, have this moment a large amount of ammonias to generate, stir to distill down and be blown into air and remove ammonia, ammonia reclaims also and SO by the ammonia absorber water
2Prepared in reaction ammonium sulphite aqueous solution recycled, with the centrifuging of still kettle raffinate cooling back, and with 100 kg of water with filter cake washing 2 times, filtrate and washing lotion merging, to wherein slowly dripping 210 kilograms of vitriol oils and stirring 0.5 hour, reaction solution centrifuging, with filter cake washing, filtrate and washing lotion merge with 60 kg of water, underpressure distillation goes out most water, the concentration kettle raffinate obtains methylsulphonic acid through underpressure distillation again, and product is a colourless transparent liquid, Cl
-Ion content equals 0ppm, SO
4 2-Ion content is less than 10ppm, and distillation still residue is circulated to together distillation in the next batch acid adjustment liquid, and the average yield of methylsulphonic acid product is 82% (pressing methyl-sulfate calculates).
Example 3: to stirring is housed, constant pressure funnel, the aqueous solution (the ammonium sulphite content 28% (wt%) that adds 380 gram ammonium sulphites and ammonium bisulfite mixture in the 1L four-hole boiling flask of reflux exchanger (being connected to device for absorbing tail gas) and thermometer, ammonium bisulfite content 12% (wt%)) unlatching is stirred and is warming up to 100 ± 2 ℃, keep this temperature and in 1.5 hours, drip 65.6 gram methyl-sulfates, after dripping off methyl-sulfate, isothermal reaction is 1 hour under said temperature, reaction finishes the back system and connects water distilling apparatus and device for absorbing tail gas, the methyl alcohol that distillation water outlet and side reaction generate adds in reaction solution then and contains 70 gram Ca (OH)
2Emulsion, have this moment a large amount of ammonias to generate, stir distillation down and be blown into air and remove ammonia, the ammonia water absorbs and and SO
2Prepared in reaction bisulfite aqueous ammonium recycled is after the ammonia displacement fully, with vinasse cooling back suction filtration, and with 100 ml waters with filter cake washing 2 times, filtrate and washing lotion merge, to wherein slowly dripping the 44 gram vitriol oils and stirring 0.5 hour, the reaction solution suction filtration, and with 100 ml waters with filter cake washing 2 times, filtrate and washing lotion merge, first underpressure distillation goes out most water, concentrated raffinate obtains methylsulphonic acid through rectification under vacuum again, product 72 grams (by pure product), colourless transparent liquid, Cl
-Ion content equals 0ppm, SO
4 2-Ion content is less than 10ppm, productive rate (by methyl-sulfate) 72%.
Claims (7)
1, a kind of method for preparing methylsulphonic acid, it is characterized in that: the aqueous solution of the mixture of methyl-sulfate and ammonium sulphite or ammonium sulphite and ammonium bisulfite or solid mixture are 50～150 ℃ in temperature of reaction and reacted 0.5～10 hour down, reaction solution is handled with calcium oxide or calcium hydroxide, resulting methylsulphonic acid calcium is used vitriolization again behind deamination, after underpressure distillation obtains methylsulphonic acid;
Wherein, the mol ratio of ammonium salt and methyl-sulfate is 1.5～5: 1, and reaction pressure is 0.01～1.0Mpa.
2, the method for preparing methylsulphonic acid according to claim 1 is characterized in that: the ammonium salt that reacts with methyl-sulfate is the ammonium sulphite aqueous solution.
3, the method for preparing methylsulphonic acid according to claim 1 and 2 is characterized in that: the massfraction of ammonium sulfite solution is 10%～50%.
4, the method for preparing methylsulphonic acid according to claim 1 is characterized in that: the mol ratio of ammonium salt and methyl-sulfate (2～3): 1.
5, the method for preparing methylsulphonic acid according to claim 1 is characterized in that: reaction pressure is a normal pressure.
6, the method for preparing methylsulphonic acid according to claim 1 is characterized in that: temperature of reaction is 80～110 ℃.
7, the method for preparing methylsulphonic acid according to claim 1 is characterized in that: add the sulfuric acid with the stoichiometry such as metilsulfate that generated during processing reaction liquid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108463455A (en) * | 2015-11-10 | 2018-08-28 | 巴斯夫欧洲公司 | The method for reprocessing alkanesulfonic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101219975B (en) * | 2007-01-10 | 2010-07-21 | 河北亚诺化工有限公司 | Process for producing methanesulfonic acid |
| BR112012010092B1 (en) | 2009-11-03 | 2018-06-05 | Basf Se | USE OF AUSTENIC STAINLESS STEELS |
| CN105237441B (en) * | 2015-11-02 | 2017-06-13 | 中国石油天然气股份有限公司 | A kind of apparatus and method for reclaiming Loprazolam |
| KR20180081577A (en) | 2015-11-10 | 2018-07-16 | 바스프 에스이 | Method for purification of alkanesulfonic acid |
| CN106748907B (en) * | 2017-01-18 | 2019-02-05 | 湖北星火化工有限公司 | A kind of method of purification of methane sulfonic acid |
| TW201841881A (en) | 2017-04-18 | 2018-12-01 | 德商巴斯夫歐洲公司 | Process for purifying alkanesulfonic anhydride and process for producing alkanesulfonic acid using the purified alkanesulfonic anhydride |
| KR102632030B1 (en) | 2017-05-30 | 2024-01-31 | 바스프 에스이 | Method for producing methane sulfonic acid |
| FR3070686B1 (en) * | 2017-09-01 | 2019-08-30 | Arkema France | SULFONIC ACID LOW COLOR |
| CN112079751B (en) * | 2020-09-24 | 2022-11-29 | 辽宁科隆精细化工股份有限公司 | Preparation method of high-purity methane sulfonic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1350328A (en) * | 1971-05-28 | 1974-04-18 | Pennwalt Corp | Method for the preparation of alkane sulphonic acids |
| US6060621A (en) * | 1997-10-04 | 2000-05-09 | Grillo-Werke A.G. | Process for the preparation of methanesulfonic acid |
-
2005
- 2005-01-26 CN CNB200510002684XA patent/CN100348579C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1350328A (en) * | 1971-05-28 | 1974-04-18 | Pennwalt Corp | Method for the preparation of alkane sulphonic acids |
| US6060621A (en) * | 1997-10-04 | 2000-05-09 | Grillo-Werke A.G. | Process for the preparation of methanesulfonic acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108463455A (en) * | 2015-11-10 | 2018-08-28 | 巴斯夫欧洲公司 | The method for reprocessing alkanesulfonic acid |
| CN108463455B (en) * | 2015-11-10 | 2021-06-15 | 巴斯夫欧洲公司 | Process for reprocessing alkanesulfonic acids |
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| CN1810780A (en) | 2006-08-02 |
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