CN101875623A - Method for preparing methylsulphonic acid from halogenated methane - Google Patents
Method for preparing methylsulphonic acid from halogenated methane Download PDFInfo
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Abstract
The invention discloses a method for preparing methylsulphonic acid from halogenated methane, which comprises the following steps of: reacting aqueous solution of sulfite with the halogenated methane at the temperature of between 60 and 105 DEG C to form methylsulfonate; acidifying the methylsulfonate with strong acid to form solution of methylsulphonic acid and corresponding halate precipitate; and performing distillation under reduced pressure after filtering to obtain the methylsulphonic acid with high yield and purity, wherein the reclaimed acid aqueous solution can be recycled. The method has the advantages of high reaction specificity, no pungent smell, no waste water and residue, high product purity, a few trace impurities, readily available raw materials, simple operation, low cost and industrial mass production application prospect.
Description
Technical field
The invention belongs to technical field of organic chemistry, be specifically related to a kind of method for preparing methylsulphonic acid with methyl halide.
Background technology
The unique applications that demonstrated in the circuit board manufacture of electronic product of methylsulphonic acid in recent years, the application in electroplating industry is more and more wider.The report that methylsulphonic acid and salt system thereof are used in plating increases year by year, and market increases year by year.Methylsulphonic acid and salt thereof have unique purposes when brush copper facing, zinc-plated, the zinc-plated and cadmium plating as main salt, in brush plating copper plating solution, just there are two types as copper methanesulfonate, be acid high speed copper and the high alkali copper of piling up, its excellent performance, of many uses, be that other mantoquita can't be by comparison.The methylsulphonic acid cadmium mainly is the plating that is used for the low hydrogen embrittlement cadmium on the ultrahigh-strength steel, uses more in aircraft industry.In addition, methylsulphonic acid also is the important source material on medicine, agricultural chemicals and the chemical industry.Methylsulphonic acid is the catalyzer of esterification, polyreaction, and the purposes of the aspects such as agent of tachy steroling of printing ink, coating is also very extensive.
China begins to produce methylsulphonic acid and Methanesulfonyl chloride in the nineties in 20th century, its synthetic method more report, and real operable method and technology are mainly as follows:
Thiomethyl alcohol-chlorine oxidation hydrolysis method (US3392095; US4239696), dimethyl disulfide-chlorine oxidation hydrolysis method (US2697722; US3509206; US3948922, WO0210123) above two processing method maturations, reaction process may command; but there is serious air and water pollution; the prices of raw and semifnished materials are higher, and corrosive equipment is unfavorable for environment protection and enterprise development.
At patent documentation US3392095, US4239696, among CN1031838A (1989) and the CN1165136A (1996), adopt thiomethyl alcohol or Methyl disulfide and hydrogen peroxide oxidation can make methylsulphonic acid satisfactorily, and Methyl disulfide is that raw material is synthesized by sodium sulphite, sulphur and methyl-sulfate; But the recovery problem of a large amount of acidic and alkaline waste waters and exhaust gas emission is serious.Improved (CN93110559.5,1993) through Nanjing Pharmaceuticals Inst afterwards, technology realizes pollution-free, non-wastewater discharge, but the methyl-sulfate that uses is highly toxic product, and hydrogen peroxide is easily sudden and violent thing, stores and transport inconvenient, thiomethyl alcohol is a gas, and smell stimulates, and its consumption is big; Adopt methyl disulfide to replace thiomethyl alcohol to react to have overcome the shortcoming of thiomethyl alcohol, reaction conditions gentleness, but prices of raw and semifnished materials height are unfavorable for that also medium-sized and small enterprises keep the safety in production on a large scale.
Use the reaction of S-WAT and methyl-sulfate to generate the technology of methylsulfonic acid, existing a lot of reports over past ten years, the Germany CN1218040A of BASF AG (1998, right of priority DE19743901.2), among the CN1343200A (2000), its productive rate is between 75%-85%, but the employing sulfuric acid acidation is unfavorable to the refining purification of methylsulfonic acid; China system of Hebei Yanao Chemical Co., Ltd. has improved this method (CN1810780A, 2005), adopts the reaction of sulfurous acid (hydrogen) salt and methyl-sulfate, utilizes calcium hydroxide sulfate precipitate radical ion, and obtaining productive rate is the high-quality methylsulfonic acid of 75%-84%; Maybe with the metilsulfate that generates and vitriol by salting-out crystallization and alkaline earth salt precipitate and separate, obtain high purity methylsulfonic acid (CN101219975A, 2007) with the hydrogen chloride gas acidifying again.But methyl-sulfate is highly toxic product, and is unfavorable to transporting and storing.
Also useful Methanesulfonyl chloride hydrolysis makes methylsulfonic acid (US4859373), and Methanesulfonyl chloride can be synthetic by following method:
(1) methyl-isothiourea method: make methyl-isourea by thiocarbamide and methyl-sulfate reaction, make Methanesulfonyl chloride through chlorine oxidation again:
H
2N-C(＝S)-NH
2+(CH
3)
2SO
4→H
2N-C(＝SCH
3)-NH
2·HSO
4
H
2N-C(＝SCH
3)-NH
2·HSO
4+3C1
2+2H
2O→CH
3SO
2Cl+H
2SO
4
This method cost is higher, and acid waste water is serious, is unfavorable for environment protection and enterprise's long-run development.
Methylsulphonic acid is that two-step reaction is carried out in a reactor, asks the separation and the purification of product in having reduced, and product yield is brought up to 85% (in thiocarbamide).This method operational condition gentleness, equipment is simple, and is easy to implement.But because the price of thiocarbamide is higher.
(2) by methylthiocyanide methylthiocyanate oxidation style direct production (US1313853), its technology is simple, and product is single-minded, and multiple oxygenant is arranged, but all generates the nitrogen protoxide toxic gas, is unfavorable for environmental protection.And material cost is higher.
CH
3SCN+[O]→2CH
3SO
3H+8H
2O+NO
(3) directly use nitric acid catalytic oxidation (US6531629, BASF AG, 2003) with mercaptan or dimethyl disulfide, (US6124497,2000) are synthetic:
CH
3SH+2HNO
3→CH
3SO
3H+H
2O+2NO
CH
3SSCH
3+4HNO
3→2CH
3SO
3H+2H
2O+4NO
Though the technology of this method can make methylsulphonic acid satisfactorily with nitric acid catalyzed oxidation thiomethyl alcohol and dimethyl disulfide, though these method reaction conditions gentlenesses; Nitric acid is oxygenant, the reaction yield height; But there is wayward phenomenon in reaction process, and air and water pollution is serious, stores and the transportation inconvenience; Prices of raw and semifnished materials height is unfavorable for that medium-sized and small enterprises keep the safety in production on a large scale.Do not meet China's chemistry environmental protection strategy of sustainable development yet.
(4) German BASF AG is by sulphur trioxide and methane or acetic acid reaction (US6207025,2001) method:
2CH
4+2SO
2+H
2O→2CH
3SO
3H
CH
3COOH+SO
2→2CH
3SO
3H+CO
2
The prices of raw and semifnished materials of this method are lower, and synthetic yield is all very high, but technology catalytic unit and catalyzer cost are higher, the equipment requirements strictness, and exist tail gas to absorb problem, also be unfavorable for the development of the batch production scale of Small and Medium Enterprises in China:
(5) adopt chloroparaffin and S-WAT or Sulfothiorine to react being higher than under the 120 degree left and right sides high pressure, also obtain methylsulphonic acid (US5312974):
Na
2S
2O
3+CH
3C1→CH
3S
2O
3Na+NaC1
2CH
3SSO
3Na+Cl
2→2CH
3SO
2Cl+Na
2SO
3
CH
3SO
2Cl+H
2O→CH
3SO
3H+HCl
This method is suitable for suitability for industrialized production, and environmental problem is less.But Sulfothiorine is on the high side, and productive rate is on the low side; And be suitable for the production of continuity reactor, be not suitable for the middle and small scale batch production.Present this technology imperfection, the improvement of still needing, equipment flowsheet also has problems; Have only stabilization process condition and equipment flowsheet, stablize yield and quality could be produced use:
In a word, all there are different relative merits in these methylsulphonic acid synthesis techniques, particularly all have deficiency aspect the sustainable developments such as the feature of environmental protection, cost, technology operability and equipment utilization.
In line with reducing environmental pollution, reducing cost is purpose, and the present invention is a basic raw material with a halomethane, on the basis of existing processing unit, inquires into other synthetic methods of methylsulphonic acid, to satisfy the methylsulphonic acid market demand that grows stronger day by day.
Summary of the invention
The objective of the invention is to avoid having the weak point in the production technology now and providing a kind of no waste water capable of being industrialized, odorlessness, no waste residue, environment amenable methyl halide to prepare the novel method of methylsulphonic acid, this method avoids using those poisonous and strong materials of pungency, and has therefore reduced security costs and production cost is low.
In order to realize this purpose, the present invention adopts a methyl halide and sulfite solution reaction, generate the mesylate solution of equimolar amount, obtain methylsulphonic acid solution and halogen precipitate and separate with the strong acid acidifying again, obtain high yield, high-purity methanesulfonic acid through underpressure distillation.Its principal reaction equation is as follows:
M
2SO
3+CH
3X→CH
3SO
3M+MX
CH
3SO
3M+HX→CH
3SO
3H+MX↓
The present invention is a kind of method for preparing methylsulphonic acid, and its purpose can reach by following measure:
The sulfite solution and the methyl halide of preparation are reacted under certain temperature and pressure, generate the methylsulphonic acid salts solution, obtain methylsulphonic acid with the strong acid acidifying again, and separate and remove the halate of separating out, filtrate is through behind the concentrating under reduced pressure, obtains purity greater than 99.5% methylsulphonic acid product through underpressure distillation again.
Described sulphite is S-WAT (potassium), sodium bisulfite (potassium), ammonium sulphite, ammonium bisulfite, Sodium Pyrosulfite (potassium, ammonium), pyrosulphite hydrogen sodium (potassium, ammonium); Preferred Sodium Pyrosulfite and S-WAT.
The sulfite solution concentration expressed in percentage by weight of described preparation is about 15～50% (wt%).
The mol ratio of described sulfite solution and methyl halide reaction is 1: (1～1.20), optimum mole ratio are 1: (1～1.05).
Described reactant methyl halide is monochloro methane or a monobromethane or a methyl iodide or methyl-sulfate.
Described reaction vessel is a pressurized vessel, and the pressure of its methyl halide is 0.1～1.5MPa, and temperature of reaction is 60 ℃～105 ℃, and the reaction times is at 3～10 hours.
And the halogen that the X-common-ion effcet of utilizing excessive hydracid (HX) makes generation fully, precipitate fully and separate, filtrate decompression dephlegmate part and excessive halo acid ion, obtain the methylsulphonic acid crude product, obtain high-purity methanesulfonic acid through underpressure distillation again.The salts contg that present method generates does not have other impurity more than 98%, and is nontoxic, helps recycling.
The present invention replaces methyl-sulfate with a halomethane, mainly is because methyl-sulfate is highly toxic product, transportation and production operation inconvenience.One halomethane is by the product of methyl alcohol generation halogenating reaction or the halogenated byproduct of methane, aboundresources, and price is low, and toxicity is little, and production process is easy to control.
Sulphite among the present invention or bisulfite solution mainly are to exist with the inferior sulfate radical form, and this sulphite can be S-WAT, potassium sulfite, ammonium sulphite, Sodium Pyrosulfite (Na
2S
2O
5) and ammonium pyrosulfite, potassium pyrosulfite etc., hydrosulphite can be sodium bisulfite (potassium, ammonium) and pyrosulphite hydrogen sodium (potassium, ammonium).Sulfurous acid ion concentration is preferably 25%-35% about 15%-50% (wt%).Increase equipment input that concentration is low reduces production efficiency; The concentration height easily separate out the sulphite crystallization, be unfavorable for production operation.
Methyl halide among the present invention can be monochloro methane, a monobromethane or a methyl iodide.Wherein the iodomethane reaction activity is the highest, and the methyl chloride reactive behavior is lower.In the reaction of preparation methylsulphonic acid, adopt the temperature of reaction of a methyl iodide lower, temperature needs only 55 ℃-75 ℃, just reacts completely in 2-3 hour, and the productive rate that obtains methylsulphonic acid is about 98%.Adopt a monobromethane to react 3-4 hour between 70 ℃-80 ℃, just can react completely, the productive rate of methylsulphonic acid is more than 95%.And the employing monochloro methane then needs to react 3-5 hour between 80 ℃-100 ℃, could change into metilsulfate fully, and productive rate is about 85%-95%.But the price of a monobromethane and a methyl iodide is more expensive, is unfavorable for the big production of large-scale industrialization; And monochloro methane market turnout is very big, and price is lower.From economic angle, select for use monochloro methane favourable to industrial production.Therefore, the present invention preferentially selects for use monochloro methane to prepare methylsulphonic acid.
Because the boiling point of a halomethane is lower than temperature of reaction, reaction unit need be selected autoclave pressure for use, and reaction pressure is controlled between the 0.1-1.5MPa.Present method is preferentially selected 0.3-0.5MPa, so that safety operation.
Present method can adopt strong acid acidifyings such as appropriate strong phosphoric acid, sulfuric acid and concentrated hydrochloric acid after generating metilsulfate, and precipitates and handle by product phosphate radical, sulfate radical and chlorion by generating salt.But phosphoric acid salt, vitriol can only obtain the mixing salt solid in aftertreatment separates, and are not easy to reclaim and use.Therefore, preferentially select the concentrated hydrochloric acid acidifying, obtain high-purity halogen, content is used so that reclaim more than 95% again.In the filtrate after the process filtering separation mainly is methylsulphonic acid, hydrogenchloride and water, remove de-chlorine hydride, water and hydrochloric acid solution by the rough vacuum underpressure distillation, obtain purity greater than 99.5% water white transparency methylsulphonic acid liquid through the high vacuum underpressure distillation again, chloride ion content is lower than 5 μ g/ml, sulfate ion is lower than 10 μ g/ml, metal ion content is lower than 3 μ g/ml, and its reaction yield (is calculated with sulphite) between 85%-95%.And,, can reclaim recycled owing to contain a small amount of methylsulfonic acid (salt) for water that distills out and hydrochloric acid soln (hydrogen chloride content is about 20-25%), to improve reaction yield.
The present invention compares with technology in the past has following progress: the reaction specificity is strong, and reaction yield height, starting material are easy to get, cost is low, and the methylsulphonic acid purity height of generation can obtain the methylsulphonic acid more than 99.9%; React no waste water, no waste residue, the generation that has no irritating odor, the starting material toxicological harmless, the by product halogen purity height of generation can be used as industrial raw material.
Embodiment
Embodiment one:
The sodium sulfite solution of 1000 grams 21% is added in the autoclave of 2L, be heated to 70 ℃, feed monochloro methane to 0.5MPa, open and stir, be warming up to 90 ℃, pressure is reduced to below the 0.15MPa after half an hour approximately, feed monochloro methane to pressure again and reach 0.5MPa, feed altogether 5 times, add up to feed 103 gram monochloro methanes, 3.5 pressure remains unchanged after hour, pressurize 1 hour.Stop heating, be cooled to 60 ℃, extract reaction solution out, revolve to steam and dewater, steam till the white solid.Add 500 gram concentrated hydrochloric acids (～35%), stir, produce a large amount of white precipitates, reaction solution is heated to 60 ℃, still aging spending the night leaches NaCl salt, gets yellow solution.Yellow solution is revolved steaming to dewater, underpressure distillation does not steam to there being moisture, scavenge oil pump distillation again, in temperature is 167 ℃, and pressure is under the condition of 1.33kPa, collects colourless transparent liquid 137.3 grams, productive rate 86%, purity 〉=99.5%, chloride ion content≤5 μ g/ml, sulfate ion content≤5 μ g/ml.
Embodiment two:
The sodium sulfite solution of 1250 grams 26.5% is added in the autoclave of 2L, open and stir, be heated to 70 ℃, feed a monobromethane to the 3.5MPa, be warming up to 75 ℃, heated and stirred is after 2.5 hours, after absorbing 186 grams, one monobromethane, close air intake valve, reactor pressure is constant, continues to stir 0.5 hour.Stop heating, when cooling to 60 ℃, extract reaction solution out, revolve to steam and remove moisture content till the white solid.Add 620ml concentrated hydrochloric acid (～35%), stir, produce a large amount of white precipitates, standing over night obtains pale yellow solution after leaching salt.This solution is revolved steaming eliminate moisture content, underpressure distillation is 167 ℃ in temperature, pressure is under the condition of 1.33kPa, collects colourless transparent liquid 242.1 grams, productive rate 96%, purity 〉=99.5%, maximum chloride ion content≤5 μ g/ml, maximum sulfate ion content≤10 μ g/ml.
Embodiment three:
456 gram 27.6% sodium sulfite solutions and 142 gram methyl iodide are joined in the autoclave of 1L, be heated to 60 ℃, stirred 2.5 hours.Stop heating, extract reaction solution out, revolve to steam and remove moisture content till the white solid.Add 300ml concentrated hydrochloric acid (～35%), stir, produce a large amount of white precipitates, standing over night leaches salt, gets yellow solution.This solution is revolved steaming eliminate moisture content, underpressure distillation is 167 ℃ in temperature, pressure is under the condition of 1.33kPa, collects colourless transparent liquid 93.1 grams, productive rate 97.1%, purity 〉=99.5%, maximum chloride ion content≤5 μ g/ml, maximum sulfate ion content≤10 μ g/ml.
Embodiment four:
466 grams, 24.6% ammonium sulfite solution is joined in the autoclave of 1L, open to stir, be heated to 80 ℃, feed monochloro methane to the 0.5MPa, be warming up to 85-90 ℃, approximately feed 52 gram monochloro methanes.Air intake valve, heated and stirred be after 3.5 hours, stops heating and stir, and cools to 50 ℃, opens autoclave, extracts reaction solution out, revolves to steam to remove moisture content till the white solid.Add 300ml concentrated hydrochloric acid (～35%), stir, produce a large amount of white precipitates, standing over night leaches solid, gets yellow solution.This solution is revolved steaming eliminate moisture content, underpressure distillation is 147 ℃ in temperature, pressure is under the condition of 1kPa, collects colourless transparent liquid 82.6 grams, productive rate 86%, purity 〉=99.5%, maximum chloride ion content≤5 μ g/ml, maximum sulfate ion content≤10 μ g/ml.
Embodiment five:
650 gram 25.5% potassium sulfite solution (recycle-water preparation) are joined in the autoclave of 1L, open and stir, be heated to 60 ℃, feed 130 grams, one monobromethane to the 0.25MPa in batches, be warming up to 70 ℃ and stir after 3 hours, close heating and air intake valve, cool to 50 ℃, extract reaction solution out, revolve to steam and remove moisture content till the white solid.Add 400ml concentrated hydrochloric acid (～35%), stir, produce a large amount of white precipitates, standing over night leaches salt, gets yellow solution.This solution is revolved steaming eliminate moisture content, underpressure distillation is 145 ℃ in temperature, pressure is under the condition of 0.93kPa, collects colourless transparent liquid 99.8 grams, productive rate 95.1%, purity 〉=99.5%, maximum chloride ion content≤5 μ g/ml, maximum sulfate ion content≤10 μ g/ml.
Embodiment six:
650 gram 27.5% sodium sulfite solutions (recycle-water preparation) are joined in the autoclave of 1L, open to stir, be heated to 80 ℃, feed monochloro methane to the 0.5MPa, be warming up to 85-95 ℃, approximately feed 75 and restrain monochloro methanes.Air intake valve, heated and stirred be after 4.5 hours, stops heating and stir, and cools to 50 ℃, opens autoclave, extracts reaction solution out, revolves to steam to remove moisture content till the white solid.Add 400ml concentrated hydrochloric acid (～35%), stir, produce a large amount of white precipitates, standing over night leaches salt, gets yellow solution.This solution is revolved steaming eliminate moisture content, underpressure distillation is 165 ℃ in temperature, pressure is under the condition of 1.33kPa, collects colourless transparent liquid 121.2 grams, productive rate 89%, purity 〉=99.5%, maximum iodide ion content≤5 μ g/ml, maximum sulfate ion content≤10 μ g/ml.
Claims (9)
1. method for preparing methylsulphonic acid with methyl halide, it is characterized in that the sulfite solution and the methyl halide of preparation are reacted under certain temperature and pressure, generate the methylsulphonic acid salts solution, obtain methylsulphonic acid with the strong acid acidifying again, and separate out a large amount of halates, prepare high-purity methanesulfonic acid through underpressure distillation after the filtration.
2. a kind of method for preparing methylsulphonic acid with methyl halide according to claim 1, it is characterized in that sulphite is S-WAT (potassium) or sodium bisulfite (potassium) or ammonium sulphite or ammonium bisulfite or Sodium Pyrosulfite (potassium, ammonium) or pyrosulphite hydrogen sodium (potassium, ammonium); Preferred Sodium Pyrosulfite or S-WAT.
3. according to claim 1 and 2 described a kind of methods that prepare methylsulphonic acid with methyl halide, the sulfite solution that it is characterized in that described preparation, concentration expressed in percentage by weight (wt%) is about 15%～50%, preferred sulfite concentration (wt%) 20%～35%.
4. according to claim 1ly a kind ofly prepare the method for methylsulphonic acid with methyl halide, it is characterized in that the mol ratio of sulfite solution and methyl halide reaction is 1: (1～1.20), preferred molar ratio are 1: (1～1.05).
5. according to claim 1ly a kind ofly prepare the method for methylsulphonic acid, it is characterized in that described reactant methyl halide is monochloro methane or a monobromethane and a methyl iodide or methyl-sulfate, a preferred monochloro methane or a monobromethane with methyl halide.
6. according to claim 1ly a kind ofly prepare the method for methylsulphonic acid with methyl halide, it is characterized in that this is reflected in the pressurized vessel carries out, and the pressure of its methyl halide is 0.1～1.5MPa, and preferred reaction pressure is 0.3～0.5MPa.
7. according to claim 1ly a kind ofly prepare the method for methylsulphonic acid with methyl halide, it is characterized in that described this temperature of reaction is 60 ℃～105 ℃, preferable reaction temperature is at 80 ℃～90 ℃.
8. according to claim 1ly a kind ofly prepare the method for methylsulphonic acid with methyl halide, it is characterized in that this reaction times at 3-10 hour, the preferred reaction time was at 3-5 hour.
9. a kind of method for preparing methylsulphonic acid with methyl halide according to claim 1, it is characterized in that utilizing the common-ion effcet of excessive hydracid that the halogen of generation is precipitated out fully, filtrate decompression dephlegmate part and excessive halo acid ion, obtain the methylsulphonic acid crude product, underpressure distillation obtains high-purity methanesulfonic acid again, and moisture content that is steamed and acid solution can reclaim again and use.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108516944A (en) * | 2018-05-04 | 2018-09-11 | 苏州华新能源科技有限公司 | A kind of preparation method of methane-disulfonic acid |
| WO2019154681A1 (en) * | 2018-02-07 | 2019-08-15 | Basf Se | Process for the manufacturing of alkanesulfonic acids |
| CN110678443A (en) * | 2017-05-30 | 2020-01-10 | 巴斯夫欧洲公司 | Process for producing methanesulfonic acid |
| CN111620795A (en) * | 2020-04-27 | 2020-09-04 | 华东师范大学 | Aryl and alkyl sulfonic acid compounds, and construction method and application of inorganic sulfur salt |
| CN117986162A (en) * | 2024-04-02 | 2024-05-07 | 寿光诺盟化工有限公司 | Preparation method of ethyl sulfonyl chloride |
| CN117986162B (en) * | 2024-04-02 | 2024-06-21 | 寿光诺盟化工有限公司 | Preparation method of ethyl sulfonyl chloride |
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|---|---|---|---|---|
| CN110678443A (en) * | 2017-05-30 | 2020-01-10 | 巴斯夫欧洲公司 | Process for producing methanesulfonic acid |
| CN110678443B (en) * | 2017-05-30 | 2022-10-25 | 巴斯夫欧洲公司 | Process for producing methanesulfonic acid |
| CN111683925B (en) * | 2018-02-07 | 2022-12-27 | 巴斯夫欧洲公司 | Process for preparing alkanesulfonic acids |
| WO2019154681A1 (en) * | 2018-02-07 | 2019-08-15 | Basf Se | Process for the manufacturing of alkanesulfonic acids |
| CN111683925A (en) * | 2018-02-07 | 2020-09-18 | 巴斯夫欧洲公司 | Process for preparing alkanesulfonic acids |
| TWI822727B (en) * | 2018-02-07 | 2023-11-21 | 德商巴斯夫歐洲公司 | Process for the manufacturing of methanesulfonic acids |
| US11247967B2 (en) | 2018-02-07 | 2022-02-15 | Basf Se | Process for the manufacturing of alkanesulfonic acids |
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| CN108516944B (en) * | 2018-05-04 | 2021-03-09 | 苏州华一新能源科技有限公司 | Preparation method of methane disulfonic acid |
| CN111620795A (en) * | 2020-04-27 | 2020-09-04 | 华东师范大学 | Aryl and alkyl sulfonic acid compounds, and construction method and application of inorganic sulfur salt |
| CN111620795B (en) * | 2020-04-27 | 2021-11-19 | 华东师范大学 | Aryl and alkyl sulfonic acid compounds, and construction method and application of inorganic sulfur salt |
| CN117986162A (en) * | 2024-04-02 | 2024-05-07 | 寿光诺盟化工有限公司 | Preparation method of ethyl sulfonyl chloride |
| CN117986162B (en) * | 2024-04-02 | 2024-06-21 | 寿光诺盟化工有限公司 | Preparation method of ethyl sulfonyl chloride |
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