CN1129213A - Technical process for preparation of water-soluble methy-disulfonate - Google Patents
Technical process for preparation of water-soluble methy-disulfonate Download PDFInfo
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- CN1129213A CN1129213A CN 95101622 CN95101622A CN1129213A CN 1129213 A CN1129213 A CN 1129213A CN 95101622 CN95101622 CN 95101622 CN 95101622 A CN95101622 A CN 95101622A CN 1129213 A CN1129213 A CN 1129213A
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Abstract
The preparation process of water-soluble methyl disulfonate includes four procedures of sulfonating reaction, reaction by addition of barium, salt conversion and concentration and drying. Said water-soluble methyl disulfonate is made up by using methylene dichloride and sodium sulfite as raw materials to react to prepare water-soluble sodium methyl disulfonate, then using barium chloride to treat said solution to obtain the insoluble barium methyl disulfonate, and then making water-soluble sulfate and barium methyl disulfonate react to obtain the invented product. The preparation method is simple, and its raw material source is extensive.
Description
The present invention relates to a kind of preparation method of water-soluble methy-disulfonate.
Alkylsulfonate is the catalyzer of novel alkoxylated polymerization reaction (as synthesizing glycol ethers, propylene glycol ethers).This class catalyzer Heat stability is good, the catalytic activity height, selectivity is good, the product yield height, nontoxic, nonirritant is to the equipment non-corrosiveness.Wherein the most frequently used kind is trifluoromethane sulfonic acid aluminium (magnesium, zinc), methyl disulfonic acid zinc (aluminium, magnesium) etc.The general method of preparation methy-disulfonate is at first to prepare the methyl disulfonic acid, uses metal replacement then, to produce corresponding salt.The preparation method of water-soluble methy-disulfonate mainly contains three kinds at present:
(a). with methylene dichloride, potassium sulfite is feedstock production methyl disulfonic acid potassium, methyl disulfonic acid potassium and bariumchloride reaction make methyl disulfonic acid barium, with sulfuric acid acidation methyl disulfonic acid barium, obtain the methyl disulfonic acid, the barium sulfate of generation precipitates from reaction soln separates out.Carry out replacement(metathesis)reaction with metal powder (aluminium, magnesium, zinc) with the methyl disulfonic acid, make corresponding methy-disulfonate (aluminium, magnesium, zinc).(Recueil?des?Travaux?Chimiques?des?Pays-Bas?48，Pg949-952(1929))
(b). make the methyl disulfonic acid with chlorsulfonic acid and methylsulphonic acid reaction, carry out replacement(metathesis)reaction with metal powder again, make corresponding methy-disulfonate.(day special public clear 64-45355)
(c). acetylene and oleum acid system are with SO
2Be solvent, with acetylene and SO
3Dissolving is wherein reacted under-20 ℃～-30 ℃ temperature and is made intermediate product OHCCH (SO
3H)
2, and then its decomposition made the methyl disulfonic acid.Replace with metal powder and to obtain methy-disulfonate.(US2506417US2552421)
Preparation method (a), methyl disulfonic acid corrodibility is strong, and replacement(metathesis)reaction produces hydrogen, and is inflammable and explosive; Preparation method (b), raw material sources are more in short supply, and stronger corrodibility is arranged; Preparation method (c), reaction conditions is difficult for reaching, and energy consumption is big, and raw material corrodibility is big.
It is wider to the objective of the invention is to design a kind of raw material sources, and technology is simple, the processing method of the preparation water-soluble methy-disulfonate of operational safety.
The processing method of preparation methy-disulfonate provided by the invention is to be raw material with methylene dichloride and S-WAT, transforms, concentrates and operation such as drying through oversulfonate, bariumization, salt, makes white powder methyl disulfonic acid zinc (aluminium, magnesium) at last.
(1). sulfonation operation: with Na
2SO
3Be mixed with the aqueous solution that concentration is 100-260g/l, the input reactor, temperature should be less than 30 ℃, adding methylene dichloride to reactor then reacts, make S-WAT/methylene dichloride=2.05-2.4 (mol ratio): control still internal pressure is at 0.8-1.2MPa, temperature 160-200 ℃, reacted 2-6 hour, then material is cooled to below 70 ℃.
(2). barium chemical industry preface: in the barium reactor, add the bariumchloride solid that surpasses theoretical amount slightly, make bariumchloride/methyl sodium disulfonate=1.05-1.4 (mol ratio), be dissolved in water, the concentration that makes bariumchloride is in the 200-300g/l scope, in the barium reactor, be added in the material methyl sodium disulfonate that the sulfonation operation obtains then, stirring reaction 20-50 minute.This reaction is normal pressure, temperature 30-60 ℃.After reaction finishes, carry out centrifuging, filter cake is a methyl disulfonic acid barium.
(3). salt conversion procedure: in salt conversion reaction still, add a certain amount of vitriol (aluminium, magnesium, zinc salt etc.), add water and make it dissolving, concentration is in the 400-500g/l scope, to go up the filter cake methyl disulfonic acid barium that operation obtains then joins in the salt conversion reaction still, make vitriol/methyl disulfonic acid barium=0.8-0.9 (mol ratio) start stirring, sealing was reacted 2-4 hour.Reaction pressure is a normal pressure, temperature of reaction≤100 ℃.Reaction is cooled to about 40 ℃ material after finishing.With material filtering, filtrate is the aqueous solution of methy-disulfonate.
(4). concentrated, drying process: in the aqueous solution input concentration kettle with methy-disulfonate, be warming up to 100 ℃, concentrate.Along with the evaporation of moisture, feed temperature increases.When feed temperature rises to 110-120 ℃, stop heating, feed liquid is put in the stainless steel vessel, make it spontaneous nucleation.Methy-disulfonate after the crystallization is put into moisture eliminator and is carried out drying, dries by the fire fully until moisture.Dried block is pulverized, promptly obtained Powdered methy-disulfonate product.
Product MTZ, promptly methyl disulfonic acid zinc is white powder, and zinc content is 26.3-28.3%, and sulphur content is 25.7-27.7%.Product methyl disulfonic acid aluminium, aluminium content is 7.4-11.4%, sulphur content is 31.3-35.3%.The alkoxylation that is used for catalytic epoxyethane and propyl carbinol, under the condition of oxyethane/propyl carbinol (mol ratio)=1/3, the oxyethane transformation efficiency is greater than 99%, selectivity is greater than 5.0 (selectivity=ethylene glycol mono-ether weight/ethylene glycol polyether weight), and the butyl glycol ether productive rate is greater than 76%; When oxyethane/propyl carbinol (mol ratio)=1/6, the oxyethane transformation efficiency is greater than 99%, and selectivity is about 12, and the butyl glycol ether productive rate is 95-96%.Be used for catalytic epoxyethane and alcoholic acid alkoxylation, under the condition of oxyethane/ethanol (mol ratio)=1/5, the oxyethane transformation efficiency is greater than 99%, and selectivity is greater than 8.5, and the ethylene glycol ethyl ether productive rate is greater than 82%.
Embodiment 1:
(1). measure filtering sodium sulfite aqueous solution (concentration is 240.6g/l) 300ml and join in the 0.5L still, add the 23.2g methylene dichloride again,, heat up and stir the still good seal.When temperature rises to 180 ℃, insulation reaction four hours.After reaction finished, logical water coolant reached about 80 ℃ feed temperature in still, obtains sulfonation reaction liquid, and discharging is stand-by.
(2). add 80g bariumchloride solid and 350ml water in glass beaker, stirring adds above-mentioned sulfonation reaction liquid after making its dissolving, produces a large amount of white precipitates.With the feed liquid vacuum filtration, filter cake is a methyl disulfonic acid barium solid then.
(3). in the glass there-necked flask of 1000ml, add zinc sulfate solid and the 350ml water of 60.6g, after stirring makes the zinc sulfate dissolving, add methyl disulfonic acid barium solid.Be warming up to 100 ℃, zinc sulfate and methyl disulfonic acid barium were reacted four hours under the water reflux conditions.After reaction finished, with the reaction solution vacuum filtration, filtrate was the methyl disulfonic acid zinc aqueous solution.
(4). the methyl disulfonic acid zinc aqueous solution is concentrated, dries, pulverizes, promptly obtain methyl disulfonic acid zinc finished product of the present invention.
Embodiment 2:
(1). measure oneself filtering sodium sulfite aqueous solution (concentration is 216.2g/l) 7000ml and join in the 10L still, add the 486.07g methylene dichloride again,, heat up and stir the still good seal.When temperature rises to 180 ℃, insulation reaction four hours.After reaction finished, logical water coolant reached about 80 ℃ feed temperature in still, obtains sulfonation reaction liquid, and discharging is stand-by.
(2). add 1676g bariumchloride solid and 6270ml water in the 20L stainless steel cask, stirring adds above-mentioned sulfonation reaction liquid after making its dissolving, produces a large amount of white precipitates.With feed liquid centrifuging, filter cake is a methyl disulfonic acid barium solid then.
(3). in the glass there-necked flask of 5000ml, add zinc sulfate solid and the 4000ml water of 1480g, after stirring makes the zinc sulfate dissolving, add methyl disulfonic acid barium solid.Be warming up to 100 ℃, zinc sulfate and methyl disulfonic acid barium were reacted four hours under the water reflux conditions.After reaction finished, with reaction solution centrifuging, filtrate was the methyl disulfonic acid zinc aqueous solution.
(4). the methyl disulfonic acid zinc aqueous solution is concentrated, dries, pulverizes, promptly obtain methyl disulfonic acid zinc finished product of the present invention.
Embodiment 3:
(1). get filtering sodium sulfite aqueous solution (concentration is 200.9g/l) 1600ml and join in the 2L still, add the 103.3g methylene dichloride again,, heat up and stir the still good seal.When temperature rises to 180 ℃, insulation reaction four hours.After reaction finished, logical water coolant reached about 80 ℃ feed temperature in still, obtains sulfonation reaction liquid, and discharging is stand-by.
(2). add 356g bariumchloride solid and 1000ml water in glass beaker, stirring adds above-mentioned sulfonation reaction liquid after making its dissolving, produces a large amount of white precipitates.With feed liquid centrifuging, filter cake is a methyl disulfonic acid barium solid then.
(3). in the glass there-necked flask of 3000ml, add the 18 water Tai-Ace S 150 solid of 242.7g, add water stir make the Tai-Ace S 150 dissolving after, add methyl disulfonic acid barium solid.Be warming up to 100 ℃, zinc sulfate and methyl disulfonic acid barium were reacted four hours under the water reflux conditions.After reaction finished, with reaction solution centrifuging, filtrate was methyl disulfonic acid aluminum water solution.
(4). methyl disulfonic acid aluminum water solution is concentrated, dries, pulverizes, promptly obtain methyl disulfonic acid aluminium finished product of the present invention.
Claims (2)
1. one kind is the processing method of feedstock production water-soluble methy-disulfonate by methylene dichloride and S-WAT, comprises operations such as sulfonation, bariumization, salt conversion, concentrate drying, it is characterized in that:
1) in the sulfonation operation, S-WAT is mixed with the aqueous solution earlier, reacts with methylene dichloride in reactor, and temperature of reaction 160-200 ℃, pressure is 0.80-1.2MPa;
2) in barium chemical industry preface, the feed liquid that bariumchloride and sulfonation operation are sent here is reacted in the barium still, generates methyl disulfonic acid precipitated barium, by filtering it is separated with sodium chloride solution;
3) at the salt conversion procedure, the methyl disulfonic acid barium that water-soluble zinc sulfate (aluminium, magnesium) and barium chemical industry preface obtain carries out the salt conversion reaction in reactor, temperature of reaction≤100 ℃, and reaction pressure is a normal pressure; Reaction is isolated throw out barium sulfate with filter after ending, and filtrate is sent into next process;
4), the filtrate that the salt conversion procedure obtains is carried out evaporation concentration, when feed temperature rises to 110-120 ℃ in the concentrate drying operation, stop heating, cooling makes it spontaneous nucleation then, and crystallized stock carries out drying again, and dried methyl disulfonic acid zinc (aluminium, magnesium) is crushed to powdery.
2. according to the processing method of the described preparation water-soluble methy-disulfonate of claim 1, it is characterized in that:
1) sulfonation operation, sodium sulfite aqueous solution concentration are 100-260g/l, S-WAT/methylene dichloride=2.05-2.4 (mol ratio):
2) barium chemical industry preface, bariumchloride/methyl sodium disulfonate=1.05-1.4 (mol ratio), barium chloride solution concentration 200-300g/l;
3) salt conversion procedure, vitriol/methyl disulfonic acid barium=0.8-0.9 (mol ratio).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95101622A CN1054371C (en) | 1995-02-17 | 1995-02-17 | Technical process for preparation of water-soluble methy-disulfonate |
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| CN95101622A CN1054371C (en) | 1995-02-17 | 1995-02-17 | Technical process for preparation of water-soluble methy-disulfonate |
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| CN1129213A true CN1129213A (en) | 1996-08-21 |
| CN1054371C CN1054371C (en) | 2000-07-12 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011066706A1 (en) * | 2009-12-03 | 2011-06-09 | 湖南阿斯达生化科技有限公司 | Non-halogen activating agent used as flux |
| CN102219654A (en) * | 2011-04-29 | 2011-10-19 | 南通德益化工有限公司 | Method for preparing ethylene glycol monopropyl ether |
| CN102887840A (en) * | 2011-07-23 | 2013-01-23 | 联化科技股份有限公司 | Method for preparing low-water-content solid methyl disulfonic acid through taking methylene chloride as raw material |
| CN103086929A (en) * | 2013-02-04 | 2013-05-08 | 合肥艾普拉斯环保科技有限公司 | Solid acrylamidealkyl sulfonate preparation method |
| CN104487417A (en) * | 2012-09-28 | 2015-04-01 | 湖南阿斯达生化科技有限公司 | Method for preparing methanedisulfonic acid |
| CN106748907A (en) * | 2017-01-18 | 2017-05-31 | 湖北星火化工有限公司 | A kind of method of purification of pyrovinic acid |
| CN106866465A (en) * | 2017-01-20 | 2017-06-20 | 中卫市创科知识产权投资有限公司 | A kind of high-purity sodium methanedisulfonate production technology |
| WO2022017286A1 (en) * | 2020-07-23 | 2022-01-27 | 浙江皇马科技股份有限公司 | Preparation method and system for ethylene glycol monopropyl ether |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN169052B (en) * | 1987-06-01 | 1991-08-24 | Pennwalt Corp |
-
1995
- 1995-02-17 CN CN95101622A patent/CN1054371C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011066706A1 (en) * | 2009-12-03 | 2011-06-09 | 湖南阿斯达生化科技有限公司 | Non-halogen activating agent used as flux |
| US8853417B2 (en) | 2009-12-03 | 2014-10-07 | Hunan Astar Biotechnology Ltd. | Non-halogen activating agent used as flux |
| CN102219654A (en) * | 2011-04-29 | 2011-10-19 | 南通德益化工有限公司 | Method for preparing ethylene glycol monopropyl ether |
| CN102887840A (en) * | 2011-07-23 | 2013-01-23 | 联化科技股份有限公司 | Method for preparing low-water-content solid methyl disulfonic acid through taking methylene chloride as raw material |
| CN102887840B (en) * | 2011-07-23 | 2015-04-22 | 联化科技股份有限公司 | Method for preparing low-water-content solid methyl disulfonic acid through taking methylene chloride as raw material |
| US9440915B2 (en) | 2012-09-28 | 2016-09-13 | Hunan Astar Bio-Chemical Technology Co., Ltd. | Method for preparing methanedisulfonic acid |
| CN104487417B (en) * | 2012-09-28 | 2018-06-01 | 湖南阿斯达生化科技有限公司 | A kind of preparation method of methylene-disulfonic acid |
| CN104487417A (en) * | 2012-09-28 | 2015-04-01 | 湖南阿斯达生化科技有限公司 | Method for preparing methanedisulfonic acid |
| CN103086929A (en) * | 2013-02-04 | 2013-05-08 | 合肥艾普拉斯环保科技有限公司 | Solid acrylamidealkyl sulfonate preparation method |
| CN103086929B (en) * | 2013-02-04 | 2014-11-05 | 梅龙毅 | Solid acrylamidealkyl sulfonate preparation method |
| CN106748907A (en) * | 2017-01-18 | 2017-05-31 | 湖北星火化工有限公司 | A kind of method of purification of pyrovinic acid |
| CN106866465A (en) * | 2017-01-20 | 2017-06-20 | 中卫市创科知识产权投资有限公司 | A kind of high-purity sodium methanedisulfonate production technology |
| WO2022017286A1 (en) * | 2020-07-23 | 2022-01-27 | 浙江皇马科技股份有限公司 | Preparation method and system for ethylene glycol monopropyl ether |
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|---|---|
| CN1054371C (en) | 2000-07-12 |
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