CN107954975A - A kind of processing method of 1,3- propane sultones distillation still raffinate - Google Patents
A kind of processing method of 1,3- propane sultones distillation still raffinate Download PDFInfo
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- CN107954975A CN107954975A CN201711407979.4A CN201711407979A CN107954975A CN 107954975 A CN107954975 A CN 107954975A CN 201711407979 A CN201711407979 A CN 201711407979A CN 107954975 A CN107954975 A CN 107954975A
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- distillation still
- propane
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- distillation
- hydroxypropanesulfonic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/04—Five-membered rings
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Abstract
The invention discloses a kind of processing method of 1,3 propane sultone distillation still raffinates, comprise the following steps：S1, saponification：Strong base solution is added into reaction kettle, simultaneously 1,3 propane sultones and temperature rising reflux reaction is added dropwise in heating water bath while stirring, up to saponification is completed；S2, condensing crystallizing：1, the 3 propane sultone distillation still raffinates vacuum distillation that step S1 is completed to hydrolysis process is condensed into solid, up to 3 hydroxypropanesulfonic acid alkali metal salts；S3, acidifying are free：The 3 hydroxypropanesulfonic acid alkali metal salts obtained to step S2 condensing crystallizings add inorganic acid, are uniformly mixed standing, separation liquid obtains 3 hydroxypropanesulfonic acids after vacuum distillation water removal.The present invention provides a kind of processing method of 1,3 propane sultone distillation still raffinates, and environmental protection treatment cost is low, and recovery utilization rate is high, and processing step is simple, and processing is quick.
Description
Technical field
The present invention relates to the field of waste liquid treatment of battery electrolyte, especially one kind 1,3- propane sultone distillation still residues
The processing of liquid, the method for preparing byproduct 3- hydroxypropanesulfonic acids sodium and 3- hydroxypropanesulfonic acids.
Background technology
1,3- propane sultones are a kind of widely used lithium-ion battery electrolytes additives.Contribute to SEI films
Formed, the cycle performance of lithium ion battery can be improved and lift the security of battery.
The prior art 1, the preparation method of 3- propane sultones is using 3- hydroxypropanesulfonic acids dehydration esterification cyclization, to production
The purification process of product mainly distills repeatedly.Produced when especially rectifying prepares high-purity electron level 1,3- propane sultones black
The slightly sticky 1,3- propane sultone distillation still raffinates of brown.The main component of the waste liquid be propane sulfonic acid oligoesters simultaneously
Graininess mechanical admixture containing tarry and carbonization, general processing mode, which is that committee is outer, burns, but due to its sulfur content
Height, burning a large amount of oxysulfides of generation increases the intractability of incineration tail gas, and environmental protection treatment is of high cost.
For above-mentioned technical problem, there is provided a kind of environmental protection treatment cost is low, in high 1, the 3- propane sulfonic acids of recovery utilization rate
The processing method of ester distillation still raffinate is technical problem in the urgent need to address at present.
The content of the invention
The technical problem to be solved is that the 1,3- propane sultones distillation produced for the prior art for the invention
Kettle raffinate environmental protection treatment is of high cost, and recovery utilization rate is low, propose one kind to 1,3- propane sultone distillation still raffinates at
Reason, the method for converting recycling.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：A kind of 1,3- propane sultones distillation still raffinate
Processing method, the treating method comprises following steps：
S1, saponification：Strong base solution is added into reaction kettle, it is 40 DEG C~80 DEG C that heating water bath, which controls strong base solution temperature,
1,3- propane sultone distillation still Liquid Residues are added dropwise while stirring, reflux temperature and back flow reaction 4 are warming up to after being added dropwise to complete
~12 it is small when, up to complete hydrolysis process 1,3- propane sultone distillation still raffinates；Heating water bath can be controlled preferably by force
Aqueous slkali temperature, guarantee, which is heated evenly, avoids local temperature too high or too low, if strong base solution temperature can cause water less than 40 DEG C
Solution is incomplete, if strong base solution temperature can cause material colourity significantly raised higher than 80 DEG C, and high-temperature heating can accelerate solvent
Loss is so as to influence mixing effect；Be added dropwise to complete the rear temperature rising reflux reaction time it is small less than 4 when hydrolysis can be caused incomplete, reaction
Time be more than 12 it is small when can caused by heating time is long material colourity it is significantly raised, and solvent loss influence mixing effect.
S2, condensing crystallizing：The 1,3- propane sultone distillation stills raffinate that step S1 is completed to hydrolysis process is evaporated under reduced pressure
Solid is condensed into, up to 3- hydroxypropanesulfonic acid alkali metal salts；Solvent can effectively be removed using vacuum distillation, form 3- hydroxyls third
Alkyl sulfonic acid alkali metal salt solid.
S3, acidifying are free：The 3- hydroxypropanesulfonic acids alkali metal salt obtained to step S2 condensing crystallizings adds inorganic acid,
Be uniformly mixed standing 2~5 it is small when, vacuum distillation water removal after separation liquid obtain 3- hydroxypropanesulfonic acids.By to 3- hydroxyls
Base propane sulfonic acid alkali metal salt adds inorganic acid by 3- hydroxypropanesulfonic acid separate outs, and it is small to be uniformly mixed rear time of repose
When 2 is small then can not by 3- hydroxypropanesulfonic acid separate outs, time of repose be more than 5 it is small when then reduce treatment effeciency, and pass through
The free impurity that can further remove 3- hydroxypropanesulfonic acids of acidifying, improves purity.
Further, the step S1 strong base solutions are dissolved in alcoholic solution by sodium hydroxide or potassium hydroxide is made, institute
It is water and alcohols by 1 to state alcoholic solution:1~1:50 ratio is mixed, and the strong base solution concentration is 10%~35%.Due to 1,
3- propane sultones are insoluble in water, and alcoholic solution can improve its solubility, ensure abundant saponification, if but alcohol institute in alcoholic solution
The excessive product that also results in of accounting example largely separates out, and influences reaction process stirring and later separation, and strong base solution concentration is less than 10%
Then the concentration ratio ester bond concentration of alkali is low causes reaction rate slow, and strong base solution concentration adds reaction treatment cost higher than 35%.
Yet further, the alcohols is any one in methanol, ethanol, propyl alcohol, the tert-butyl alcohol.Methanol, ethanol, propyl alcohol and
The low boiling point of the tert-butyl alcohol, and it is soluble easily in water, solvent is easily distilled off.
Yet further, the reflux temperature of the step S1 is 64 DEG C~98 DEG C.Reflux temperature less than 64 DEG C then solvent without
Method evaporates the effect for not reaching back flow reaction, and reflux temperature then accelerates evaporation of the solvent to reduce quantity of solvent higher than 98 DEG C reduces by 1,3- third
The meltage of sultone causes reflux incomplete, and temperature is excessive that material colourity can be caused significantly raised.
Yet further, the inorganic acid that the step S3 is added is any one in hydrochloric acid, sulfuric acid and nitric acid.Add
Acid strong inorganic acid can dissociate 3- hydroxypropanesulfonic acid alkali metal salts to obtain the 3- hydroxyls available for 1,3- propane sultones
Base propane sulfonic acid.
Yet further, the step S3 adds the molal quantity of inorganic acid and mole of 3- hydroxypropanesulfonic acid alkali metal salts
Number is than being 1:1.The mole ratio of the molal quantity and 3- hydroxypropanesulfonic acid alkali metal salts that add inorganic acid is 1:1 can ensure 3- hydroxyls
Base propane sulfonic acid alkali metal salt dissociates for 3- hydroxypropanesulfonic acids completely.
Compared with prior art, the advantageous effects of the invention：
Firstth, environmental protection treatment cost is low.It is slightly viscous that rectifying produces dark brown when preparing high-purity electron level 1,3- propane sultones
Thick 1,3- propane sultone distillation still raffinates.The main component at the residual night is propane sulfonic acid oligoesters and contains tar
Shape and the graininess mechanical admixture of carbonization, general processing mode, which is that committee is outer, burns, but since its sulfur content is high, burns production
Raw a large amount of oxysulfides increase the intractability of incineration tail gas, and environmental protection treatment is of high cost.The present invention is in 1,3- propane sulfonic acids
The processing step of ester distillation still raffinate includes saponification, condensing crystallizing and free three steps of acidifying, and processing step is simple and need not
Add special reagent and participate in reaction, processing cost is low and obtained product be 3- hydroxypropanesulfonic acids, available for preparation 1,3-
Propane sultone, reduces waste discharge, and whole processing procedure non-secondary pollution thing generation, environmental protection treatment cost are low.
Secondth, recovery utilization rate is high.1,3- propane sultone distillation stills raffinate is carried out the present invention by the present invention successively
Saponification, condensing crystallizing and free hydrolyze 1,3- propane sultones of acidifying generate 3- hydroxypropanesulfonic acids, maimed liquid warp
It can be recycled substantially after processing and be used to prepare 1,3- propane sultones, the rate of recovery reaches more than 80%..
3rd, processing step is simple, and processing is quick.The present invention by being by saponification, condensing crystallizing and free three steps of acidifying
The processing of 1,3- propane sultone distillation still raffinates can be completed, processing step is simple, and each step reaction time is short, waste liquid
Processing is quick, can be set with production lines matching, the 3- hydroxypropanesulfonic acids handled be re-used as raw material be used for synthesize 1,3- third
Sultone.
Embodiment
Technical scheme is more fully understood for ease of those skilled in the art, in conjunction with embodiment to this
Invention is described further.
Embodiment 1
S1, saponification：The potassium hydroxide solution that concentration is 10% is added into reaction kettle, the potassium hydroxide solution is hydrogen-oxygen
Change potassium, which is dissolved in methanol solution, to be prepared, and the methanol solution presses 1 for water and methanol:25 ratio is mixed, water-bath
Computer heating control potassium hydroxide solution temperature is 40 DEG C, and 1,3- propane sultone distillation still Liquid Residues are added dropwise while stirring, is added dropwise
After the completion of be warming up to reflux temperature for 65 DEG C and back flow reaction 4 it is small when, up to complete hydrolysis process 1,3- propane sultones
Distillation still Liquid Residue；
S2, condensing crystallizing：The 1,3- propane sultone distillation stills Liquid Residue vacuum distillation that step S1 is completed to hydrolysis process is dense
Solid is shortened into, up to 3- hydroxypropanesulfonic acid sylvite；
S3, acidifying are free：The 3- hydroxypropanesulfonic acids sylvite obtained to step S2 condensing crystallizings adds hydrochloric acid, and the addition of hydrochloric acid rubs
The mole ratio of that number and 3- hydroxypropanesulfonic acid sylvite is 1:1, be uniformly mixed standing 5 it is small when, vacuum distillation water removal after
Separation liquid, which is acidified to dissociate, obtains 3- hydroxypropanesulfonic acids.
Embodiment 2
S1, saponification：The sodium hydroxide solution that concentration is 15% is added into reaction kettle, the sodium hydroxide solution is hydrogen-oxygen
Change sodium, which is dissolved in ethanol solution, to be prepared, and the ethanol solution presses 1 for water and ethanol:1 ratio is mixed, and water-bath adds
Thermal control sodium hydroxide solution temperature is 50 DEG C, and 1,3- propane sultone distillation still Liquid Residues are added dropwise while stirring, drip
Be warming up to after reflux temperature for 78 DEG C and back flow reaction 8 it is small when, up to complete hydrolysis process 1,3- propane sultones steam
Evaporate kettle Liquid Residue；
S2, condensing crystallizing：The 1,3- propane sultone distillation stills Liquid Residue vacuum distillation that step S1 is completed to hydrolysis process is dense
Solid is shortened into, up to 3- hydroxypropanesulfonic acid sodium salts；
S3, acidifying are free：The 3- hydroxypropanesulfonic acids sodium salt obtained to step S2 condensing crystallizings adds hydrochloric acid, and the addition of hydrochloric acid rubs
The mole ratio of that number and 3- hydroxypropanesulfonic acid sodium salts is 1:1, be uniformly mixed standing 3 it is small when, vacuum distillation water removal after
Separation liquid, which is acidified to dissociate, obtains 3- hydroxypropanesulfonic acids.
Embodiment 3
S1, saponification：The sodium hydroxide solution that concentration is 25% is added into reaction kettle, the sodium hydroxide solution is hydrogen-oxygen
Change sodium, which is dissolved in t-butanol solution, to be prepared, and the t-butanol solution presses 1 for water and the tert-butyl alcohol:35 ratio mixing system
Into it is 60 DEG C that heating water bath, which controls sodium hydroxide solution temperature, and 1,3- propane sultones distillation still residual is added dropwise while stirring
Liquid, be warming up to after being added dropwise to complete reflux temperature for 80 DEG C and back flow reaction 10 it is small when, up to complete hydrolysis process 1,3- propane
Sultones distillation still Liquid Residue；
S2, condensing crystallizing：The 1,3- propane sultone distillation stills Liquid Residue vacuum distillation that step S1 is completed to hydrolysis process is dense
Solid is shortened into, up to 3- hydroxypropanesulfonic acid sodium salts；
S3, acidifying are free：The 3- hydroxypropanesulfonic acids sodium salt obtained to step S2 condensing crystallizings adds sulfuric acid, and the addition of sulfuric acid rubs
The mole ratio of that number and 3- hydroxypropanesulfonic acid alkali metal salts is 1:1, be uniformly mixed standing 4 it is small when, vacuum distillation removes
It is to be acidified to dissociate to obtain 3- hydroxypropanesulfonic acids that liquid is separated after water.
Embodiment 4
S1, saponification：The potassium hydroxide solution that concentration is 35% is added into reaction kettle, the potassium hydroxide solution is hydrogen-oxygen
Change potassium, which is dissolved in propanol solution, to be prepared, and the propanol solution presses 1 for water and propyl alcohol:50 ratio is mixed, water-bath
Computer heating control potassium hydroxide solution temperature is 60 DEG C, and 1,3- propane sultone distillation still Liquid Residues are added dropwise while stirring, is added dropwise
After the completion of be warming up to reflux temperature for 75 DEG C and back flow reaction 12 it is small when, up to complete hydrolysis process 1,3- propane sultones
Distillation still Liquid Residue；
S2, condensing crystallizing：The 1,3- propane sultone distillation stills raffinate that step S1 is completed to hydrolysis process is evaporated under reduced pressure concentration
Into solid, up to 3- hydroxypropanesulfonic acid sylvite；
S3, acidifying are free：The 3- hydroxypropanesulfonic acids sylvite obtained to step S2 condensing crystallizings adds nitric acid, and the addition of nitric acid rubs
The mole ratio of that number and 3- hydroxypropanesulfonic acid alkali metal salts is 1:1, be uniformly mixed standing 5 it is small when, vacuum distillation removes
It is to be acidified to dissociate to obtain 3- hydroxypropanesulfonic acids that liquid is separated after water.
The foregoing is only a preferred embodiment of the present invention, not makees limitation in any form to the present invention；It is all
The those of ordinary skill of the industry can swimmingly implement the present invention by described above；But all it is familiar with this professional technology people
Member without departing from the scope of the present invention, a little change, the modification made using disclosed above technology contents
It is equivalent embodiment of the invention with the equivalent variations of differentiation；Meanwhile all substantial technologicals according to the present invention are implemented to more than
Variation, modification and evolution of any equivalent variations for being made of example etc., still fall within technical scheme protection domain it
It is interior.
Claims (6)
1. one kind 1, the processing method of 3- propane sultone distillation still raffinates, it is characterised in that：The treating method comprises with
Lower step：
S1, saponification：Strong base solution is added into reaction kettle, it is 40 DEG C~80 DEG C that heating water bath, which controls strong base solution temperature,
1,3- propane sultone distillation still raffinates are added dropwise while stirring, be warming up to after being added dropwise to complete reflux temperature and back flow reaction 4~
12 it is small when, up to complete hydrolysis process 1,3- propane sultone distillation still raffinates；
S2, condensing crystallizing：The 1,3- propane sultone distillation stills Liquid Residue vacuum distillation that step S1 is completed to hydrolysis process is dense
Solid is shortened into, up to 3- hydroxypropanesulfonic acid alkali metal salts；
S3, acidifying are free：The 3- hydroxypropanesulfonic acids alkali metal salt obtained to step S2 condensing crystallizings adds inorganic acid, stirring
Be uniformly mixed stand 2~5 it is small when, vacuum distillation water removal after separation liquid obtain 3- hydroxypropanesulfonic acids.
2. the processing method of 1,3- propane sultones distillation still raffinate according to claim 1, it is characterised in that：It is described
Step S1 strong base solutions are dissolved in alcoholic solution by sodium hydroxide or potassium hydroxide and are made, and the alcoholic solution presses 1 for water and alcohols:
1~1:50 ratio is mixed, and the strong base solution concentration is 10%~35%.
3. the processing method of 1,3- propane sultones distillation still raffinate according to claim 2, it is characterised in that：It is described
Alcohols is methanol, any one in ethanol, propyl alcohol, the tert-butyl alcohol.
4. the processing method of 1,3- propane sultones distillation still raffinate according to claim 1, it is characterised in that：It is described
The reflux temperature of step S1 is 64 DEG C~98 DEG C.
5. the processing method of 1,3- propane sultones distillation still raffinate according to claim 1, it is characterised in that：It is described
The inorganic acid that step S3 is added is any one in hydrochloric acid, sulfuric acid and nitric acid.
6. the processing method of 1,3- propane sultones distillation still raffinate according to claim 1, it is characterised in that：It is described
The mole ratio of molal quantity and 3- hydroxypropanesulfonic acid alkali metal salts that step S3 adds inorganic acid is 1:1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483473A (en) * | 2019-09-08 | 2019-11-22 | 淮安瀚康新材料有限公司 | A kind of solvent-free method for preparing 1,3- propane sultone |
| CN114315656A (en) * | 2021-12-07 | 2022-04-12 | 常熟聚和化学有限公司 | Decomposition and recovery treatment method of propane sultone oligomer |
| CN115872973A (en) * | 2022-11-09 | 2023-03-31 | 贵州聚瑞新材料科技有限公司 | 5363 purification method of 1,3-propane sultone |
| CN116178335A (en) * | 2023-02-06 | 2023-05-30 | 常熟聚和化学有限公司 | Recovery method of residual liquid of 1, 3-propane sultone distillation still |
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| CN106146453A (en) * | 2016-07-26 | 2016-11-23 | 张家港瀚康化工有限公司 | The preparation method of 1,3 propane sultone |
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2017
- 2017-12-22 CN CN201711407979.4A patent/CN107954975A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106146453A (en) * | 2016-07-26 | 2016-11-23 | 张家港瀚康化工有限公司 | The preparation method of 1,3 propane sultone |
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| 林锦明: "《化学实验工作手册》", 31 January 2016, 第二军医大学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483473A (en) * | 2019-09-08 | 2019-11-22 | 淮安瀚康新材料有限公司 | A kind of solvent-free method for preparing 1,3- propane sultone |
| CN110483473B (en) * | 2019-09-08 | 2022-12-23 | 江苏瀚康新材料有限公司 | Method for preparing 1, 3-propane sultone |
| CN114315656A (en) * | 2021-12-07 | 2022-04-12 | 常熟聚和化学有限公司 | Decomposition and recovery treatment method of propane sultone oligomer |
| CN115872973A (en) * | 2022-11-09 | 2023-03-31 | 贵州聚瑞新材料科技有限公司 | 5363 purification method of 1,3-propane sultone |
| CN116178335A (en) * | 2023-02-06 | 2023-05-30 | 常熟聚和化学有限公司 | Recovery method of residual liquid of 1, 3-propane sultone distillation still |
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