CN101219980A - Method for extraction separation of phenyl-sulfhydrate compounds - Google Patents
Method for extraction separation of phenyl-sulfhydrate compounds Download PDFInfo
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- CN101219980A CN101219980A CNA2008100593177A CN200810059317A CN101219980A CN 101219980 A CN101219980 A CN 101219980A CN A2008100593177 A CNA2008100593177 A CN A2008100593177A CN 200810059317 A CN200810059317 A CN 200810059317A CN 101219980 A CN101219980 A CN 101219980A
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Abstract
The invention discloses a method for separating thiophenol compounds from an aqueous liquor of thiophenol compounds. The method adopts an amides ionic liquid listed in formula (I) as an extraction agent. In format (I), R<1> and R <2> are separated as the amide of C1 to C 10 or the alkyl of C1 to C 10, and L<-> is one of the followings: BF4<->, PF6<->, OAC<->, CF3SO3<-> or N(SO2CF3)2<->. The thiophenol compounds are a thiophenol and/or a substituted thiophenol, and the substituent of the substituted thiophenol can be a halogen, a hydroxyl, a methyl, an ethyl, a hepatitis, a propyl, an isopropyl, an amino, methoxy group, ethoxy group, aldehyde group, carboxy group etc. The method for separating thiophenol compounds from an aqueous liquor of thiophenol compounds adopts the amides ionic liquid as an extraction agent, and realizes the separation of the thiophenol compounds. Besides, the extraction agent can be reused safely and stably and has no pollution to the environment; the invention is an economical and practical environment-protection technique.
Description
(1) technical field
The present invention relates to a kind of from the aqueous solution of phenyl-sulfhydrate compounds the method for extraction separation of phenyl-sulfhydrate compounds.
(2) background technology
Thiophenol is important chemical material and organic synthesis intermediate, can be widely used in the reductive agent of synthetic and Polymer Synthesizing raw material, aluminium alloy inhibiter, heavy metal ion complexing analytical reagent, sensitive materials of medicine and dyestuff and stopper etc.Along with developing rapidly of chemical industry, the isolation and purification method of research and development phenyl-sulfhydrate compounds has certain application prospect.
It is a kind of effective separation method that liquid-liquid extraction separates, and range of application is very extensive.The solvent that this method adopts benzene generally commonly used, light oil, N-BUTYL ACETATE, methyl iso-butyl ketone (MIBK), isopropyl ether, tributyl phosphate, N, extraction agents such as N one or two (1 monomethyl heptyl) ethanamide.Only paid attention to the extraction agent effect of extracting in the extracting operation process in the past, environmental factors is considered less, this caused the organic solvent high volatility that uses, toxicity big, to variety of issues such as environmental hazard are serious.In recent years, we just are being devoted to the research of Green Chemistry and clearer production technology, and in the present invention, we select green solvent, eliminate the shortcoming the extraction process in the past from the source, and whole process is become environmental protection technology.
The more traditional fluent meterial of ionic liquid is compared, and ionic liquid has following advantage:
1. almost there is not vapour pressure, not volatile, thus in use can not cause very big pollution to environment; 2. has bigger equilibrium temperature scope (100～200 ℃) and better chemical stability; 3. can regulate its solvability by the design of zwitterion, and its acidity can transfer to hyper acidic, therefore can construct functionalized ion liquid by certain anionic unitized design to inorganics, water, organism and polymkeric substance.In extraction separation process, during with the ion liquid abstraction volatile organic matter, because of ionic liquid does not have vapour pressure, Heat stability is good, ionic liquid was easy to recycle after extraction was finished.
The scholar of the U.S. utilizes ionic liquid to carry out extraction research the earliest, and they are with hydrophobic ionic liquid [bmim] [PF
6] derivative of benzene extraction such as toluene, aniline, phenylformic acid, chlorobenzene etc. from water, and studied the partition ratio of various extracts in ionic liquid.With organic substance in the ion liquid abstraction aqueous solution, show some character similar with other extraction agent.And discovery [bmim] [PF
6] derivative of benzene extraction such as toluene, aniline, phenylformic acid, chlorobenzene etc. from water, solute partition ratio in ionic liquid/water two-phase system has linear relationship substantially with partition ratio at the octanol/water two-phase system.But, the application ionic liquid is ion liquid loss from the difficulty of aqueous solution extraction organism maximum at present, no matter how little the solubleness of ionic liquid in water is, extraction process all can cause a part of ionic liquid to enter into aqueous phase, because ion liquid high price and make its extraction process at present can't large-scale industrial application to the unknown toxicity of environment.
Therefore, in the present invention, utilize the amides ionic liquid to study the method that from the aqueous solution of phenyl-sulfhydrate compounds, extracts phenyl-sulfhydrate compounds, also provide effective means simultaneously for handling thiophenol waste water as extraction agent.This is a Green Chemical Technology, has not yet to see report.
(3) summary of the invention
The technical problem to be solved in the present invention provide a kind of with the amides ionic liquid as extraction agent, from the aqueous solution of phenyl-sulfhydrate compounds the extraction phenyl-sulfhydrate compounds method, reach separation and purification and the protection environment purpose.
The technical solution used in the present invention is as follows: use the amides ionic liquid as extraction agent, and the method for extraction phenyl-sulfhydrate compounds from the aqueous solution of phenyl-sulfhydrate compounds, used amides ionic liquid is suc as formula shown in (I):
In the formula (I), R
1, R
2Independent separately is the amide group of C1～C10 or the alkyl of C1～C10; L
-For one of following: BF
4 -, PF
6 -, OA
C -, CF
3SO
3 -, N (SO
2CF
3)
2 -
The aqueous solution of phenyl-sulfhydrate compounds of the present invention is meant the aqueous solution that contains phenyl-sulfhydrate compounds, the content of phenyl-sulfhydrate compounds has no special requirements in the aqueous solution of described phenyl-sulfhydrate compounds, be generally 1～20mg/mL, this concentration helps the extraction of the inventive method to phenyl-sulfhydrate compounds.
Described phenyl-sulfhydrate compounds is thiophenol and/or substituted benzene thiophenol, and the substituting group of described substituted benzene thiophenol can be halogen, hydroxyl, methyl, ethyl, propyl group, sec.-propyl, amino, methoxyl group, oxyethyl group, aldehyde radical, carboxyl etc.
Preferably, described amides ionic liquid is imidazoles a tetrafluoro borate or imidazoles hexafluorophosphate, more preferably imidazoles hexafluorophosphate.
The mass ratio of the amides ionic liquid of the present invention and the phenyl-sulfhydrate compounds aqueous solution is recommended as 1～20: 1, preferred 1～10: 1.
Concrete, described method can be according to following operation: in reaction vessel, add mass ratio and be 1～10: 1 the amides ionic liquid and the aqueous solution of phenyl-sulfhydrate compounds, be 1～9 at pH, temperature is under 10～150 ℃ of conditions, stir extraction down 0.5～50 hour, standing demix is isolated the organic phase that contains phenyl-sulfhydrate compounds.Content with gas chromatographic analysis extraction back aqueous phase phenyl-sulfhydrate compounds calculates the content that extracts phenyl-sulfhydrate compounds in the organic phase of back with minusing, calculates percentage extraction.
In the present invention, can also add salting-out agent in reaction vessel extracts again.Described salting-out agent are recommended as ammonium chloride, sodium-chlor or sodium sulfate.Among the present invention, salting-out agent can add to saturated, also can not add to saturated because can there be the composition of inorganic salt in the aqueous solution of phenyl-sulfhydrate compounds when adjust pH.
Further, among the present invention, the pH of extraction liquid is preferably 5～6; Preferred 20～30 ℃ of extraction temperature; Preferred 1～5 hour of extraction time.
The present invention is used for the amides ionic liquid extraction of phenyl-sulfhydrate compounds as extraction agent, its beneficial effect mainly is to have invented the separation that the hydrogen bond action that utilizes the agent of amides ion liquid abstraction is used for phenyl-sulfhydrate compounds, a kind of method of separation of phenyl-sulfhydrate compounds also is provided, and extraction agent can recycle, safety and stability, environmentally safe is economical and practical green technology.
(4) embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Set in the embodiment of the invention that phenyl-sulfhydrate compounds content is 5mg/mL in the phenyl-sulfhydrate compounds aqueous solution.
Embodiment 1
10 milliliters of the aqueous solution (5mg/mL) that will contain the thiophenol compound, 500 milligrams of 1-methyl-3-propionamido-imidazoles hexafluorophosphate, be placed in 100 milliliters of reaction flasks, under the condition of pH=5 and 10 ℃, stirred on magnetic stirring apparatus 1 hour, organic phase and aqueous phase separation then are behind the aqueous phase phenol content of gas chromatographic analysis extraction back, with thiophenol content in the organic phase of minusing calculating extraction back is 46mg, and percentage extraction is 92%.
Embodiment 2
To contain 10 milliliters of the aqueous solution (5mg/mL) of chlorothio-phenol compound, 50 milligrams of 1-methyl-3-propionamido-imidazoles hexafluorophosphate, be placed in 100 milliliters of reaction flasks, under the condition of pH=5 and 150 ℃, on magnetic stirring apparatus, stirred 50 hours, organic phase and aqueous phase separation then, with gas chromatographic analysis extraction back aqueous phase to chlorothio-phenol content after, calculating in the organic phase of extraction back chlorothio-phenol content with minusing is 21mg, and percentage extraction is 42%.
Embodiment 3
10 milliliters of the aqueous solution (5mg/mL) that will contain the cumic aldehyde thiol compounds, 1000 milligrams of 1-acetamidos-3-hexanoyl amido imidazoles hexafluorophosphate, be placed in 250 milliliters of reaction flasks, under the condition of pH=9 and 50 ℃, stirred on magnetic stirring apparatus 0.5 hour, organic phase and aqueous phase separation then are behind the aqueous phase p-isopropyl thiophenol content of gas chromatographic analysis extraction back, with p-isopropyl thiophenol content in the organic phase of minusing calculating extraction back is 45mg, and percentage extraction is 90%.
Embodiment 4
10 milliliters of the aqueous solution (5mg/mL) that will contain a carboxyl thiophenol compound, 500 milligrams of 1-hexanoyl amidos-3-decoyl amido imidazoleacetic acid salt, be placed in 250 milliliters of reaction flasks, under the condition of pH=1 and 100 ℃, stirred on magnetic stirring apparatus 10 hours, organic phase and aqueous phase separation then are behind carboxyl thiophenol content between the aqueous phase of gas chromatographic analysis extraction back, calculating the middle carboxyl thiophenol of extraction back organic phase content with minusing is 48mg, and percentage extraction is 96%.
Embodiment 5
10 milliliters of the aqueous solution (5mg/mL) that will contain the near amino thiophenols compound, 1,100 milligrams of 3-two-hexanoyl amido tetrafluoroborates, be placed in 250 milliliters of reaction flasks, under the condition of pH=6 and 30 ℃, on magnetic stirring apparatus, stirred 10 hours, organic phase and aqueous phase separation then, behind the aqueous phase near amino thiophenols content of gas chromatographic analysis extraction back, be 44mg with near amino thiophenols content in the organic phase of minusing calculating extraction back, percentage extraction is 88%.
Embodiment 6
10 milliliters of the aqueous solution (5mg/mL) that will contain the near amino thiophenols compound, after the recovery 1,100 milligrams of 3-two-hexanoyl amido tetrafluoroborates, be placed in 250 milliliters of reaction flasks, under the condition of pH=6 and 30 ℃, on magnetic stirring apparatus, stirred 10 hours, organic phase and aqueous phase separation then, behind the aqueous phase near amino thiophenols content of gas chromatographic analysis extraction back, be 44mg with near amino thiophenols content in the organic phase of minusing calculating extraction back, percentage extraction is 88%.
Embodiment 7
To contain 10 milliliters of the aqueous solution (5mg/mL) of methylbenzene thiol compounds, 150 milligrams of 1-hexanoyl amidos-3-caprinoyl amido imidazoles hexafluorophosphate, be placed in 250 milliliters of reaction flasks, under the condition of pH=6 and 20 ℃, on magnetic stirring apparatus, stirred 5 hours, organic phase and aqueous phase separation then, with gas chromatographic analysis extraction back aqueous phase to methylbenzene thiophenol content after, calculating in the organic phase of extraction back methylbenzene thiophenol content with minusing is 45mg, and percentage extraction is 90%.
Embodiment 8
To contain 10 milliliters of aqueous solution of fluoro thiophenol compound (5mg/mL), 250 milligrams of 1-hexanoyl amidos-3-caprinoyl amido imidazoles hexafluorophosphate, ammonium chloride 15mg, be placed in 250 milliliters of reaction flasks, under the condition of pH=6 and 20 ℃, on magnetic stirring apparatus, stirred 5 hours, organic phase and aqueous phase separation then, behind fluoro thiophenol content between the aqueous phase of gas chromatographic analysis extraction back, be 47mg with fluoro thiophenol content in the middle of the organic phase of minusing calculating extraction back, percentage extraction is 94%.
Embodiment 9
10 milliliters of the aqueous solution (5mg/mL) that will contain the thiohydroquinone compound, 150 milligrams of 1-hexanoyl amidos-3-caprinoyl amido imidazoles hexafluorophosphate, sodium-chlor 15mg, be placed in 250 milliliters of reaction flasks, under the condition of pH=6 and 50 ℃, on magnetic stirring apparatus, stirred 3 hours, organic phase and aqueous phase separation then, behind the aqueous phase thiohydroquinone content of gas chromatographic analysis extraction back, be 48mg with thiohydroquinone content in the organic phase of minusing calculating extraction back, percentage extraction is 96%.
Embodiment 10
To contain 10 milliliters of the aqueous solution (5mg/mL) of aldehyde radical thiophenol compound, 150 milligrams of 1-hexanoyl amidos-3-caprinoyl amido imidazoles hexafluorophosphate, sodium sulfate 15mg, be placed in 250 milliliters of reaction flasks, under the condition of pH=6 and 10 ℃, on magnetic stirring apparatus, stirred 10 hours, organic phase and aqueous phase separation then, with gas chromatographic analysis extraction back aqueous phase to aldehyde radical thiophenol content after, calculating in the organic phase of extraction back aldehyde radical thiophenol content with minusing is 48mg, percentage extraction is 96%.
Claims (10)
1. the method for an extraction separation of phenyl-sulfhydrate compounds is characterized in that described method is to be extraction agent suc as formula the amides ionic liquid shown in (I), extracts phenyl-sulfhydrate compounds from the aqueous solution of phenyl-sulfhydrate compounds;
In the formula (I), R
1, R
2Independent separately is the amide group of C1～C10 or the alkyl of C1～C10, L
-For one of following: BF
4 -, PF
6 -, OA
C -, CF
3SO
3 -, N (SO
2CF
3)
2 -Described phenyl-sulfhydrate compounds is thiophenol and/or substituted benzene thiophenol, and the substituting group of described substituted benzene thiophenol is halogen, hydroxyl, methyl, ethyl, propyl group, sec.-propyl, amino, methoxyl group, oxyethyl group, aldehyde radical or carboxyl.
2. the method for claim 1 is characterized in that described amides ionic liquid is imidazoles a tetrafluoro borate or imidazoles hexafluorophosphate.
3. method as claimed in claim 2 is characterized in that described amides ionic liquid is the imidazoles hexafluorophosphate.
4. the method for claim 1, the mass ratio that it is characterized in that the described amides ionic liquid and the phenyl-sulfhydrate compounds aqueous solution is 1～20: 1.
5. the method for claim 1, it is characterized in that described method carries out according to following steps: in reaction vessel, the adding mass ratio is 1～10: 1 the amides ionic liquid and the phenyl-sulfhydrate compounds aqueous solution, be 1～9 at pH, temperature is under 10～150 ℃ of conditions, stir extraction down 0.5～50 hour, standing demix is isolated the organic phase that contains phenyl-sulfhydrate compounds.
6. method as claimed in claim 5 is characterized in that also adding salting-out agent and extracts in reaction vessel.
7. method as claimed in claim 6 is characterized in that described salting-out agent are ammonium chloride, sodium-chlor or sodium sulfate.
8. method as claimed in claim 5 is characterized in that described extraction temperature is 20～30 ℃, and the extraction time is 1～5 hour.
9. method as claimed in claim 5, the pH that it is characterized in that described extraction liquid is 5～6.
10. the method for claim 1 is characterized in that the content of phenyl-sulfhydrate compounds in the aqueous solution of described phenyl-sulfhydrate compounds is 1～20mg/mL.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863477A (en) * | 2012-09-07 | 2013-01-09 | 浙江工业大学 | Method for extracting plant polyphenol from walnut shells by using ionic liquid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863477A (en) * | 2012-09-07 | 2013-01-09 | 浙江工业大学 | Method for extracting plant polyphenol from walnut shells by using ionic liquid |
| CN102863477B (en) * | 2012-09-07 | 2015-03-04 | 浙江工业大学 | Method for extracting plant polyphenol from walnut shells by using ionic liquid |
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