CN101209957A - Method for separating phenols compounds from phenol-containing waste water - Google Patents
Method for separating phenols compounds from phenol-containing waste water Download PDFInfo
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- CN101209957A CN101209957A CNA2007101646139A CN200710164613A CN101209957A CN 101209957 A CN101209957 A CN 101209957A CN A2007101646139 A CNA2007101646139 A CN A2007101646139A CN 200710164613 A CN200710164613 A CN 200710164613A CN 101209957 A CN101209957 A CN 101209957A
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Abstract
The invention discloses a method for extracting phenolic compound from the waste water containing phenol. The method adopts ionic liquid of hydroxyanilides as extracting agent; the hydroxyanilides ionic liquid shows as formula (I). In the formula, R<1>, R<2> are respectively C1-C10 of amide group or C1-C10 of alkyl; L<-> is one of BF4<->, PF6<->, OAC<->, CF3SO3<->, N (SO2CF3) 2<->. The phenolic compound is phenol and/or substituted phenol; the substituent of the substituted phenol can be halogen, hydroxyl, methyl, ethyl, formylphenyl, carboxyl, etc. The invention adopts ionic liquid of hydroxyanilides as the extracting agent for extracting phenolic compound from waste water, so as to improve extraction effect, the ion liquid can be recycled; therefore, the invention is safe and stable and causes no pollution to environment; the invention is an practical environment friendly technology.
Description
Technical field
The present invention relates to the method for a kind of amides ionic liquid as extraction agent separating phenols compounds from phenolic wastewater.
Background technology
In recent years, China's chemical industry has obtained rapidly development, but the environment that the waste water of industrial discharge is but depended on for existence to us has brought and seriously influences and harm greatly.Human body is taken in a certain amount of phenolic wastewater can cause in various degree injury to human body.Therefore the regulation for phenolic wastewater is an important research contents.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-two (1 methylheptyl) ethanamide.But ketones solvent is water-soluble bigger, and tributyl phosphate is degraded easily, and degraded product can not perfect combustion etc.This shows that the standard of slective extraction agent was to weigh scale substantially with the 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 extracts phenolic compound in the phenolic wastewater as extraction agent, this is a Green Chemical Technology, has not yet to see report.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of with the method for amides ionic liquid as extraction agent separating phenols compounds from phenolic wastewater, reaches the purpose of protection environment.
The technical solution used in the present invention is as follows: a kind of use amides ionic liquid is as extraction agent, the method for separating phenols compounds from phenolic wastewater, and used amides ionic liquid is suc as formula shown in (I):
Wherein, R
1, R
2Independent separately is the amide group of C1～C10 or the alkyl of C1～C10; L
-For following it-: BF
4 -, PF
6 -, OA
C -, CF
3SO
3 -, N (SO
2CF
3)
2 -
Phenolic wastewater of the present invention refers to contain the waste water of phenolic compound.Described phenolic compound is phenol and/or fortified phenol, and the substituting group of fortified phenol can be halogen, hydroxyl, methyl, ethyl, 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 amides ionic liquid of the present invention and phenolic wastewater is recommended as 1～10: 1.
Concrete, described method can be according to following operation: in reaction vessel, the adding mass ratio is 1～10: 1 amides ionic liquid and phenolic wastewater, be 1～9 at pH, temperature is under 15～150 ℃ the condition, stir extraction down 0.5～50 hour, standing demix is after the separation organic phase, with the content of gas chromatographic analysis extraction back aqueous phase phenolic compound.
In the present invention, can also add salting-out agent in reaction vessel extracts again.Described salting-out agent are recommended as ammonium chloride or sodium-chlor.Among the present invention, salting-out agent can add to saturated, also can not add to saturated.
Further, among the present invention, the mass ratio preferred 1～10: 1 of described amides ionic liquid and phenolic wastewater; The pH of extraction liquid is preferably 5; Preferred 20～50 ℃ of extraction temperature; Preferred 1～5 hour of extraction time.
The present invention is used for the extraction of waste water phenolic compound with the amides ionic liquid as extraction agent, and its beneficial effect mainly is to have improved effect of extracting, and ionic liquid can recycle, safety and stability, and environmentally safe is economical and practical green technology.
Embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Content of phenolic compounds in the used phenolic wastewater of the embodiment of the invention is 0.5mg/mL.
Embodiment 1
30 milliliters of the waste water (0.5mg/mL) that will contain oxybenzene compound, 15 milligrams of 1-methyl-3-propionamido-imidazoles hexafluorophosphate, be placed in 50 milliliters of reaction flasks, under the condition of pH=5 and 15 ℃, stirred on magnetic stirring apparatus 30 minutes, organic phase and aqueous phase separation then are behind the aqueous phase phenol content of gas chromatographic analysis extraction back, calculate phenol concentration 0.11mg/mL in the organic phase of extraction back with minusing, percentage extraction is 22%.
Embodiment 2
30 milliliters of the waste water (0.5mg/mL) that will contain oxybenzene compound, 30 milligrams of 1-methyl-3-propionamido-imidazoles hexafluorophosphate, be placed in 50 milliliters of reaction flasks, under the condition of pH=5 and 150 ℃, 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, calculate phenol concentration 0.22mg/mL in the organic phase of extraction back with minusing, percentage extraction is 44%.
Embodiment 3
30 milliliters of the waste water (0.5mg/mL) that will contain oxybenzene compound, 30 milligrams of 1-acetamidos-3-hexanoyl amido imidazoles hexafluorophosphate, be placed in 50 milliliters of reaction flasks, under the condition of pH=9 and 50 ℃, stirred on magnetic stirring apparatus 50 hours, organic phase and aqueous phase separation then are behind the aqueous phase phenol content of gas chromatographic analysis extraction back, calculate phenol concentration 0.41mg/mL in the organic phase of extraction back with minusing, percentage extraction is 82%.
Embodiment 4
30 milliliters of the waste water (0.5mg/mL) that will contain oxybenzene compound, 30 milligrams of 1-hexanoyl amidos-3-decoyl amido imidazoles hexafluorophosphate, be placed in 50 milliliters of reaction flasks, under the condition of pH=6 and 100 ℃, stirred on magnetic stirring apparatus 10 hours, organic phase and aqueous phase separation then are behind the aqueous phase phenol content of gas chromatographic analysis extraction back, calculate phenol concentration 0.45mg/mL in the organic phase of extraction back with minusing, percentage extraction is 90%.
Embodiment 5
30 milliliters of the waste water (0.5mg/mL) that will contain oxybenzene compound, 1,30 milligrams of 3-two-hexanoyl amido tetrafluoroborates, be placed in 50 milliliters of reaction flasks, under the condition of pH=6 and 100 ℃, on magnetic stirring apparatus, stirred 10 hours, organic phase and aqueous phase separation then, behind the aqueous phase phenol content of gas chromatographic analysis extraction back, calculate phenol concentration 0.34mg/mL in the organic phase of extraction back with minusing, percentage extraction is 68%.
Embodiment 6
30 milliliters of the waste water (0.5mg/mL) that will contain oxybenzene compound, 30 milligrams of 1-hexanoyl amidos-3-caprinoyl amido imidazoles hexafluorophosphate, be placed in 50 milliliters of reaction flasks, under the condition of pH=6 and 100 ℃, stirred on magnetic stirring apparatus 10 hours, organic phase and aqueous phase separation then are behind the aqueous phase phenol content of gas chromatographic analysis extraction back, calculate phenol concentration 0.45mg/mL in the organic phase of extraction back with minusing, percentage extraction is 90%.
Embodiment 7
30 milliliters of the waste water (0.5mg/mL) that will contain 4-methylphenol compound, 30 milligrams of 1-hexanoyl amidos-3-caprinoyl amido imidazoles hexafluorophosphate, be placed in 50 milliliters of reaction flasks, under the condition of pH=6 and 100 ℃, stirred on magnetic stirring apparatus 10 hours, organic phase and aqueous phase separation then are behind the aqueous phase phenol content of gas chromatographic analysis extraction back, calculate phenol concentration 0.45mg/mL in the organic phase of extraction back with minusing, percentage extraction is 90%.
Embodiment 8
30 milliliters of the waste water (0.5mg/mL) that will contain 4-chlorophenol compound, 30 milligrams of 1-hexanoyl amidos-3-caprinoyl amido imidazoles hexafluorophosphate, ammonium chloride 15mg, be placed in 50 milliliters of reaction flasks, under the condition of pH=6 and 100 ℃, on magnetic stirring apparatus, stirred 10 hours, organic phase and aqueous phase separation then, behind the aqueous phase phenol content of gas chromatographic analysis extraction back, calculate phenol concentration 0.47mg/mL in the organic phase of extraction back with minusing, percentage extraction is 94%.
Embodiment 8
To contain 30 milliliters of the waste water (0.5mg/mL) of biphenol compound, 150 milligrams of 1-hexanoyl amidos-3-caprinoyl amido imidazoles hexafluorophosphate, ammonium chloride 15mg, be placed in 50 milliliters of reaction flasks, under the condition of pH=6 and 100 ℃, on magnetic stirring apparatus, stirred 10 hours, organic phase and aqueous phase separation then, behind the aqueous phase phenol content of gas chromatographic analysis extraction back, calculate phenol concentration 0.48mg/mL in the organic phase of extraction back with minusing, percentage extraction is 96%.
Embodiment 9
To contain 30 milliliters of the waste water (0.5mg/mL) of biphenol compound, 150 milligrams of 1-hexanoyl amidos-3-caprinoyl amido imidazoles hexafluorophosphate, sodium-chlor 15mg, be placed in 50 milliliters of reaction flasks, under the condition of pH=6 and 100 ℃, on magnetic stirring apparatus, stirred 10 hours, organic phase and aqueous phase separation then, behind the aqueous phase phenol content of gas chromatographic analysis extraction back, calculate phenol concentration 0.48mg/mL in the organic phase of extraction back with minusing, percentage extraction is 96%.
Embodiment 10
To contain 30 milliliters of the waste water (0.5mg/mL) of carboxylic phenol compound, 150 milligrams of 1-hexanoyl amidos-3-caprinoyl amido imidazoles hexafluorophosphate, sodium-chlor 15mg, be placed in 50 milliliters of reaction flasks, under the condition of pH=6 and 100 ℃, on magnetic stirring apparatus, stirred 10 hours, organic phase and aqueous phase separation then, behind the aqueous phase phenol content of gas chromatographic analysis extraction back, calculate phenol concentration 0.48mg/mL in the organic phase of extraction back with minusing, percentage extraction is 96%.
Claims (7)
1. the method for a separating phenols compounds from phenolic wastewater is characterized in that described method is, being extraction agent suc as formula the amides ionic liquid shown in (I), and separating phenols compounds from phenolic wastewater;
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 phenolic compound is phenol and/or fortified phenol, and the substituting group in the described fortified phenol is halogen, hydroxyl, methyl, ethyl, 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 described amides ionic liquid and phenolic wastewater is 1～10: 1.
5. method as claimed in claim 4, it is characterized in that described method is: in reaction vessel, the adding mass ratio is 1～10: 1 amides ionic liquid and phenolic wastewater, be 1～9 at pH, temperature is under 15～150 ℃ the condition, stir extraction down 0.5～50 hour, standing demix is after the separation organic phase, with the content of the aqueous phase phenolic compound after the gas chromatographic analysis analytical extraction.
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 or sodium-chlor.
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| CN2007101646139A CN101209957B (en) | 2007-12-25 | 2007-12-25 | Method for separating phenols compounds from phenol-containing waste water |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709035B (en) * | 2009-11-13 | 2012-10-17 | 北京化工大学 | Method for concentrating aniline from water solution |
| 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 |
| CN103304838A (en) * | 2013-06-06 | 2013-09-18 | 天津大学 | Extraction method for recycling and reusing waste liquid from production of polyaniline by electrochemical process |
| CN104946303A (en) * | 2015-05-18 | 2015-09-30 | 太原师范学院 | Method for selectively separating phenol mixture from oil |
| CN105152869A (en) * | 2015-07-29 | 2015-12-16 | 北京仁创科技集团有限公司 | Purification method for phenol in phenol-containing wastewater |
| CN108484367A (en) * | 2018-03-14 | 2018-09-04 | 江苏极易新材料有限公司 | A method of recycling 2,4- DI-tert-butylphenol compounds from 168 mother liquor of antioxidant |
| CN109503333A (en) * | 2018-12-04 | 2019-03-22 | 青岛科技大学 | A kind of liquid-liquid extraction-flash separation phenol and water method |
| CN109534546A (en) * | 2018-12-12 | 2019-03-29 | 江苏湖大化工科技有限公司 | A kind of processing method of phenol resin production waste water |
-
2007
- 2007-12-25 CN CN2007101646139A patent/CN101209957B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709035B (en) * | 2009-11-13 | 2012-10-17 | 北京化工大学 | Method for concentrating aniline from water solution |
| 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 |
| CN103304838A (en) * | 2013-06-06 | 2013-09-18 | 天津大学 | Extraction method for recycling and reusing waste liquid from production of polyaniline by electrochemical process |
| CN104946303A (en) * | 2015-05-18 | 2015-09-30 | 太原师范学院 | Method for selectively separating phenol mixture from oil |
| CN104946303B (en) * | 2015-05-18 | 2017-04-05 | 太原师范学院 | A kind of method of phenol mixture in Selective Separation oil |
| CN105152869A (en) * | 2015-07-29 | 2015-12-16 | 北京仁创科技集团有限公司 | Purification method for phenol in phenol-containing wastewater |
| CN108484367A (en) * | 2018-03-14 | 2018-09-04 | 江苏极易新材料有限公司 | A method of recycling 2,4- DI-tert-butylphenol compounds from 168 mother liquor of antioxidant |
| CN108484367B (en) * | 2018-03-14 | 2019-04-30 | 江苏极易新材料有限公司 | A method of recycling 2,4- DI-tert-butylphenol compounds from 168 mother liquor of antioxidant |
| CN109503333A (en) * | 2018-12-04 | 2019-03-22 | 青岛科技大学 | A kind of liquid-liquid extraction-flash separation phenol and water method |
| CN109534546A (en) * | 2018-12-12 | 2019-03-29 | 江苏湖大化工科技有限公司 | A kind of processing method of phenol resin production waste water |
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