CN107501051B - Method for extracting and separating phenolic compounds in oil-phenol mixture by using quaternary amino dicationic ionic liquid - Google Patents
Method for extracting and separating phenolic compounds in oil-phenol mixture by using quaternary amino dicationic ionic liquid Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/005—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up
- C07C37/007—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up from the tar industry
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0288—Applications, solvents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
Abstract
The invention provides a method for extracting and separating phenolic compounds in an oil-phenol mixture by using quaternary amino dicationic liquid, which comprises the following steps: adding a certain amount of quaternary amino dicationic liquid extractant into the oil-phenol mixture, stirring at a certain temperature, forming a eutectic solvent by the phenolic compound in the oil-phenol mixture and the quaternary amino dicationic liquid extractant, and separating the phenolic compound from the oil phase; separating out the eutectic solvent by a liquid separation method, then adding a back-extraction agent into the eutectic solvent, separating out the quaternary amino dicationic liquid extractant in a solid form, filtering and separating to obtain the quaternary amino dicationic liquid extractant, and reusing the extractant; the phenolic compounds in the back extractant are recovered by a distillation method, and the back extractant is reused. The quaternary amino dicationic liquid extractant used in the method is environment-friendly, has good thermal stability, is insoluble in oil phase, has high extraction rate, and can be repeatedly used.
Description
Technical Field
The invention relates to a method for extracting and separating phenolic compounds in an oil-phenol mixture by using quaternary amino dicationic liquid.
Background
The phenolic compound is a compound produced by substituting a hydrogen atom on a benzene ring of an aromatic hydrocarbon with a hydroxyl group, and is a hydroxyl group-containing derivative of the aromatic hydrocarbon. The common phenolic compounds mainly include phenol, cresol, xylenol and the like. The phenolic compound is an important chemical intermediate, is widely applied to the fields of synthetic fibers, engineering plastics, insecticides, medicines, explosives and the like, and has high commercial value. The phenolic compounds are mainly derived from coal direct liquefaction oil, coal tar and biomass pyrolysis oil. Extraction of phenolic compounds from these oil mixtures has been considered an important step in the further refinement or application of these oils. The process widely used in industry for separating phenolic compounds is a chemical alkaline washing process which requires a large amount of sodium hydroxide solution to form the sodium phenolate salt with the phenolic compound. Then, the strong acid is utilized to react with the sodium phenolate, and the phenolic compound is obtained and recovered. The disadvantage of this method is that a large amount of strong base and acid is used, which not only increases the cost of extraction, but also easily causes corrosion of equipment. In addition, the phenolic compound has high solubility in water, generates a large amount of phenolic wastewater, has high treatment difficulty and can cause serious pollution to the environment. Therefore, it is necessary to develop a new extraction method without using an aqueous phase and without using a base or an acid.
In order to solve the above problems, Hou et al [ Y.C.Hou, Y.H.ren, W.Pen, S.H.ren, W.Z.Wu.separation of phenols from oil using imidazolium-based ionic liquids, Ind.Eng.Chem.Res.,2013,52:18071-18075] proposed that the extraction rate of phenolic compounds could reach 99.9%, but the ionic liquid property is unstable, i.e., decomposition at 150 [ C.P.DLFree, J.M.Crostwaite, D.G.Hert, S.N.V.K.Aki, J.F.Brennecke.Thermophilicity of halogenated compounds, J.F.Brennecichl.954, En.964, data 49 ]. Meng et al [ H.Meng, C.T.Ge, N.N.ren, W.Y.Ma, Y.Z.Lu, C.X.Li.Complex extraction of phenol and cresol from model catalysts with polymers, ethanol amines, and ionic liquids of industry. ind. Eng.chem.Res.,2014,53:355-362] found that this kind of extractant is not only thermally unstable but also easily decomposed; meanwhile, the extractant is partially dissolved in the oil phase and the back extractant (the concentration is as high as 1000ppm), so that the oil phase is easily polluted, the extractant is lost, and the separation process becomes more complicated. Meanwhile, Gao et al [ J.J.Gao, Y.F.Dai, W.Y.Ma, H.H.Xu, C.X.Li. Efficient separation of phenolic from oil by acid-base complex adsorption. chem.Eng.J.,2015,281: 749-one 758] found that some imidazole extractants are also easily soluble in the oil phase. Therefore, it is very important to find an extractant which is thermodynamically stable and insoluble in the oil phase.
The method adopts quaternary amino dicationic ionic liquid as an extracting agent to extract and separate phenolic compounds in the oil-phenol mixture, and can realize the regeneration of the extracting agent. The quaternary amino dicationic liquid used in the experiment is solid at room temperature, but the quaternary amino dicationic liquid is added into the oil-phenol mixture to form a eutectic solvent with the phenolic compound, and the eutectic solvent is insoluble in an oil phase, so that the separation of the phenolic compound in the oil-phenol mixture is realized; the phenolic compounds in the eutectic solvent and the regenerated quaternary amino dicationic liquid extractant can be recovered by a reverse extraction method. The quaternary amino dicationic liquid extractant used in the method is environment-friendly, stable in property and insoluble in oil-phenol mixture; the used quaternary amino dicationic liquid extractant can quickly and efficiently extract phenolic compounds in an oil-phenol mixture; the quaternary amino dicationic liquid extractant can be regenerated, so that the extractant can be reused, and the extraction efficiency is unchanged in the process of reuse.
Disclosure of Invention
The invention aims to provide a method for efficiently separating phenolic compounds, aiming at solving the problems existing in the separation of phenolic compounds in oil-phenol mixtures at present. The method takes the quaternary amino dicationic liquid as the extractant, and realizes the separation of the phenolic compounds in the oil-phenol mixture in a manner that the quaternary amino dicationic liquid extractant and the phenolic compounds form a eutectic solvent; the quaternary amino dicationic liquid extractant in the eutectic solvent can be regenerated by back extraction with diethyl ether, butanone or ethyl acetate.
The purpose of the invention is realized by adopting the following technical scheme.
A method for extracting and separating phenolic compounds in an oil-phenol mixture by using a quaternary amino dicationic ionic liquid extractant comprises the following steps: (1) adding a certain amount of quaternary amino dicationic liquid extractant into the oil-phenol mixture, stirring the mixture of the oil-phenol mixture and the quaternary amino dicationic liquid extractant at a certain temperature, standing, and performing phase separation to obtain oil without phenolic compounds and a eutectic solvent; (2) adding a back extractant into the eutectic solvent obtained in the step (1), precipitating the quaternary amino dicationic liquid extractant in a solid form, filtering and separating to obtain the quaternary amino dicationic liquid extractant and a back extractant solution containing phenolic compounds, and repeatedly using the quaternary amino dicationic liquid extractant. (3) And (3) distilling the back extractant solution containing the phenolic compounds obtained in the step (2) to obtain the phenolic compounds and the back extractant, wherein the back extractant is reused.
In the above method, the quaternary amino dicationic liquid extractant includes a 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt, a 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt, and a 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt.
In the above method, the oil in the oil-phenol mixture is aromatic hydrocarbon and aliphatic hydrocarbon (the aromatic hydrocarbon is one or more of benzene, toluene and xylene, the aliphatic hydrocarbon is one or more of n-hexane, n-heptane and cyclohexane), and the phenolic compound in the oil-phenol mixture is one or more of phenol, cresol, ethylphenol, dimethylphenol, naphthol and resorcinol; or a coal tar distillate fraction containing phenol.
In the method, the concentration of the phenolic compounds in the oil-phenol mixture is 10 g/L-300 g/L.
In the method, the molar ratio of the used quaternary amino dicationic liquid extractant to the phenolic compound in the oil phenol mixture is 0.1-2.0.
In the method, the temperature of the quaternary amino dicationic liquid extractant for separating phenolic compounds in the oil-phenol mixture is 0-60 ℃.
In the method, the back-extraction agent of the eutectic solvent in the step (2) is diethyl ether, ethyl acetate or butanone.
In the method, the volume ratio of the back-extraction agent to the eutectic solvent in the step (2) is 5-20.
In the method, the temperature of the quaternary amino dicationic liquid extractant regenerated by the back extractant in the step (2) in the eutectic solvent is 10-40 ℃.
In the above method, the temperature at which the stripping agent solution containing the phenolic compound in the step (3) is distilled is 60 to 110 ℃.
The principle of the method is as follows: phenolic compounds and the quaternary amino dicationic liquid extractant can form eutectic solvents through hydrogen bond interaction, and other components in the oil-phenol mixture cannot form eutectic solvents with the quaternary amino dicationic liquid extractant; the eutectic solvent formed by the quaternary amino dicationic liquid extractant and the phenolic compound is insoluble in the dephenolized oil phase, so that the phenolic compound in the oil-phenol mixture can be selectively extracted and separated by using the quaternary amino dicationic liquid extractant. The phenolic compound can be dissolved in the back-extraction agent (diethyl ether, ethyl acetate or butanone), and the quaternary amino dicationic liquid extractant is insoluble in the back-extraction agent, so when the back-extraction agent is added into the eutectic solvent, the quaternary amino dicationic liquid extractant is precipitated in a solid form, and the quaternary amino dicationic liquid extractant can be obtained by filtering, so that the regeneration of the extractant is realized. The quaternary amino dicationic liquid extractant provided by the patent has the characteristic of a symmetrical structure of dicationic liquid, and has higher stability and lower solubility in oil than a common ionic liquid extractant.
Compared with the traditional method, the method has the advantages that: (1) selectively extracting and separating phenolic compounds in the oil-phenol mixture by adopting a reproducible quaternary amino dicationic liquid extractant; (2) the used quaternary amino dicationic liquid extractant is environment-friendly and has high thermal stability, such as 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt, 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt and 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt have thermal decomposition temperatures of 238 ℃, 242 ℃ and 272 ℃ respectively; (3) the quaternary amino dicationic liquid used has very low solubility in oil, such as 6ppm, 19ppm and 31ppm of the solubility of 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt, 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt and 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt in oil at 25 ℃, which is much less than the currently reported solubility of 1000ppm (monoethanolamine extractant); (4) the method has the advantages of high extraction speed, high extraction efficiency and simple operation; (5) the used extractant and the back extractant can be reused; (6) the method does not use acid and alkali solvents, saves resources, does not generate waste water, and has low cost and environmental protection.
The following will describe the method for extracting and separating phenolic compounds from oil-phenol mixture by using quaternary amino dicationic liquid extractant and regenerating quaternary amino dicationic liquid extractant in further detail with reference to the examples, but the invention is not limited thereby.
Example 1
In this example, phenol and toluene were chosen as the analogous components of the phenolic compound and the oil, respectively, in the oil-phenol mixture. Firstly, 150.00g of phenolic compound is added into a beaker containing toluene, stirred and dissolved, then transferred into a 500mL volumetric flask, added with toluene, shaken up and subjected to constant volume to obtain a simulated oil phenol mixture, wherein the concentration of the phenolic compound is 300.00 g/L.
20mL of the above simulated oil-phenol mixture was put in a 50mL graduated tube, 12.4323g of 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt, 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt [ molecular weight 390g/mol ] and a phenolic compound were added thereto in a molar ratio of 0.5, and then placed in a water bath at 25 ℃ and magnetically stirred for 30min, left to stand for 20min, and phase separation was performed using a separatory funnel to obtain 17.2mL of an oil phase from which phenol was removed and 3.5mL of a eutectic solvent.
The composition of the dephenolized oil phase was analyzed by gas chromatography. The used gas chromatograph is an Shimadzu GC-2014 gas chromatograph, the chromatographic column is an RTX-5 capillary column, and the detector is a hydrogen flame ionization detector; the determination method is an internal standard method, dichloromethane is used as a solvent, o-nitrotoluene is used as an internal standard substance, nitrogen is used as a carrier gas, the temperature of an injection chamber is 250 ℃, the temperature of a detector is 280 ℃, and the temperature rise program is as follows: keeping at 80 deg.C for 1min, heating to 220 deg.C at 40 deg.C/min, and keeping for 3min, wherein the analysis process is 7.50 min. The analysis result showed that the concentration of phenol in the dephenolized oil phase was 10.42g/L, and the calculated extraction rate of phenol was 97.0%.
To the eutectic solvent obtained by the phase separation, 17.5mL of ethyl acetate was added, the volume ratio of ethyl acetate to the eutectic solvent was 5, the back extraction was performed by stirring at a temperature of 10 ℃, the 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt was precipitated as solid particles, and the regenerated 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt solid and the ethyl acetate solution containing phenol were obtained by filtration.
The above phenol-containing ethyl acetate solution was subjected to distillation at a temperature of 110 ℃ to obtain 5.81g of the product phenol, and 15.5mL of the recovered ethyl acetate solvent.
Example 2
In this example, phenol and toluene were chosen as the analogous components of the phenolic compound and the oil, respectively, in the oil-phenol mixture. Firstly, 50.00g of phenolic compound is added into a beaker containing toluene, stirred and dissolved, then transferred into a 500mL volumetric flask, added with toluene, shaken up and subjected to constant volume to obtain a simulated oil phenol mixture, wherein the concentration of the phenolic compound is 100.00 g/L.
20mL of the simulated oil-phenol mixture was put in a 50mL graduated tube, 0.8288g of 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt, 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt [ with a molecular weight of 390g/mol ] and a phenolic compound were added thereto at a molar ratio of 0.1, and then the mixture was placed in a water bath at 60 ℃ and magnetically stirred for 30min, and then allowed to stand for 20min, and phase separation was performed using a separatory funnel, whereby 19.5mL of an oil phase from which phenol was removed and 0.8mL of a eutectic solvent were obtained.
The composition of the dephenolized oil phase was analyzed by gas chromatography. The analytical conditions used are described in example 1. The analysis showed that the phenol concentration in the dephenolized oil phase was 80.30g/L, and the calculated extraction rate was 21.7%.
To the eutectic solvent obtained by the phase separation, 16mL of diethyl ether was added in a volume ratio of diethyl ether to the eutectic solvent of 20, and the back extraction was carried out at a temperature of 40 ℃ with stirring, and the 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt was precipitated as solid particles, which were filtered to obtain a regenerated solid of the 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt and a diethyl ether solution containing phenol.
As for the above ether solution containing phenol, distillation was carried out at 60 ℃ to obtain 0.41g of phenol as a product, and 15.5mL of the ether solvent was recovered.
Example 3
In this example, phenol and n-hexane were selected as the analogous components of the phenolic compounds and oil, respectively, in the oil-phenol mixture. Firstly, 5.00g of phenolic compound is added into a beaker containing n-hexane, stirred and dissolved, then transferred into a 500mL volumetric flask, and the n-hexane is added into the volumetric flask, shaken up and subjected to constant volume to obtain a simulated oil phenol mixture, wherein the concentration of the phenolic compound is 10.00 g/L.
20mL of the above simulated oil-phenol mixture was put in a 50mL graduated tube, 1.6577g of 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt, 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt [ molecular weight 390g/mol ] and phenolic compound were added thereto at a molar ratio of 2.0, and then placed in a water bath at 0 ℃ and magnetically stirred for 30min, left to stand for 20min, and phase separation was performed using a separatory funnel to obtain 19.5mL of an oil phase from which phenol was removed and 0.6mL of a eutectic solvent.
The composition of the dephenolized oil phase was analyzed using an ultraviolet-visible spectrophotometer (model TU-1901, manufactured by Beijing Pujingyo general instruments, Inc.). The analysis showed that the phenol concentration in the dephenolized oil phase was 1.05g/L, and the calculated extraction rate was 89.8%.
To the eutectic solvent obtained by the phase separation, 12mL of butanone was added at a volume ratio of butanone to the eutectic solvent of 20, and by performing back extraction with stirring at a temperature of 40 ℃, 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt was precipitated as solid particles, and the solid particles were filtered to obtain a regenerated 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt solid and a butanone solution containing phenol.
The methyl ethyl ketone solution containing phenol was distilled at 110 ℃ to obtain 0.19g of phenol as a product and 11.1mL of a recovered methyl ethyl ketone solvent.
Example 4
In this example, phenol and toluene were chosen as the analogous components of the phenolic compound and the oil, respectively, in the oil-phenol mixture. Firstly, 150.00g of phenolic compound is added into a beaker containing toluene, stirred and dissolved, then transferred into a 500mL volumetric flask, added with toluene, shaken up and subjected to constant volume to obtain a simulated oil phenol mixture, wherein the concentration of the phenolic compound is 300.00 g/L.
20mL of the above simulated oil-phenol mixture was put in a 50mL graduated tube, 12.8786g of 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt, 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt [ molecular weight 404g/mol ] and a phenolic compound were added thereto in a molar ratio of 0.5, and then placed in a water bath at 25 ℃ and magnetically stirred for 30min, left to stand for 20min, and phase separation was performed using a separatory funnel to obtain 17.0mL of an oil phase from which phenol was removed and 3.7mL of a eutectic solvent.
The composition of the dephenolized oil phase was analyzed by gas chromatography. The analytical conditions used are described in example 1. The analysis showed that the concentration of phenol in the dephenolized oil phase was 8.42g/L, and the calculated extraction rate was 97.6%.
To the eutectic solvent obtained by the phase separation, 18.5mL of ethyl acetate was added, the volume ratio of ethyl acetate to the eutectic solvent was 5, the back extraction was performed by stirring at a temperature of 10 ℃, the 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt was precipitated as solid particles, and the regenerated solid 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt and the ethyl acetate solution containing phenol were obtained by filtration.
The above phenol-containing ethyl acetate solution was subjected to distillation at a temperature of 110 ℃ to obtain 5.89g of the product phenol, and 17.3mL of the recovered ethyl acetate solvent.
Example 5
In this example, phenol and toluene were chosen as the analogous components of the phenolic compound and the oil, respectively, in the oil-phenol mixture. Firstly, 50.00g of phenolic compound is added into a beaker containing toluene, stirred and dissolved, then transferred into a 500mL volumetric flask, added with toluene, shaken up and subjected to constant volume to obtain a simulated oil phenol mixture, wherein the concentration of the phenolic compound is 100.00 g/L.
20mL of the above simulated oil-phenol mixture was put in a 50mL graduated tube, 0.8590g of 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt, 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt [ molecular weight 404g/mol ] and a phenolic compound were added thereto in a molar ratio of 0.1, and then placed in a water bath at 60 ℃ and magnetically stirred for 30min, left to stand for 20min, and phase separation was performed using a separatory funnel to obtain 19.3mL of an oil phase from which phenol was removed and 1.0mL of a eutectic solvent.
The composition of the dephenolized oil phase was analyzed by gas chromatography. The analytical conditions used are described in example 1. The analysis showed that the phenol concentration in the dephenolized oil phase was 78.4g/L, and the calculated extraction rate was 24.3%.
For the eutectic solvent obtained by the phase separation, 20mL of diethyl ether was added thereto in a volume ratio of diethyl ether to the eutectic solvent of 20, and the back extraction was carried out at a temperature of 40 ℃ with stirring, and 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt was precipitated as solid particles, and filtered to obtain a regenerated solid of 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt and a diethyl ether solution containing phenol.
As for the above ether solution containing phenol, distillation was carried out at 60 ℃ to obtain 0.41g of phenol as a product, and 19.5mL of the ether solvent was recovered.
Example 6
In this example, phenol and cyclohexane were chosen as the analogous components of the phenolic compounds and oil, respectively, in the oil-phenol mixture. Firstly, 5.00g of phenolic compound is added into a beaker containing cyclohexane, stirred and dissolved, then transferred into a 500mL volumetric flask, and added with cyclohexane, shaken up and fixed to volume to obtain a simulated oil phenol mixture, wherein the concentration of the phenolic compound is 10.00 g/L.
20mL of the above simulated oil-phenol mixture was put in a 50mL graduated tube, 1.7172g of 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt, 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt [ molecular weight 404g/mol ] and a phenolic compound were added thereto at a molar ratio of 2.0, and then placed in a water bath at 0 ℃ and magnetically stirred for 30min, left to stand for 20min, and phase separation was performed using a separatory funnel to obtain 19.4mL of an oil phase from which phenol was removed and 0.7mL of a eutectic solvent.
The composition of the dephenolized oil phase was analyzed using an ultraviolet-visible spectrophotometer (model TU-1901, manufactured by Beijing Pujingyo general instruments, Inc.). The analysis showed that the phenol concentration in the dephenolized oil phase was 0.84g/L, and the calculated extraction rate was 91.9%.
For the eutectic solvent obtained by the phase separation, 14mL of butanone was added thereto at a volume ratio of butanone to the eutectic solvent of 20, and by performing back extraction with stirring at a temperature of 40 ℃, 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt was precipitated as solid particles, and filtration was performed to obtain a regenerated solid of 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt and a butanone solution containing phenol.
The methyl ethyl ketone solution containing phenol was distilled at 110 ℃ to obtain 0.19g of phenol as a product and 13.2mL of a recovered methyl ethyl ketone solvent.
Example 7
In this example, phenol and toluene were chosen as the analogous components of the phenolic compound and the oil, respectively, in the oil-phenol mixture. Firstly, 150.00g of phenolic compound is added into a beaker containing toluene, stirred and dissolved, then transferred into a 500mL volumetric flask, added with toluene, shaken up and subjected to constant volume to obtain a simulated oil phenol mixture, wherein the concentration of the phenolic compound is 300.00 g/L.
20mL of the above simulated oil-phenol mixture was put in a 50mL graduated tube, 13.3249g of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt, 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt [ having a molecular weight of 418g/mol ] and a phenolic compound were added thereto in a molar ratio of 0.5, and then placed in a water bath at 25 ℃ and magnetically stirred for 30min, left to stand for 20min, and phase separation was performed using a separatory funnel to obtain 16.8mL of an oil phase from which phenol was removed and 4.1mL of a eutectic solvent.
The composition of the dephenolized oil phase was analyzed by gas chromatography. The analytical conditions used are described in example 1. The analysis showed that the concentration of phenol in the dephenolized oil phase was 4.31g/L, and the calculated extraction rate was 98.8%.
To the eutectic solvent obtained by the phase separation, 82mL of diethyl ether was added in a volume ratio of diethyl ether to the eutectic solvent of 20, and the back extraction was carried out at a temperature of 25 ℃ with stirring, and 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt was precipitated as solid particles, and filtered to obtain a regenerated solid of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt and a diethyl ether solution containing phenol.
As for the above ether solution containing phenol, distillation was conducted at 60 ℃ to obtain 5.92g of the product phenol, and 80.1mL of the recovered ether solvent.
Example 8
In this example, phenol and n-hexane were selected as the analogous components of the phenolic compounds and oil, respectively, in the oil-phenol mixture. Firstly, 5.00g of phenolic compound is added into a beaker containing n-hexane, stirred and dissolved, then transferred into a 500mL volumetric flask, and the n-hexane is added into the volumetric flask, shaken up and subjected to constant volume to obtain a simulated oil phenol mixture, wherein the concentration of the phenolic compound is 10.00 g/L.
20mL of the above simulated oil-phenol mixture was put in a 50mL graduated tube, 1.7767g of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt, 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt [ having a molecular weight of 418g/mol ] and a phenolic compound were added thereto in a molar ratio of 2.0, and then placed in a water bath at 0 ℃ and magnetically stirred for 30min, left to stand for 20min, and phase separation was performed using a separatory funnel to obtain 19.3mL of an oil phase from which phenol was removed and 0.9mL of a eutectic solvent.
The composition of the dephenolized oil phase was analyzed using an ultraviolet-visible spectrophotometer (model TU-1901, manufactured by Beijing Pujingyo general instruments, Inc.). The analysis showed that the concentration of phenol in the dephenolized oil phase was 0.32g/L, and the calculated extraction rate was 96.9%.
To the eutectic solvent obtained by the phase separation, 18mL of ethyl acetate was added at a volume ratio of ethyl acetate to the eutectic solvent of 20, and the back extraction was carried out at a temperature of 25 ℃ with stirring, and the 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt was precipitated as solid particles, and filtered to obtain a regenerated solid of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt and an ethyl acetate solution containing phenol.
As to the above-mentioned ethyl acetate solution containing phenol, distillation was carried out at a temperature of 110 ℃ to obtain 0.20g of the product phenol, and 17.0mL of the recovered ethyl acetate solvent.
Example 9
In this example, phenol was selected as the phenolic compound mimic component of the oil-phenol mixture, and benzene, toluene, o-xylene, m-xylene, and p-xylene were selected as the mimic component of the oil in the oil-phenol mixture, respectively. Benzene, toluene, o-xylene, m-xylene and p-xylene are mixed in a 1L beaker according to the volume ratio of 1:1:1:1:1, and are stirred uniformly to prepare a simulation oil component. 50.00g of the phenolic compound was added to a beaker containing the simulated oil component, stirred to dissolve, and then transferred to a 500mL volumetric flask, to which the simulated oil component was added, shaken up, and fixed to volume to obtain a simulated oil phenol mixture in which the concentration of the phenolic compound was 100.00 g/L.
20mL of the above simulated oil-phenol mixture was put in a 50mL graduated tube, 8.8833g of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt (1, 4-bis (N-triethyl) -1, 4-dibromobutane salt [ molecular weight 418g/mol ] was added thereto in a molar ratio of 1.0 to the phenolic compound), and then placed in a water bath at 25 ℃ and magnetically stirred for 30min, left to stand for 20min, and phase separation was performed using a separatory funnel to obtain 17.9mL of an oil phase from which phenol was removed and 3.1mL of a eutectic solvent.
The composition of the dephenolized oil phase was analyzed by gas chromatography. The analytical conditions used are described in example 1. The analysis showed that the concentration of phenol in the dephenolized oil phase was 4.12g/L, and the calculated extraction rate was 96.3%.
To the eutectic solvent obtained by the phase separation, 31mL of butanone was added at a volume ratio of butanone to the eutectic solvent of 10, and by performing back extraction with stirring at a temperature of 25 ℃, 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt was precipitated as solid particles, and filtration was performed to obtain a regenerated solid of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt and a butanone solution containing phenol.
The methyl ethyl ketone solution containing phenol was distilled at 110 ℃ to obtain 1.91g of phenol as a product and 30.5mL of a methyl ethyl ketone solvent.
Example 10
In this example, phenol was selected as the phenolic compound mimic component of the oil-phenol mixture, and n-hexane, n-heptane, and cyclohexane were selected as the mimic component of the oil in the oil-phenol mixture, respectively. Firstly, n-hexane, n-heptane and cyclohexane are mixed in a 1L beaker according to the volume ratio of 1:1:1, and are stirred uniformly to prepare a simulation oil component. 5.00g of the phenolic compound was added to a beaker containing the simulated oil component, stirred to dissolve, and then transferred to a 500mL volumetric flask, to which the simulated oil component was added, shaken up, and brought to constant volume, to obtain a simulated oil phenol mixture in which the concentration of the phenolic compound was 10.00 g/L.
20mL of the above simulated oil-phenol mixture was put in a 50mL graduated tube, 1.7767g of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt (1, 4-bis (N-triethyl) -1, 4-dibromobutane salt [ molecular weight 418g/mol ] was added thereto in a molar ratio of 2.0 to the phenolic compound), and then placed in a water bath at 60 ℃ and magnetically stirred for 30min, left to stand for 20min, and phase separation was performed using a separatory funnel to obtain 19.5mL of an oil phase from which phenol was removed and 0.8mL of a eutectic solvent.
The composition of the dephenolized oil phase was analyzed using an ultraviolet-visible spectrophotometer (model TU-1901, manufactured by Beijing Pujingyo general instruments, Inc.). The analysis showed that the phenol concentration in the dephenolized oil phase was 0.34g/L, and the calculated extraction rate was 97.0%.
To the eutectic solvent obtained by the phase separation, 16mL of diethyl ether was added in a volume ratio of diethyl ether to the eutectic solvent of 20, and the back extraction was carried out at a temperature of 25 ℃ with stirring, and 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt was precipitated as solid particles, and filtered to obtain a regenerated solid of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt and a diethyl ether solution containing phenol.
As for the above ether solution containing phenol, distillation was carried out at 60 ℃ to obtain 0.19g of the product phenol, and 15.0mL of the ether solvent was recovered.
Example 11
In this example, phenol, cresol, ethylphenol, xylenol, naphthol, resorcinol were selected as the phenolic compound mimic component in the oil-phenol mixture, and toluene was selected as the mimic component for the oil in the oil-phenol mixture. Firstly, 10.00g of phenol, 10.00g of cresol, 10.00g of ethyl phenol, 10.00g of xylenol, 5.00g of naphthol and 5.00g of resorcinol are added into a beaker containing toluene, stirred and dissolved, then transferred into a 500mL volumetric flask, added with toluene, shaken and subjected to constant volume to obtain a simulated oil phenol mixture, wherein the concentration of phenolic compounds is 100.00 g/L.
20mL of the above simulated oil-phenol mixture was put in a 50mL graduated tube, 3.7042g of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt, 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt [ having a molecular weight of 418g/mol ] and a phenolic compound were added thereto in a molar ratio of 0.5, and then placed in a water bath at 25 ℃ and magnetically stirred for 30min, left to stand for 20min, and phase separation was performed using a separatory funnel to obtain 17.5mL of an oil phase from which phenol was removed and 3.1mL of a eutectic solvent.
The composition of the dephenolized oil phase was analyzed by gas chromatography. The analytical conditions used are described in example 1. The analysis showed that the concentration of phenol in the dephenolized oil phase was 4.21g/L, and the calculated extraction rate was 96.3%.
For the eutectic solvent obtained by the phase separation, 62mL of diethyl ether was added thereto in a volume ratio of diethyl ether to the eutectic solvent of 20, and the back extraction was carried out at a temperature of 25 ℃ with stirring, and 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt was precipitated as solid particles, and filtered to obtain a regenerated solid of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt and a diethyl ether solution containing phenol.
As for the above ether solution containing phenol, distillation was carried out at 60 ℃ to obtain 1.95g of the product phenol, and 60.5mL of the ether solvent was recovered.
Example 12
In this example, phenol and toluene were chosen as the analogous components of the phenolic compound and the oil, respectively, in the oil-phenol mixture. Firstly, 50.00g of phenolic compound is added into a beaker containing toluene, stirred and dissolved, then transferred into a 500mL volumetric flask, added with toluene, shaken up and subjected to constant volume to obtain a simulated oil phenol mixture, wherein the concentration of the phenolic compound is 100.00 g/L.
20mL of the above simulated oil-phenol mixture was put in a 50mL graduated tube, 4.4420g of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt (1, 4-bis (N-triethyl) -1, 4-dibromobutane salt [ molecular weight 418g/mol ]) was added thereto at a molar ratio of 0.5 to the phenolic compound, and then the mixture was placed in a water bath at 25 ℃ and magnetically stirred for 30min, left to stand for 20min, and phase separation was performed using a separatory funnel to obtain 17.4mL of an oil phase from which phenol was removed and 3.1mL of a eutectic solvent.
The composition of the dephenolized oil phase was analyzed by gas chromatography. The analytical conditions used are described in example 1. The analysis showed that the concentration of phenol in the dephenolized oil phase was 4.20g/L, and the calculated extraction rate was 96.3%.
To the eutectic solvent obtained by the phase separation, 15.5mL of diethyl ether was added in a volume ratio of diethyl ether to the eutectic solvent of 5, and the back extraction was carried out at a temperature of 25 ℃ with stirring, and the 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt was precipitated as solid particles, and filtered to obtain a regenerated solid of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt and a diethyl ether solution containing phenol.
As for the above ether solution containing phenol, distillation was conducted at 60 ℃ to obtain 1.90g of the product phenol, and 14.6mL of the ether solvent was recovered.
Example 13
In this example, phenol and toluene were chosen as the analogous components of the phenolic compound and the oil, respectively, in the oil-phenol mixture. Firstly, 50.00g of phenolic compound is added into a beaker containing toluene, stirred and dissolved, then transferred into a 500mL volumetric flask, added with toluene, shaken up and subjected to constant volume to obtain a simulated oil phenol mixture, wherein the concentration of the phenolic compound is 100.00 g/L.
20mL of the above simulated oil-phenol mixture was put in a 50mL graduated tube, 4.4420g of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt (1, 4-bis (N-triethyl) -1, 4-dibromobutane salt [ molecular weight 418g/mol ]) was added thereto at a molar ratio of 0.5 to the phenolic compound, and then the mixture was placed in a water bath at 25 ℃ and magnetically stirred for 30min, left to stand for 20min, and phase separation was performed using a separatory funnel to obtain 17.5mL of an oil phase from which phenol was removed and 3.0mL of a eutectic solvent.
The composition of the dephenolized oil phase was analyzed by gas chromatography. The analytical conditions used are described in example 1. The analysis showed that the phenol concentration in the dephenolized oil phase was 4.18g/L, and the calculated extraction rate was 96.4%.
To the eutectic solvent obtained by the phase separation, 60mL of ethyl acetate was added, the volume ratio of ethyl acetate to the eutectic solvent was 20, the back extraction was performed by stirring at a temperature of 40 ℃, the 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt was precipitated as solid particles, and the regenerated 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt solid and the ethyl acetate solution containing phenol were obtained by filtration.
The above phenol-containing ethyl acetate solution was distilled at 110 ℃ to obtain 1.93g of the product phenol, and 58.6mL of the recovered ethyl acetate solvent.
Example 14
This example shows the repeated use experiments of a quaternary ammonium salt dicationic liquid extractant.
In this example, phenol and toluene were chosen as the analogous components of the phenolic compound and the oil, respectively, in the oil-phenol mixture. Firstly, 50.00g of phenolic compound is added into a beaker containing toluene, stirred and dissolved, then transferred into a 500mL volumetric flask, added with toluene, shaken up and subjected to constant volume to obtain a simulated oil phenol mixture, wherein the concentration of the phenolic compound is 100.00 g/L.
20mL of the above simulated oil-phenol mixture was put in a 50mL graduated tube, 4.4420g of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt (1, 4-bis (N-triethyl) -1, 4-dibromobutane salt [ molecular weight 418g/mol ]) was added thereto at a molar ratio of 0.5 to the phenolic compound, and then the mixture was placed in a water bath at 25 ℃ and magnetically stirred for 30min, left to stand for 20min, and phase separation was performed using a separatory funnel to obtain 17.4mL of an oil phase from which phenol was removed and 3.1mL of a eutectic solvent.
The composition of the dephenolized oil phase was analyzed by gas chromatography. The analytical conditions used are described in example 1. The analysis showed that the concentration of phenol in the dephenolized oil phase was 4.21g/L, and the calculated extraction rate was 96.4%.
To the eutectic solvent obtained by the phase separation, 15.5mL of diethyl ether was added in a volume ratio of diethyl ether to the eutectic solvent of 5, and the back extraction was carried out at a temperature of 25 ℃ with stirring, and the 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt was precipitated as solid particles, and filtered to obtain a regenerated solid of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt and a diethyl ether solution containing phenol.
As for the above ether solution containing phenol, distillation was conducted at 60 ℃ to obtain 1.90g of the product phenol, and 14.6mL of the ether solvent was recovered.
The regenerated 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt extractant was used repeatedly to extract phenolic compounds from the simulated oil phenol mixture described above, and this operation was repeated five times. The extraction rates of the phenolic compounds in the five experiments were 96.2%, 96.5%, 96.4%, 96.1% and 96.6%, respectively.
Example 15
200g of real coal tar phenol oil fraction is taken, and the concentration of phenolic compounds in the coal tar is analyzed to be 21.23 percent (mass fraction) by adopting a national standard method (GB/T24200-. 65.73g of 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt extractant is added, the molar ratio of the 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt extractant to the phenolic compound (measured according to cresol) is about 0.4, then the mixture is placed in a constant temperature water bath at 25 ℃ for magnetic stirring for 30min, then the mixture is transferred to a 500mL insulated separating funnel, the temperature is controlled at 25 ℃, the mixture is kept still for phase separation for 2 h, and then the mixture is separated to obtain coal tar of the upper dephenolized compound and a lower eutectic solvent phase. The composition of the coal tar of the dephenolized compound is analyzed by adopting a national standard method (GB/T24200-2009). The analysis result shows that the content of the phenolic compound in the coal tar of the dephenolized compound is 0.96 percent, and the extraction rate is 95.7 percent by calculation. Taking 70.2mL of lower-phase eutectic solvent, directly adding 560mL of stripping agent diethyl ether into the lower-phase eutectic solvent, wherein the volume ratio of the diethyl ether to the eutectic solvent is about 8, stirring for 30min at the temperature of 25 ℃, filtering, taking a liquid phase, performing rotary evaporation in an oil bath at the temperature of 110 ℃, rotating at a speed of 50r/min, and performing rotary distillation for 2 hours to obtain 41.21g of the product phenolic compound.
Claims (8)
1. A method for extracting and separating phenolic compounds in an oil-phenol mixture by using a quaternary amino dicationic ionic liquid comprises the following steps:
(1) adding a quaternary amino dicationic liquid extractant into the oil-phenol mixture, stirring the mixture of the oil-phenol mixture and the quaternary amino dicationic liquid extractant at a given temperature, standing, and performing phase separation to obtain oil without phenolic compounds and a eutectic solvent;
(2) adding a back extractant into the eutectic solvent obtained in the step (1), precipitating the quaternary amino dicationic liquid extractant in a solid form, filtering and separating to obtain the quaternary amino dicationic liquid extractant and a back extractant solution containing a phenolic compound, and repeatedly using the quaternary amino dicationic liquid extractant;
(3) distilling the back extractant solution containing the phenolic compounds obtained in the step (2) to obtain the phenolic compounds and a back extractant, and reusing the back extractant;
wherein the quaternary amino dicationic liquid extractant in step (1) is selected from 1, 2-bis (N-triethyl) -1, 2-dibromoethane salt, 1, 3-bis (N-triethyl) -1, 3-dibromopropane salt or 1, 4-bis (N-triethyl) -1, 4-dibromobutane salt;
the molar ratio of the quaternary amino dicationic liquid extractant used in the step (1) to the phenolic compound in the oil phenol mixture is 0.5-2.0.
2. The method according to claim 1, wherein the oil in the oil-phenol mixture is aromatic hydrocarbon and aliphatic hydrocarbon, wherein the aromatic hydrocarbon is one or more of benzene, toluene and xylene, and the aliphatic hydrocarbon is one or more of n-hexane, n-heptane and cyclohexane; the phenolic compound in the oil phenol mixture is one or more of phenol, cresol, ethyl phenol, dimethyl phenol, naphthol and resorcinol; or a coal tar distillate fraction containing phenol.
3. The method according to claim 1, wherein the concentration of the phenolic compounds in the oil-phenol mixture is 10-300 g/L.
4. The method of claim 1, wherein the quaternary amino dicationic liquid extractant in step (1) is used to separate phenolic compounds from an oil-phenol mixture at a temperature of 0%oC ~ 60oC。
5. The method according to claim 1, wherein the stripping agent of the eutectic solvent in the step (2) is diethyl ether, ethyl acetate or butanone.
6. The method according to claim 1, wherein the volume ratio of the stripping agent to the eutectic solvent in the step (2) is 5-20.
7. The process of claim 1, wherein the temperature for regenerating the quaternary amino dicationic liquid extractant in the eutectic solvent with the stripping agent in step (2) is 10%oC ~ 40oC。
8. The process according to claim 1, wherein the temperature at which the stripping agent solution containing phenolic compounds in step (3) is distilled is 60 ℃oC ~ 110oC。
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