CN106831455A - A kind of method of the neutral oil in removal eutectic solvent - Google Patents
A kind of method of the neutral oil in removal eutectic solvent Download PDFInfo
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- CN106831455A CN106831455A CN201611127155.7A CN201611127155A CN106831455A CN 106831455 A CN106831455 A CN 106831455A CN 201611127155 A CN201611127155 A CN 201611127155A CN 106831455 A CN106831455 A CN 106831455A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C07C209/86—Separation
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- 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
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- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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Abstract
The invention provides a kind of minimizing technology of the neutral oil in eutectic solvent.The method comprises the following steps：To adding a certain proportion of low-carbon alkanes extractant in the eutectic solvent containing neutral oil, under conditions of being 10 DEG C~50 DEG C in temperature, neutral oil in eutectic solvent is removed by extracting process, the mixture of low-carbon alkanes and neutral oil is separated by the method distilled, and realizes the regeneration of low-carbon alkanes extractant.This method extractant can be recycled, and extraction process is quick, efficient, the purity that eutectic method separates phenolic compound in carbolic oil product can be significantly improved, while can avoid the waste of neutral oil again.
Description
Technical field
The present invention relates to a kind of minimizing technology of the neutral oil in eutectic solvent.Specifically, the present invention relates to one kind
It is solvent with low-carbon alkanes, the method that the neutral oil in eutectic solvent is removed by extracting process.
Background technology
Phenolic compound such as phenol, cresols, xylenol etc. are widely used industrial chemicals, are widely used in fiber, modeling
Other production fields such as the synthesis of material, agricultural chemicals, the preparation of medicine, and spices, dyestuff.It is mainly from biomass pyrolytic, coal
Obtained in tar and liquefied coal coil.There is abundant coal and biomass resource in China, from biomass pyrolysis oil, coal tar and coal
Phenolic compound is efficiently separated out in liquefaction oil huge economic benefit.The oily phenol mixture of current industrial comparative maturity
Separation method is NaOH alkali cleaning method, i.e., react generation phenol with the phenolic compound in oily phenol mixture with sodium hydroxide solution
Sodium salt, the sodium phenolate is soluble in the aqueous phase, so that and separation of oil；Then to removing neutral oil the sodium phenolate aqueous solution in add sulfuric acid
It is acidified, the phenolic compound insoluble in salt solution is generated, so as to realize the separation of phenolic compound.This process needs consumption
Substantial amounts of inorganic acid and aqueous slkali, high cost；Substantial amounts of phenol wastewater can be produced, it is necessary to subsequent treatment simultaneously；In addition, using sulphur
Acid acidifying is big to the corrosivity of equipment.In order to solve the above problems, it is necessary to develop the separation method of new nonaqueous phase.
By the method for eutectic, quaternary ammonium salt efficiently can separate phenolic compound from oily phenol mixture；
Then it is stripped to addition ether in eutectic solvent, it is possible to take out phenolic compound back extraction, and quaternary ammonium salt is obtained
To regeneration, the purpose that oily phenol mixture is separate is reached.The process need not use inorganic base and acid, and whole process is not produced containing phenol
Waste water；The process extractant quaternary ammonium salt consumption is few, cost-effective；The process separative efficiency, can be at room temperature to temperature-insensitive
Operation；Quaternary ammonium salt is renewable.As can be seen here, eutectic solvent method is deposited in can efficiently solving traditional oils phenol mixture separation process
Problem
But, during eutectic solvent method separates oily phenol mixture, formed using quaternary ammonium salt and phenolic compound
A certain amount of neutral oil (mainly aromatic substance) is carried in eutectic solvent secretly.It is reported that [Wang Zhen, Hou Yucui, Ren Shuhang,
The entrainment Journal of Chemical Industry and Engineering of oil, 2015,66,247- during the eutectic methods extract and separate oil phenol mixture of Kong Jie, Wu Wei pool
252], using toluene as neutral oil, with Choline Chloride as extractant, extraction phenol concentration is phenol in the oily phenol mixture of 200g/L
During, it is 1 with the mol ratio of phenol when Choline Chloride is added:1, the neutral oil mass fraction carried secretly in eutectic solvent is reachable
15%, wherein in eutectic solvent, the mass ratio of neutral oil and phenol is up to 30%.If the neutral oil carried secretly in eutectic solvent
It is not removed, it is also the mixed phenol mask work in later stage not only to waste the neutral oil carried secretly in neutral oil, and eutectic solvent
Difficulty is brought, causes the purity of product phenol not high.Therefore the neutral oil carried secretly in removal eutectic solvent is extremely important.
A certain proportion of low-carbon alkanes extractant is added in the eutectic solvent that our normal direction contains neutral oil, is in temperature
Under conditions of 10 DEG C~50 DEG C, the neutral oil in eutectic solvent is removed by extracting process, low-carbon alkanes and neutral oil it is mixed
Compound is separated by the method distilled, and realizes the regeneration of low-carbon alkanes extractant.This method extractant can be recycled, extraction
Take process quick, efficient, can significantly show the purity for improving phenolic compound, while the waste of neutral oil can be avoided again.
The content of the invention
It is molten present invention aim to address the eutectic formed during eutectic solvent method extract and separate oil phenol mixture
The problem of the neutral oil entrainment in agent.By to low-carbon alkanes extractant is added in the eutectic solvent containing neutral oil, one
Determine to extract neutral oil at temperature, obtain the low-carbon alkanes containing neutral oil, then separated low-carbon alkanes and neutral oil, low-carbon (LC)
Alkane is reclaimed and used.
The purpose of the present invention adopts the following technical scheme that to realize.
A kind of method of the neutral oil carried secretly in removal eutectic solvent, the method includes molten to the eutectic containing neutral oil
Extractant low-carbon alkanes extraction neutral oil, and extractant low-carbon alkanes are added in agent (being formed by quaternary ammonium salt and phenolic compound)
The step of regeneration.
In the above method, described low-carbon alkanes are selected from n-hexane, hexamethylene, normal heptane.
In the above method, described quaternary ammonium salt includes Choline Chloride, tetramethyl ammonium chloride, etamon chloride.
In the above method, the mass ratio of neutral oil in described eutectic solvent and phenolic compound for 0.05~
0.35。
In the above method, phenolic compound and the mol ratio of quaternary ammonium salt are 1.0~3.0 in described eutectic solvent.
In the above method, extraction temperature is 10 DEG C~50 DEG C.
In the above method, the low-carbon alkanes of addition are 1.0~8.0 with the volume ratio of eutectic solvent.
In the above method, the separated temperature of extractant low-carbon alkanes and neutral oil mixture is 80 DEG C~110 DEG C.
Principle of the invention
Neutral oil and above-mentioned low-carbon alkanes have a good intersolubility, and above-mentioned low-carbon alkanes in eutectic solvent almost
It is insoluble；The polarity very little of low-carbon alkanes, and the polarity of phenolic compound is larger；Phenolic compound is small with the effect of low-carbon alkanes,
Effect with quaternary ammonium salt is strong.It is therefore possible to use the neutrality in the method choice removal eutectic solvent of low-carbon alkanes extraction
Oil.
Advantages of the present invention
The present invention uses the neutral oil in low-carbon alkanes selective extraction eutectic solvent, and advantage is：(1) can be efficient
Neutral oil in ground, optionally removal eutectic solvent, improves the purity of phenolic product；(2) neutral oil for being extracted can be with
Reclaim, it is to avoid neutral oil waste；(3) extractant low-carbon alkanes can be reused.
Specific embodiment
Below in conjunction with embodiment to the present invention provide removal eutectic solvent in entrainment neutral oil method make into
One step is described in detail, but not thereby limiting the invention.
Embodiment 1
Weigh 13.69g Choline Chlorides to be placed in 100mL beakers, then weigh 18.82g phenol and be added in Choline Chloride,
6.59g toluene is subsequently adding, at room temperature magnetic agitation 1 hour, after stirring terminates, is formed and contain neutral oil toluene and eutectic
The solution of solvent, the Phenol in Aqueous Solution is 2.0 with the mol ratio of Choline Chloride, and toluene is 0.35 with phenol quality ratio.Take this molten
In scale test tube, to the n-hexane for adding 40mL in the test tube, (n-hexane is liquid 5mL with the volume ratio of eutectic solvent
8.0), the magnetic agitation 30min at 20 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase n-hexane phase in test tube with
Lower phase eutectic solvent is mutually separated.The sample of phase n-hexane phase is taken, using gas-chromatography (Shimadzu GC-2014 gas phases
Chromatograph, chromatographic column is RTX-5 capillary columns, and detector is flame ionization ditector, and assay method is internal standard method, dichloro
Methane is solvent, and ortho-methylnitrobenzene is internal standard compound, and nitrogen is carrier gas, and 250 DEG C of injection room temperature, 260 DEG C of detector temperature heats up
Program is：80 DEG C of reservation 1min, are warming up to 220 DEG C with 40 DEG C/min speed afterwards, retain 3min, and analysis process is 7.5min)
The concentration of toluene is 23.10g/L in phase n-hexane phase in analysis, and the clearance of the neutral oil toluene in eutectic solvent is
92.1%.For upper phase hexane solution, hexane solution is distilled 2 hours in 80 DEG C of oil baths using Rotary Evaporators, obtained
To neutral oil toluene 1.1mL and n-hexane 39.8mL.
Embodiment 2
Weigh 13.69g Choline Chlorides to be placed in 100mL beakers, then weigh 9.41g phenol and be added in Choline Chloride,
3.30g toluene is subsequently adding, at room temperature magnetic agitation 1 hour, after stirring terminates, is formed and contain neutral oil toluene and eutectic
The solution of solvent, the Phenol in Aqueous Solution is 1.0 with the mol ratio of Choline Chloride, and toluene is 0.35 with phenol quality ratio.Take this molten
Liquid 5mL in scale test tube, to the n-hexane (volume ratio of n-hexane and eutectic solvent is 1.0) that 5mL is added in the test tube,
The magnetic agitation 30min at 20 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase n-hexane and lower phase in test tube
Eutectic solvent is separated.The sample of phase n-hexane phase is taken, (concrete analysis condition and method are shown in embodiment using gas-chromatography
1) concentration for analyzing toluene in upper phase n-hexane phase is 73.13g/L, and the clearance of the neutral oil toluene in eutectic solvent is
77.5%.For upper phase hexane solution, hexane solution is distilled 2 hours in 80 DEG C of oil baths using Rotary Evaporators, obtained
To neutral oil toluene 0.9mL and n-hexane 4.8mL.
Embodiment 3
Weigh 4.56g Choline Chlorides to be placed in 100mL beakers, then weigh 9.41g phenol and be added in Choline Chloride, so
0.47g toluene is added afterwards, at room temperature magnetic agitation 1 hour, after stirring terminates, form molten containing neutral oil toluene and eutectic
The solution of agent, the Phenol in Aqueous Solution is 3.0 with the mol ratio of Choline Chloride, and toluene is 0.05 with phenol quality ratio.Take the solution
5mL in scale test tube, to the n-hexane (volume ratio of n-hexane and eutectic solvent is 8.0) that 40mL is added in the test tube,
The magnetic agitation 30min at 10 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase n-hexane and lower phase in test tube
Eutectic solvent is separated.The sample of phase n-hexane phase is taken, (concrete analysis condition and method are shown in embodiment using gas-chromatography
1) concentration for analyzing toluene in upper phase n-hexane phase is 1.80g/L, and the clearance of the neutral oil toluene in eutectic solvent is
56.0%.For upper phase hexane solution, hexane solution is distilled 2 hours in 80 DEG C of oil baths using Rotary Evaporators, obtained
To neutral oil toluene 0.1mL and n-hexane 39.9mL.
Embodiment 4
Weigh 6.85g Choline Chlorides to be placed in 100mL beakers, then weigh 9.41g phenol and be added in Choline Chloride, so
2.35g toluene is added afterwards, at room temperature magnetic agitation 1 hour, after stirring terminates, form molten containing neutral oil toluene and eutectic
The solution of agent, the Phenol in Aqueous Solution is 2.0 with the mol ratio of Choline Chloride, and toluene is 0.25 with phenol quality ratio.Take the solution
5mL in scale test tube, to the n-hexane (volume ratio of n-hexane and eutectic solvent is 8.0) that 40mL is added in the test tube,
The magnetic agitation 30min at 25 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase n-hexane and lower phase in test tube
Eutectic solvent is separated.The sample of phase n-hexane phase is taken, (concrete analysis condition and method are shown in embodiment using gas-chromatography
1) concentration for analyzing toluene in upper phase n-hexane phase is 16.22g/L, and the clearance of the neutral oil toluene in eutectic solvent is
89.0%.For upper phase hexane solution, hexane solution is distilled 2 hours in 80 DEG C of oil baths using Rotary Evaporators, obtained
To neutral oil toluene 0.6mL and n-hexane 39.8mL.
Embodiment 5
Weigh 6.85g Choline Chlorides to be placed in 100mL beakers, then weigh 9.41g phenol and be added in Choline Chloride, so
2.82g toluene is added afterwards, at room temperature magnetic agitation 1 hour, after stirring terminates, form molten containing neutral oil toluene and eutectic
The solution of agent, the Phenol in Aqueous Solution is 2.0 with the mol ratio of Choline Chloride, and toluene is 0.30 with phenol quality ratio.Take the solution
5mL in scale test tube, to the n-hexane (volume ratio of n-hexane and eutectic solvent is 8.0) that 40mL is added in the test tube,
The magnetic agitation 30min under temperature 50 C, stands 20min.Using separatory funnel by the upper phase n-hexane and lower phase in test tube
Eutectic solvent is separated.The sample of phase n-hexane phase is taken, (concrete analysis condition and method are shown in embodiment using gas-chromatography
1) concentration for analyzing toluene in upper phase n-hexane phase is 19.86g/L, and the clearance of the neutral oil toluene in eutectic solvent is
90.9%.For upper phase hexane solution, hexane solution is distilled 2 hours in 80 DEG C of oil baths using Rotary Evaporators, obtained
To neutral oil toluene 0.8mL and n-hexane 40.0mL.
Embodiment 6
Weigh 6.85g Choline Chlorides to be placed in 100mL beakers, then weigh 9.41g phenol and be added in Choline Chloride, so
3.30g toluene is added afterwards, at room temperature magnetic agitation 1 hour, after stirring terminates, form molten containing neutral oil toluene and eutectic
The solution of agent, the Phenol in Aqueous Solution is 2.0 with the mol ratio of Choline Chloride, and toluene is 0.35 with phenol quality ratio.Take the solution
5mL in scale test tube, to the normal heptane (volume ratio of normal heptane and eutectic solvent is 8.0) that 40mL is added in the test tube,
The magnetic agitation 30min at 25 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase normal heptane and lower phase in test tube
Eutectic solvent is separated.The sample of phase normal heptane phase is taken, (concrete analysis condition and method are shown in embodiment using gas-chromatography
1) concentration for analyzing toluene in upper phase normal heptane phase is 22.8g/L, and the clearance of the neutral oil toluene in eutectic solvent is
92.2%.For upper phase n-heptane solution, n-heptane solution is distilled 2 hours in 100 DEG C of oil baths using Rotary Evaporators, obtained
To neutral oil toluene 1.0mL and normal heptane 39.9mL.
Embodiment 7
Weigh 13.69g Choline Chlorides to be placed in 100mL beakers, then weigh 9.41g phenol and be added in Choline Chloride,
0.47g toluene is subsequently adding, at room temperature magnetic agitation 1 hour, after stirring terminates, is formed and contain neutral oil toluene and eutectic
The solution of solvent, the Phenol in Aqueous Solution is 1.0 with the mol ratio of Choline Chloride, and toluene is 0.05 with phenol quality ratio.Take this molten
In scale test tube, to the normal heptane for adding 40mL in the test tube, (normal heptane is liquid 5mL with the volume ratio of eutectic solvent
8.0), the magnetic agitation 30min at 25 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase normal heptane phase in test tube with
Lower phase eutectic solvent is separated.The sample of phase normal heptane phase is taken, (concrete analysis condition and method are shown in reality using gas-chromatography
Apply example 1) concentration of toluene is 1.65g/L, the clearance of the neutral oil toluene in eutectic solvent in phase normal heptane phase in analysis
It is 55%.For upper phase n-heptane solution, n-heptane solution is distilled 2 hours in 100 DEG C of oil baths using Rotary Evaporators, obtained
To neutral oil toluene 0.1mL and normal heptane 39.8mL.
Embodiment 8
Weigh 4.56g Choline Chlorides to be placed in 100mL beakers, then weigh 9.41g phenol and be added in Choline Chloride, so
3.30g toluene is added afterwards, at room temperature magnetic agitation 1 hour, after stirring terminates, form molten containing neutral oil toluene and eutectic
The solution of agent, the Phenol in Aqueous Solution is 3.0 with the mol ratio of Choline Chloride, and toluene is 0.35 with phenol quality ratio.Take the solution
5mL in scale test tube, to the normal heptane (volume ratio of normal heptane and eutectic solvent is 8.0) that 40mL is added in the test tube,
The magnetic agitation 30min at 25 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase normal heptane and lower phase in test tube
Eutectic solvent is separated.The sample of phase normal heptane phase is taken, (concrete analysis condition and method are shown in embodiment using gas-chromatography
1) concentration for analyzing toluene in upper phase normal heptane phase is 22.1g/L, and the clearance of the neutral oil toluene in eutectic solvent is
91.4%.For upper phase n-heptane solution, n-heptane solution is distilled 2 hours in 100 DEG C of oil baths using Rotary Evaporators, obtained
To neutral oil toluene 0.9mL and normal heptane 39.9mL.
Embodiment 9
Weigh 13.69g Choline Chlorides to be placed in 100mL beakers, then weigh 9.41g phenol and be added in Choline Chloride,
0.47g toluene is subsequently adding, at room temperature magnetic agitation 1 hour, after stirring terminates, is formed and contain neutral oil toluene and eutectic
The solution of solvent, the Phenol in Aqueous Solution is 1.0 with the mol ratio of Choline Chloride, and toluene is 0.05 with phenol quality ratio.Take this molten
In scale test tube, to the hexamethylene for adding 40mL in the test tube, (hexamethylene is liquid 5mL with the volume ratio of eutectic solvent
8.0), the magnetic agitation 30min at 25 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase hexamethylene phase in test tube with
Lower phase eutectic solvent is separated.The sample of phase hexamethylene phase is taken, (concrete analysis condition and method are shown in reality using gas-chromatography
Apply example 1) concentration of toluene is 1.55g/L, the clearance of the neutral oil toluene in eutectic solvent in phase hexamethylene phase in analysis
It is 51.2%.For upper phase cyclohexane solution, cyclohexane solution is distilled 2 hours in 100 DEG C of oil baths using Rotary Evaporators,
Obtain neutral oil toluene 0.1mL and hexamethylene 39.9mL.
Embodiment 10
Weigh 4.56g Choline Chlorides to be placed in 100mL beakers, then weigh 9.41g phenol and be added in Choline Chloride, so
3.30g toluene is added afterwards, at room temperature magnetic agitation 1 hour, after stirring terminates, form molten containing neutral oil toluene and eutectic
The solution of agent, the Phenol in Aqueous Solution is 3.0 with the mol ratio of Choline Chloride, and toluene is 0.35 with phenol quality ratio.Take the solution
5mL in scale test tube, to the hexamethylene (volume ratio of hexamethylene and eutectic solvent is 8.0) that 40mL is added in the test tube,
The magnetic agitation 30min at 25 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase hexamethylene and lower phase in test tube
Eutectic solvent is separated.The sample of phase hexamethylene phase is taken, (concrete analysis condition and method are shown in embodiment using gas-chromatography
1) concentration for analyzing toluene in upper phase hexamethylene phase is 21.6g/L, and the clearance of the neutral oil toluene in eutectic solvent is
85.7%.For upper phase cyclohexane solution, cyclohexane solution is distilled 2 hours in 100 DEG C of oil baths using Rotary Evaporators, obtained
To neutral oil toluene 0.9mL and hexamethylene 39.9mL.
Embodiment 11
Weigh 5.48g tetramethyl ammonium chlorides to be placed in 100mL beakers, then weigh 9.41g phenol and be added to tetramethyl chlorine
Change in ammonium, be subsequently adding 3.30g toluene, at room temperature magnetic agitation 1 hour, after stirring terminates, formed and contain neutral oil toluene
With the solution of eutectic solvent, the Phenol in Aqueous Solution is 2.0 with the mol ratio of tetramethyl ammonium chloride, and toluene is with phenol quality ratio
0.35.Solution 5mL is taken in scale test tube, to normal heptane (normal heptane and eutectic solvent that 40mL is added in the test tube
Volume ratio is 8.0) the magnetic agitation 30min at 25 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase in test tube just
Heptane is separated with lower phase eutectic solvent.Take the sample of phase normal heptane phase, using gas-chromatography (concrete analysis condition and
Method is shown in embodiment 1) concentration of toluene is 22.8g/L, the neutral oil toluene in eutectic solvent in phase normal heptane phase in analysis
Clearance be 92.0%.For upper phase n-heptane solution, n-heptane solution is steamed in 100 DEG C of oil baths using Rotary Evaporators
Evaporate 2 hours, obtain neutral oil toluene 1.0mL and normal heptane 39.9mL.
Embodiment 12
Weigh 5.48g tetramethyl ammonium chlorides to be placed in 100mL beakers, then weigh 9.41g phenol and be added to tetramethyl chlorine
Change in ammonium, be subsequently adding 3.30g toluene, at room temperature magnetic agitation 1 hour, after stirring terminates, formed and contain neutral oil toluene
With the solution of eutectic solvent, the Phenol in Aqueous Solution is 2.0 with the mol ratio of tetramethyl ammonium chloride, and toluene is with phenol quality ratio
0.35.Solution 5mL is taken in scale test tube, to n-hexane (n-hexane and eutectic solvent that 40mL is added in the test tube
Volume ratio is 8.0) the magnetic agitation 30min at 25 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase in test tube just
Hexane is separated with lower phase eutectic solvent.Take the sample of phase n-hexane phase, using gas-chromatography (concrete analysis condition and
Method is shown in embodiment 1) concentration of toluene is 23.0g/L, the neutral oil toluene in eutectic solvent in phase n-hexane phase in analysis
Clearance be 92.1%.For upper phase hexane solution, hexane solution is steamed in 80 DEG C of oil baths using Rotary Evaporators
Evaporate 2 hours, obtain neutral oil toluene 1.1mL and n-hexane 39.8mL.
Embodiment 13
Weigh 8.29g etamon chlorides to be placed in 100mL beakers, then weigh 9.41g phenol and be added to tetraethyl chlorine
Change in ammonium, be subsequently adding 3.30g toluene, at room temperature magnetic agitation 1 hour, after stirring terminates, formed and contain neutral oil toluene
With the solution of eutectic solvent, the Phenol in Aqueous Solution is 2.0 with the mol ratio of etamon chloride, and toluene is with phenol quality ratio
0.35.Solution 5mL is taken in scale test tube, to normal heptane (normal heptane and eutectic solvent that 40mL is added in the test tube
Volume ratio is 8.0) the magnetic agitation 30min at 25 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase in test tube just
Heptane is separated with lower phase eutectic solvent.Take the sample of phase normal heptane phase, using gas-chromatography (concrete analysis condition and
Method is shown in embodiment 1) concentration of toluene is 23.2g/L, the neutral oil toluene in eutectic solvent in phase normal heptane phase in analysis
Clearance be 92.2%.For upper phase n-heptane solution, n-heptane solution is steamed in 100 DEG C of oil baths using Rotary Evaporators
Evaporate 2 hours, obtain neutral oil toluene 1.0mL and normal heptane 39.9mL.
Embodiment 14
Weigh 8.29g etamon chlorides to be placed in 100mL beakers, then weigh 9.41g phenol and be added to tetraethyl chlorine
Change in ammonium, be subsequently adding 3.30g toluene, at room temperature magnetic agitation 1 hour, after stirring terminates, formed and contain neutral oil toluene
With the solution of eutectic solvent, the Phenol in Aqueous Solution is 2.0 with the mol ratio of etamon chloride, and toluene is with phenol quality ratio
0.35.Solution 5mL is taken in scale test tube, to n-hexane (n-hexane and eutectic solvent that 40mL is added in the test tube
Volume ratio is 8.0) the magnetic agitation 30min at 25 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase in test tube just
Hexane is separated with lower phase eutectic solvent.Take the sample of phase n-hexane phase, using gas-chromatography (concrete analysis condition and
Method is shown in embodiment 1) concentration of toluene is 23.0g/L, the neutral oil toluene in eutectic solvent in phase n-hexane phase in analysis
Clearance be 92.4%.For upper phase hexane solution, hexane solution is steamed in 80 DEG C of oil baths using Rotary Evaporators
Evaporate 2 hours, obtain neutral oil toluene 1.1mL and n-hexane 39.8mL.
Embodiment 15
The reuse experiment of extractant.
Weigh 13.69g Choline Chlorides to be placed in 100mL beakers, then weigh 18.82g phenol and be added in Choline Chloride,
6.59g toluene is subsequently adding, at room temperature magnetic agitation 1 hour, after stirring terminates, is formed and contain neutral oil toluene and eutectic
The solution of solvent, the Phenol in Aqueous Solution is 2.0 with the mol ratio of Choline Chloride, and toluene is 0.35 with phenol quality ratio.Take this molten
In scale test tube, to the n-hexane for adding 40mL in the test tube, (n-hexane is liquid 5mL with the volume ratio of eutectic solvent
8.0), the magnetic agitation 30min at 25 DEG C of temperature, stands 20min.Using separatory funnel by the upper phase n-hexane phase in test tube with
Lower phase eutectic solvent is separated.The sample of phase n-hexane phase is taken, (concrete analysis condition and method are shown in reality using gas-chromatography
Apply example 1) concentration of toluene is 23.0g/L, the clearance of the neutral oil toluene in eutectic solvent in phase n-hexane phase in analysis
It is 92.2%.For upper phase hexane solution, hexane solution is distilled 2 hours in 80 DEG C of oil baths using Rotary Evaporators,
Obtain neutral oil toluene 1.1mL and n-hexane 39.8mL.
Hexane solution after regeneration is recycled and reused for extracting the neutral oil toluene in above-mentioned eutectic solvent, and this operation is repeated
Five times.The clearance of five neutral oil toluene of experiment is respectively 92.2%, 92.0%, 92.3%, 92.4%, 91.9%.
Embodiment 16
Take true coal tar (180 DEG C~230 DEG C fraction sections of coal direct liquefaction oil, the mass fraction containing total phenol of 150.92g
For the Choline Chloride that 33.53%) in 1000mL beakers, is added thereto to 35.33g, (total phenol is measured according to cresols, total phenol and chlorine
Change choline mol ratio to be about 2.0), be placed in magnetic agitation 30min in 25 DEG C of waters bath with thermostatic control, be subsequently transferred to 500mL separatory funnels
In, it is layered after standing 2 hours, then divide liquid, phase eutectic solvent phase is removed, volume is 66.1mL, and the part is true oil
Eutectic solvent containing neutral oil in phenol separation process.The eutectic solvent point is 2 parts.
Part 1 is contrast experiment.To 500mL back washing agent ethyl acetate is directly added into part 1 eutectic solvent, stir
After mixing 30min, filtering takes liquid phase, the rotary evaporation in the oil bath that temperature is 110 DEG C, speed of rotation 50r/min, rotary distillation
Time 2 h, obtains product 27.1g.The yield of product is 108%, and wherein product form is：Total phenol mass content 77.10%,
Neutral oil mass content 21.70%, ethyl acetate mass content 1.20%.
Part 2 is extraction removal neutral oil experiment.250mL n-hexanes are being added in part 2 eutectic solvent (just
Hexane is that 8.0), being transferred into separatory funnel after stirring 30min carries out a point liquid, obtains lower phase with the volume ratio of eutectic solvent
Volume be 25.4mL.Phase eutectic solvent is removed, 500mL back washing agent ethyl acetate is added thereto to, after stirring 30min, mistake
Filter, takes liquid phase, and the rotary evaporation in the oil bath that temperature is 110 DEG C, speed of rotation 50r/min, rotary distillation time 2 h is obtained
To product 21.3g.The yield of product is 85%, and wherein product form is：Total phenol mass content 96.86%, neutral oil quality contains
Amount 1.92%, ethyl acetate mass content 1.22%.
From above-mentioned contrast experiment, using the neutral oil in extraction removal eutectic solvent after, in product phenol in
Property oil content be greatly reduced.
Claims (8)
1. a kind of method of the neutral oil carried secretly in removal eutectic solvent, the method is included to the eutectic solvent containing neutral oil
Extractant low-carbon alkanes extraction neutral oil and extractant low-carbon alkanes are added in (being formed by quaternary ammonium salt and phenolic compound) again
Raw step.
2. process according to claim 1, it is characterised in that described low-carbon alkanes are selected from n-hexane, hexamethylene,
Normal heptane.
3. process according to claim 1, it is characterised in that described quaternary ammonium salt includes Choline Chloride, tetramethyl
Ammonium chloride, etamon chloride.
4. process according to claim 1, it is characterised in that neutral oil and phenols in described eutectic solvent
The mass ratio of compound is 0.05~0.35.
5. process according to claim 1, it is characterised in that phenolic compound and season in described eutectic solvent
The mol ratio of ammonium salt is 1.0~3.0.
6. process according to claim 1, it is characterised in that extraction temperature is 10 DEG C~50 DEG C.
7. process according to claim 1, it is characterised in that the low-carbon alkanes of addition and the volume of eutectic solvent
Than being 1.0~8.0.
8. process according to claim 1, it is characterised in that the steaming of extractant low-carbon alkanes and neutral oil mixture
Separation temperature is evaporated for 80 DEG C~110 DEG C.
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| CN113200869B (en) * | 2021-04-28 | 2023-06-23 | 南京长江江宇环保科技股份有限公司 | Method for recycling tetramethyl ammonium chloride from semiconductor development wastewater |
| CN114247178A (en) * | 2021-12-22 | 2022-03-29 | 中国石油天然气集团有限公司 | Extractant for treating oil-based drilling cuttings and application thereof |
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