CN104946303A - Method for selectively separating phenol mixture from oil - Google Patents
Method for selectively separating phenol mixture from oil Download PDFInfo
- Publication number
- CN104946303A CN104946303A CN201510254744.0A CN201510254744A CN104946303A CN 104946303 A CN104946303 A CN 104946303A CN 201510254744 A CN201510254744 A CN 201510254744A CN 104946303 A CN104946303 A CN 104946303A
- Authority
- CN
- China
- Prior art keywords
- oil
- phenol
- congruent melting
- cresols
- melting solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a method for selectively separating a phenol mixture from oil, which comprises the following steps: by using a quaternary ammonium salt as a separating agent, selectively forming a congruent melting liquid from the separating agent and phenol compounds (phenol, cresol and dimethyl phenol) in the oil at 0-30 DEG C, thereby separating the phenol compounds from the oil; and carrying out back extraction on the phenol compounds containing the congruent melting liquid to separate the phenol substances from the quaternary ammonium salt, thereby obtaining the product and recovering the extractant. The method has the advantages of simple technique, low separate cost and environment friendliness.
Description
Technical field
The present invention relates to the selective separation method containing phenol mixture in a kind of aromatic hydrocarbons and fat hydrocarbon mixture.
Background technology
Phenolic compound is the important industrial chemicals of a class, is widely used in the fields such as fiber, plastics, agricultural chemicals, medicine, sanitas, Shattering rate.Pyrolysis of coal is oily, Coal Liquefaction is oily and contain a large amount of phenolic compounds in biomass pyrolysis oil, as materials such as phenol, cresols, xylenols.From these oil, first the traditional method of separating phenols compounds is adopt alkali lye chemical extraction method, it is utilize phenolic compound to have slightly acidic that alkali lye (as sodium hydroxide solution) extracts ratio juris, after reacting with sodium hydroxide, form sodium phenolate solution soluble in water, phenolic compound is transferred to aqueous phase from oil phase, reaches the object of separation.The regenerative process of sodium phenolate is: with the carbonic acid stronger than phenol acidity and sulfate reduction phenolic compound, obtain phenol mixture (crude phenols); Next is separated phenol mixture with rectification method.Although this separation method selectivity is higher, need to consume a large amount of acid-base solution, high to equipment requirements; After pickling terminates, produce a large amount of phenolic wastewater, cause last handling process complicated, environmental pollution is serious; Because the boiling point of phenol mixture is close, cause separating energy consumption high.Except above-mentioned separation method, the method studied at present comprises superheated water extraction process, brine method and alcohol water extraction separation method etc., although these to a certain extent can from oil separating phenols mixture, but still with a large amount of organic solvents or water, exist equally seriously polluted, separation efficiency is low.Use water can produce a large amount of phenolic wastewater, with an organic solvent then, then the solvent loss that the dissolving of organic solvent in oil cannot be avoided to cause, causes separation costs higher.
As mentioned above, the phenol mixture obtained from pyrolysis of coal oil, the oily and biomass pyrolysis oil of Coal Liquefaction is mainly made up of materials such as phenol, cresols, xylenols, these matter selectives can not be separated in above-mentioned extraction separation process, and then need follow-up being separated again.
Summary of the invention
The object of this invention is to provide that a kind of technique is simple, separation costs is low, the environmentally friendly method taking quaternary ammonium salt as extraction agent and carry out phenol mixture in selective separation oil (phenol, cresols, xylenol).
The present invention take quaternary ammonium salt as separating agent, in the scope and oil of temperature 0 DEG C-30 DEG C, phenolic compound (phenol, cresols, xylenol) selectivity forms congruent melting liquid, thus the separation of phenolic compound in realization oil, the mode of phenolic compound containing congruent melting liquid by stripping, aldehydes matter is separated with quaternary ammonium salt, obtain product, reclaim extraction agent.
The invention provides the method for phenol mixture in a kind of selective separation oil, comprise the steps:
(1) by the add-on of quaternary ammonium salt be 0.3 times-0.6 times of phenol mole number, quaternary ammonium salt is added in oil, at separation temperature is 0 DEG C-30 DEG C, after churning time 1min-30min, leave standstill 1min-20min, system is divided into two-phase, and the phenol that quaternary ammonium salt is optionally stronger with reactive force first forms congruent melting solvent, this congruent melting solvent and oil phase do not dissolve each other thus and separation of oil, obtain the congruent melting solvent of phenol-rich and the oil of de-phenol after separation;
(2) by the add-on of quaternary ammonium salt be 0.4 times-0.7 times of cresols mole number, quaternary ammonium salt is added in step (1) dephenolize oil, at separation temperature is 0 DEG C-30 DEG C, after churning time 1min-30min, leave standstill 1min-20min, the cresols that quaternary ammonium salt optionally takes second place with reactive force forms congruent melting solvent, this congruent melting solvent and oil phase do not dissolve each other and and separation of oil, obtain being rich in the congruent melting solvent of cresols and the oil of de-phenol and cresols after separation;
(3) by the add-on of quaternary ammonium salt be 0.5 times-0.9 times of xylenol mole number, quaternary ammonium salt is added again in step (2) dephenolize oil, at separation temperature is 0 DEG C-30 DEG C, after churning time 1min-30min, leave standstill 1min-20min, the xylenol that quaternary ammonium salt is optionally less with reactive force forms congruent melting solvent, this congruent melting solvent and oil phase do not dissolve each other and and separation of oil, obtain being rich in the congruent melting solvent of xylenol and the neutral oil of de-phenol, cresols and xylenol after separation;
(4), after above-mentioned separation terminates, respectively under pressure 0.01atm-0.06atm, temperature 60 C-90 DEG C of conditions, underpressure distillation is carried out to three kinds of congruent melting solvents, remove the neutral oil wherein carried;
(5) be 4-7:1 by the volume ratio of solvent resistant and congruent melting solvent, remove in the congruent melting solvent of neutral oil respectively to above-mentioned three kinds and add solvent resistant, at separation temperature 0 DEG C-30 DEG C, quaternary ammonium salt recrystallization is separated out in solid form, filter, realize the regeneration of quaternary ammonium salt, obtain three kinds of solvent resistant solution containing phenol;
(6) distill the solvent resistant solution that three kinds contain phenol respectively, be separated by phenolic compound with solvent resistant, obtain phenol, cresols, xylenol and solvent resistant respectively, solvent resistant is reused.
In aforesaid method, described oil is the mixture of aromatic hydrocarbons, aliphatic hydrocarbon and phenolic compound, and wherein aromatic hydrocarbons and aliphatic hydrocarbon are neutral oil.
In aforesaid method, in oil, phenolic compound concentration is 50g/L-300g/L.
In aforesaid method, described quaternary ammonium salt is choline chloride 60, tetramethyl ammonium chloride, etamon chloride, methyl triethyl ammonium chloride, tetraethylammonium bromide or 4 bromide.The quaternary ammonium salt that step (1)-(3) add is identical.
In aforesaid method, solvent resistant is ether, isopropyl ether, n-butyl ether, ethyl acetate or methyl-formiate.
In quaternary ammonium salt selective extraction separating oil, the principle of phenolic compound is: the phenolic compound in oil contains the functional groups such as hydroxyl, these functional groups can form intermolecular hydrogen bonding with the halogen ion of quaternary ammonium salt, thus reduce quaternary ammonium salt and phenolic compound reactive force in molecule separately, and then form congruent melting solvent.This congruent melting solvent and oil phase do not dissolve each other, and form cenotype, thus achieve the separation of oily phenol.Because phenol, cresols are different with the structure of xylenol, when they and quaternary ammonium salt form congruent melting solvent, reactive force is different, the different reason of reactive force be on cresols and xylenol containing methyl, produce sterically hindered, cause reactive force different.In three kinds of phenol, the reactive force of phenol is the strongest, and forming congruent melting solvent at first with quaternary ammonium salt, is secondly cresols, is finally xylenol.If add-on is inexcessive when adding quaternary ammonium salt, competes and acting between different phenol and quaternary ammonium salt, the first formation congruent melting solvent that reactive force is large, the method like this by progressively adding quaternary ammonium salt realizes the separation of different phenol.If the quaternary ammonium salt amount once added is too much, all phenol simultaneously with quaternary ammonium salt effect, form congruent melting solvent, neutral oil can only be separated with phenolic compound.
Compared with prior art, the present invention at least possesses following beneficial effect.
1, compared with traditional sodium hydroxide solution elution method, the present invention adopts quaternary ammonium salt to be separating agent, and separating agent can be reused, and can also avoid the use of a large amount of acid-base solution and the generation of phenolic wastewater, reduce separation costs.
2, compared with traditional sodium hydroxide solution elution method, the present invention adopts phenol mixture in the mode extraction oil of stepwise solvent extraction, and extraction agent has selectivity, and realize the separation of three kinds of phenol, separation efficiency is high simultaneously.
3, do not use water in sepn process of the present invention, do not have phenolic wastewater to produce, reduce environmental pollution;
4, aldehydes matter close for character can be separated by the present invention from oily phenol mixture, and realize extracting and separating and complete simultaneously, separation efficiency is high;
5, compare with traditional extraction process, extraction agent quaternary ammonium salt consumption of the present invention is few, and can reuse, and substantially reduces separator volume.
6, solvent resistant of the present invention is also reusable, substantially reduces separation costs.
Embodiment
Below in conjunction with embodiment to provided by the invention be separating agent with quaternary ammonium salt, in selective separation oil, the processing method of phenolic compound is described in further detail, but not thereby limiting the invention.
Embodiment 1
Simulated oil is 80% toluene+20% normal hexane (volume ratio) solution containing different phenol, and wherein phenol content 100.1g/L, o-cresol content 99.2g/L, 2,6-xylenol content are 99.5g/L.Get simulated oil 500mL, under temperature 5 DEG C of conditions, with choline chloride 60 extracting and separating phenolic compound.
First time adds choline chloride 60 37.1g in simulated oil, is 50% of phenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and removes the simulated oil after phenol mutually with upper.First time extraction obtains 98.1g congruent melting solvent, and (take a morsel sample, dissolves phenol and neutral oil with methylene dichloride, then adopts gas chromatographic analysis composition, calculate amount in congruent melting solvent to analyze composition.Following analytical procedure is identical, no longer repeat specification), neutral oil (referring to toluene and normal hexane, lower same) content is wherein 9.9%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.5%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim choline chloride 60.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (phenol-rich), its quality is 51.6g, consist of phenol 85.3%, cresols 9.7%, xylenol 4.4%, neutral oil 0.6%, be all massfraction (embodiment is identical) below.
Second time removes in the simulated oil after phenol to first time and adds choline chloride 60 38.4g, for 60% of cresols mole number, stir 10min, leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and the upper simulated oil removed mutually after phenol and ortho-cresol.Second time extraction obtains 89.8g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 9.1%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.6%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim choline chloride 60.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (being rich in cresols), its quality is 43.4g, consists of phenol 3.7%, cresols 87.5%, xylenol 8.0%, neutral oil 0.8%.
Third time adds choline chloride 60 39.8g in the simulated oil after first time and second time remove phenol and cresols, is 70% of xylenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory shifts out lower phase congruent melting solvent phase.Employing silver nitrate titration method is analyzed, and does not find that there is choline chloride 60 in upper phase oil phase.Third time extraction obtains 45.7g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 2.1%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.7%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim choline chloride 60.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (being rich in xylenol), its quality is 5.1g, consists of phenol 9.3%, cresols 9.3%, xylenol 80.4%, neutral oil 1.0%.
Embodiment 2
Simulated oil is 80% toluene+20% normal hexane (volume ratio) solution containing different phenol, and wherein phenol content 100.1g/L, o-cresol content 99.2g/L, 2,6-xylenol content are 99.5g/L.Get simulated oil 500mL, under temperature 5 DEG C of conditions, with tetramethyl ammonium chloride extracting and separating phenolic compound.
First time adds tetramethyl ammonium chloride 29.1g in simulated oil, is 50% of phenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and removes the simulated oil after phenol mutually with upper.First time extraction obtains 96.1g congruent melting solvent, and analyze composition, wherein neutral oil content is 11.2%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.4%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ether of 6 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim tetramethyl ammonium chloride.To the above-mentioned diethyl ether solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ether, and obtain product phenolic compound (phenol-rich), its quality is 56.6g, consists of containing phenol 83.2%, cresols 11.5%, xylenol 4.8%, neutral oil 0.5%.
Second time adds tetramethyl ammonium chloride 30.2g to removing in the simulated oil after phenol through first time, for 60% of cresols mole number, stir 10min, leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and the upper simulated oil removed mutually after phenol and ortho-cresol.Second time extraction obtains 79.4g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 10.0%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.6%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ether of 6 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim tetramethyl ammonium chloride.To the above-mentioned diethyl ether solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ether, and obtain product phenolic compound (being rich in cresols), its quality is 41.6g, consists of phenol 3.5%, cresols 89.5%, xylenol 6.0%, neutral oil 1.0%.
Third time adds tetramethyl ammonium chloride 31.3g in the simulated oil after first time and second time remove phenol and cresols, is 70% of xylenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory shifts out lower phase congruent melting solvent phase.Employing silver nitrate titration method is analyzed, and does not find that there is tetramethyl ammonium chloride in upper phase oil phase.Third time extraction obtains 47.5g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 5.5%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.4%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ether of 6 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim tetramethyl ammonium chloride.To the above-mentioned diethyl ether solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ether, and obtain product phenolic compound (being rich in xylenol), its quality is 13.7g, consists of phenol 2.9%, cresols 1.8%, xylenol 94.5%, neutral oil 0.8%.
Embodiment 3
Simulated oil is 80% toluene+20% normal hexane (volume ratio) solution containing different phenol, and wherein phenol content 100.1g/L, o-cresol content 99.2g/L, 2,6-xylenol content are 99.5g/L.Get simulated oil 500g, under temperature 5 DEG C of conditions, with etamon chloride extracting and separating phenolic compound.
First time adds etamon chloride 44.1g in simulated oil, is 50% of phenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and removes the simulated oil after phenol mutually with upper.First time extraction obtains 117.2g congruent melting solvent, and analyze composition, neutral oil content is 10.3%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.4%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (phenol-rich), its quality is 61.4g, consists of phenol 78.1%, cresols 15.2%, xylenol 6.0%, neutral oil 0.7%.
Second time adds etamon chloride 45.6g to removing in the simulated oil after phenol through first time, for 60% of cresols mole number, stir 10min, leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and the upper simulated oil removed mutually after phenol and ortho-cresol.Second time extraction obtains 97.3g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 9.1%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.3%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (being rich in cresols), its quality is 43.1g, consists of phenol 2.0%, cresols 83.6%, xylenol 13.9%, neutral oil 0.5%.
Third time adds etamon chloride 47.3g in the simulated oil after first time and second time remove phenol and cresols, is 70% of xylenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory shifts out lower phase congruent melting solvent phase.Employing silver nitrate titration method is analyzed, and does not find that there is etamon chloride in upper phase oil phase.Third time extraction obtains 83.6g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 7.7%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.3%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (being rich in xylenol), its quality is 30.1g, consists of phenol 1.1%, cresols 2.2%, xylenol 96.1%, neutral oil 0.6%.
Embodiment 4
Simulated oil is 80% toluene+20% normal hexane (volume ratio) solution containing different phenol, and wherein phenol content 100.1g/L, o-cresol content 99.2g/L, 2,6-xylenol content are 99.5g/L.Get simulated oil 500g, under temperature 5 DEG C of conditions, with methyl triethyl ammonium chloride extracting and separating phenolic compound.
First time adds methyl triethyl ammonium chloride 40.3g in simulated oil, is 50% of phenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and removes the simulated oil after phenol mutually with upper.First time extraction obtains 109.2g congruent melting solvent, and analyze composition, neutral oil content is 10.4%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.4%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim methyl triethyl ammonium chloride.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (phenol-rich), its quality is 57.8g, consists of phenol 82.5%, cresols 10.4%, xylenol 6.4%, neutral oil 0.7%.
Second time adds methyl triethyl ammonium chloride 41.8g to removing in the simulated oil after phenol through first time, for 60% of cresols mole number, stir 10min, leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and the upper simulated oil removed mutually after phenol and ortho-cresol.Second time extraction obtains 91.6g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 9.1%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.3%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim methyl triethyl ammonium chloride.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (being rich in cresols), its quality is 41.8g, consists of phenol 1.7%, cresols 91.7%, xylenol 5.9%, neutral oil 0.7%.
Third time adds methyl triethyl ammonium chloride 43.3g in the simulated oil after first time and second time remove phenol and cresols, is 70% of xylenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory shifts out lower phase congruent melting solvent phase.Employing silver nitrate titration method is analyzed, and does not find that there is methyl triethyl ammonium chloride in upper phase oil phase.Third time extraction obtains 80.2g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 7.8%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.3%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim methyl triethyl ammonium chloride.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (being rich in xylenol), its quality is 30.8g, consists of phenol 1.1%, cresols 2.6%, xylenol 95.7%, neutral oil 0.6%.
Embodiment 5
Simulated oil is 80% toluene+20% normal hexane (volume ratio) solution containing different phenol, and wherein phenol content 100.1g/L, o-cresol content 99.2g/L, 2,6-xylenol content are 99.5g/L.Get simulated oil 500g, under temperature 5 DEG C of conditions, with tetraethylammonium bromide extracting and separating phenolic compound.
First time adds tetraethylammonium bromide 55.9g in simulated oil, is 50% of phenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and removes the simulated oil after phenol mutually with upper.First time extraction obtains 127.2g congruent melting solvent, and analyze composition, neutral oil content is 9.0%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.4%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim tetraethylammonium bromide.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (phenol-rich), its quality is 60.3g, consists of phenol 79.4%, cresols 13.0%, xylenol 7.0%, neutral oil 0.6%.
Second time adds tetraethylammonium bromide 57.8g to removing in the simulated oil after phenol through first time, for 60% of cresols mole number, stir 10min, leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and the upper simulated oil removed mutually after phenol and ortho-cresol.Second time extraction obtains 104.5g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 7.3%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.3%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim tetraethylammonium bromide.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (being rich in cresols), its quality is 39.4g, consists of phenol 1.4%, cresols 90.5%, xylenol 7.6%, neutral oil 0.5%.
Third time adds tetraethylammonium bromide 60.0g in the simulated oil after first time and second time remove phenol and cresols, is 70% of xylenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory shifts out lower phase congruent melting solvent phase.Employing silver nitrate titration method is analyzed, and does not find that there is tetraethylammonium bromide in upper phase oil phase.Third time extraction obtains 95.3g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 6.3%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.3%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim tetraethylammonium bromide.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (being rich in xylenol), its quality is 29.5g, consists of phenol 0.5%, cresols 2.2%, xylenol 96.7%, neutral oil 0.6%.
Embodiment 6
Simulated oil is 90% toluene+10% normal hexane (volume ratio) solution containing different phenol, and wherein phenol content 100.6g/L, o-cresol content 60.2g/L, 2,6-xylenol content are 60.0g/L.Get simulated oil 500g, under temperature 15 DEG C of conditions, with etamon chloride extracting and separating phenolic compound.
First time adds etamon chloride 35.4g in simulated oil, is 40% of phenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and removes the simulated oil after phenol mutually with upper.First time extraction obtains 99.8g congruent melting solvent, and analyze composition, neutral oil content is 11.5%.Under the condition of temperature 80 DEG C, pressure 0.015atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.3%.Under 15 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 6 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (phenol-rich), its quality is 53.2g, consists of phenol 85.6%, cresols 8.3%, xylenol 5.6%, neutral oil 0.5%.
Second time adds etamon chloride 32.3g to removing in the simulated oil after phenol through first time, for 70% of cresols mole number, stir 10min, leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and the upper simulated oil removed mutually after phenol and ortho-cresol.Second time extraction obtains 65.3g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 9.2%.Under the condition of temperature 80 DEG C, pressure 0.015atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.3%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 6 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (being rich in cresols), its quality is 27.2g, consists of phenol 12.6%, cresols 79.5%, xylenol 7.4%, neutral oil 0.5%.
Third time adds etamon chloride 32.6g in the simulated oil after first time and second time remove phenol and cresols, is 80% of xylenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory shifts out lower phase congruent melting solvent phase.Employing silver nitrate titration method is analyzed, and does not find that there is etamon chloride in upper phase oil phase.Third time extraction obtains 52.1g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 7.5%.Under the condition of temperature 80 DEG C, pressure 0.015atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.3%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (being rich in xylenol), its quality is 15.6g, consists of phenol 2.8%, cresols 4.4%, xylenol 92.1%, neutral oil 0.7%.
Embodiment 7
Simulated oil is 80% toluene+20% normal hexane (volume ratio) solution containing different phenol, and wherein phenol content 102.4g/L, o-cresol content 61.2g/L, 2,6-xylenol content are 60.4g/L.Get simulated oil 500mL, under temperature 20 DEG C of conditions, with etamon chloride extracting and separating phenolic compound, and carry out the revision test of extraction agent.
(1) extraction agent test is used first
First time adds etamon chloride 45.1g in simulated oil, is phenol mole number 50%, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and removes the simulated oil after phenol mutually with upper.First time extraction obtains 109.3g congruent melting solvent, and analyze composition, neutral oil content is 9.7%.Under the condition of temperature 90 DEG C, pressure 0.05atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 20min, neutral oil mass content is reduced to 0.4%.Under 15 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 6 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (phenol-rich), its quality is 53.9g, consists of phenol 85.7%, cresols 8.7%, xylenol 5.0%, neutral oil 0.6%.
Second time adds etamon chloride 28.1g to removing in the simulated oil after phenol through first time, for 60% of cresols mole number, stir 10min, leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and the upper simulated oil removed mutually after phenol and ortho-cresol.Second time extraction obtains 60.6g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 9.2%.Under the condition of temperature 80 DEG C, pressure 0.05atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 20min, neutral oil mass content is reduced to 0.3%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 6 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (being rich in cresols), its quality is 27.0g, consists of phenol 12.6%, cresols 79.8%, xylenol 7.0%, neutral oil 0.6%.
Third time adds etamon chloride 28.7g in the simulated oil after first time and second time remove phenol and cresols, is 70% of xylenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory shifts out lower phase congruent melting solvent phase.Employing silver nitrate titration method is analyzed, and does not find that there is etamon chloride in upper phase oil phase.Third time extraction obtains 46.9g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 7.1%.Under the condition of temperature 90 DEG C, pressure 0.04atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 20min, neutral oil mass content is reduced to 0.3%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ethyl acetate of 5 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned ethyl acetate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ethyl acetate, and obtain product phenolic compound (being rich in xylenol), its quality is 15.1g, consists of phenol 3.3%, cresols 5.5%, xylenol 90.7%, neutral oil 0.5%.
(2) extraction agent test is reused
Carry out reusing test after the extraction agent etamon chloride drying that above-mentioned recovery is obtained.Get above-mentioned simulated oil 500mL, in simulated oil, add etamon chloride three times respectively, add-on and operational condition with use extraction agent test conditions identical first.
First time adds etamon chloride 45.1g in simulated oil, process identical after adding etamon chloride with first time in using extraction agent to test first, obtain product phenolic compound (phenol-rich), its quality is 53.2g, consists of phenol 85.4%, cresols 9.0%, xylenol 4.9%, neutral oil 0.7%.
Second time adds etamon chloride 28.1g to removing in the simulated oil after phenol through first time, process identical after adding etamon chloride with second time in using extraction agent to test first, obtain product phenolic compound (being rich in cresols), its quality is 27.2g, consists of phenol 12.9%, cresols 79.6%, xylenol 6.8%, neutral oil 0.7%.
Third time adds etamon chloride 28.7g in the simulated oil after first time and second time remove phenol and cresols, process identical after adding etamon chloride with third time in using extraction agent to test first, obtain product phenolic compound (being rich in xylenol), its quality is 15.1g, consists of phenol 3.3%, cresols 5.4%, xylenol 90.7%, neutral oil 0.6%.
(3) extraction agent test is reused
Test is reused by carrying out third time after reclaiming the extraction agent etamon chloride drying that obtains in (two) revision test.Get above-mentioned simulated oil 500mL, add etamon chloride three times respectively in simulated oil, add-on is identical with first time revision test condition with operational condition.
First time adds etamon chloride 45.1g in simulated oil, process identical after adding etamon chloride with first time in using extraction agent to test first, obtain product phenolic compound (phenol-rich), its quality is 53.3g, consists of phenol 85.2%, cresols 9.4%, xylenol 4.7%, neutral oil 0.7%.
Second time adds etamon chloride 28.1g to removing in the simulated oil after phenol through first time, process identical after adding etamon chloride with second time in using extraction agent to test first, obtain product phenolic compound (being rich in cresols), its quality is 27.4g, consists of phenol 12.9%, cresols 79.2%, xylenol 7.2%, neutral oil 0.6%.
Third time adds etamon chloride 28.7g in the simulated oil after first time and second time remove phenol and cresols, process identical after adding etamon chloride with third time in using extraction agent to test first, obtain product phenolic compound (being rich in xylenol), its quality is 14.8g, consists of phenol 3.1%, cresols 5.5%, xylenol 90.9%, neutral oil 0.5%.
Embodiment 8
Simulated oil is 90% toluene+10% normal hexane (volume ratio) solution containing different phenol, and wherein phenol content 100.6g/L, o-cresol content 60.2g/L, 2,6-xylenol content are 60.0g/L.Get simulated oil 500g, under temperature 15 DEG C of conditions, with etamon chloride extracting and separating phenolic compound.
First time adds etamon chloride 26.6g in simulated oil, is 30% of phenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and removes the simulated oil after phenol mutually with upper.First time extraction obtains 82.4g congruent melting solvent, and analyze composition, neutral oil content is 12.0%.Under the condition of temperature 80 DEG C, pressure 0.015atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 20min, neutral oil mass content is reduced to 0.3%.Under 15 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the methyl-formiate of 7 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned methyl-formiate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery methyl-formiate, and obtain product phenolic compound (phenol-rich), its quality is 46.2g, consists of phenol 95.4%, cresols 3.0%, xylenol 1.1%, neutral oil 0.5%.
Second time removes etamon chloride 32.3g in the simulated oil after phenol to through first time, for 70% of cresols mole number, stir 10min, leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and the upper simulated oil removed mutually after phenol and ortho-cresol.Second time extraction obtains 73.5g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 10.1%.Under the condition of temperature 80 DEG C, pressure 0.015atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 20min, neutral oil mass content is reduced to 0.4%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the methyl-formiate of 7 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned methyl-formiate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery methyl-formiate, and obtain product phenolic compound (being rich in cresols), its quality is 34.1g, consists of phenol 14.3%, cresols 72.0%, xylenol 13.2%, neutral oil 0.5%.
Third time adds etamon chloride 36.6g in the simulated oil after first time and second time remove phenol and cresols, is 90% of xylenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory shifts out lower phase congruent melting solvent phase.Employing silver nitrate titration method is analyzed, and does not find that there is etamon chloride in upper phase oil phase.Third time extraction obtains 56.0g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 7.0%.Under the condition of temperature 80 DEG C, pressure 0.015atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 20min, neutral oil mass content is reduced to 0.3%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the methyl-formiate of 7 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned methyl-formiate solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery methyl-formiate, and obtain product phenolic compound (being rich in xylenol), its quality is 15.5g, consists of phenol 3.2%, cresols 4.2%, xylenol 92.1%, neutral oil 0.5%.
Embodiment 9
Simulated oil is 80% toluene+20% normal hexane (volume ratio) solution containing different phenol, and wherein phenol content 100.1g/L, o-cresol content 99.2g/L, 2,6-xylenol content are 99.5g/L.Get simulated oil 500g, under temperature 5 DEG C of conditions, with etamon chloride extracting and separating phenolic compound.
First time adds etamon chloride 52.9g in simulated oil, is 60% of phenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and removes the simulated oil after phenol mutually with upper.First time extraction obtains 130.7g congruent melting solvent, and analyze composition, neutral oil content is 9.8%.Under the condition of temperature 70 C, pressure 0.01atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.4%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ether of 7 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned diethyl ether solution containing phenolic compound, 60 DEG C, under condition of negative pressure, carry out Distillation recovery ether, and obtain product phenolic compound (phenol-rich), its quality is 65.3g, consists of phenol 73.6%, cresols 19.8%, xylenol 6.1%, neutral oil 0.5%.
Second time removes etamon chloride 41.8g in the simulated oil after phenol to through first time, for 55% of cresols mole number, stir 10min, leave standstill 5min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and the upper simulated oil removed mutually after phenol and ortho-cresol.Second time extraction obtains 88.8g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 9%.Under the condition of temperature 70 C, pressure 0.01atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.4%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ether of 7 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned diethyl ether solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ether, and obtain product phenolic compound (being rich in cresols), its quality is 39.2g, consists of phenol 1.8%, cresols 83.1%, xylenol 14.7%, neutral oil 0.4%.
Third time adds etamon chloride 47.3g in the simulated oil after first time and second time remove phenol and cresols, is 70% of xylenol mole number, stirs 10min, and leave standstill 5min, system is divided into two-phase, and then separatory shifts out lower phase congruent melting solvent phase.Employing silver nitrate titration method is analyzed, and does not find that there is etamon chloride in upper phase oil phase.Third time extraction obtains 83.4g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 7.5%.Under the condition of temperature 70 C, pressure 0.01atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.3%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the ether of 7 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim etamon chloride.To the above-mentioned diethyl ether solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery ether, and obtain product phenolic compound (being rich in xylenol), its quality is 30.0g, consists of phenol 1.0%, cresols 2.5%, xylenol 96.0%, neutral oil 0.5%.
Embodiment 10
Simulated oil is 80% toluene+20% normal hexane (volume ratio) solution containing different phenol, and wherein phenol content 100.1g/L, o-cresol content 99.2g/L, 2,6-xylenol content are 99.5g/L.Get simulated oil 500mL, under temperature 5 DEG C of conditions, with tetramethyl ammonium chloride extracting and separating phenolic compound.
First time adds tetramethyl ammonium chloride 29.1g in simulated oil, is 50% of phenol mole number, stirs 2min, and leave standstill 20min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and removes the simulated oil after phenol mutually with upper.First time extraction obtains 96.2g congruent melting solvent, and analyze composition, wherein neutral oil content is 11.1%.Under the condition of temperature 90 DEG C, pressure 0.06atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 20min, neutral oil mass content is reduced to 0.4%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the isopropyl ether of 6 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim tetramethyl ammonium chloride.To the above-mentioned isopropyl ether solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery isopropyl ether, and obtain product phenolic compound (phenol-rich), its quality is 56.7g, consists of containing phenol 83.0%, cresols 11.7%, xylenol 4.9%, neutral oil 0.4%.
Second time adds tetramethyl ammonium chloride 30.2g to removing in the simulated oil after phenol through first time, for 60% of cresols mole number, stir 2min, leave standstill 20min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and the upper simulated oil removed mutually after phenol and ortho-cresol.Second time extraction obtains 79.2g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 9.9%.Under the condition of temperature 90 DEG C, pressure 0.06atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 20min, neutral oil mass content is reduced to 0.6%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the isopropyl ether of 6 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim tetramethyl ammonium chloride.To the above-mentioned isopropyl ether solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery isopropyl ether, and obtain product phenolic compound (being rich in cresols), its quality is 41.5g, consists of phenol 3.5%, cresols 89.8%, xylenol 6.0%, neutral oil 0.7%.
Third time adds tetramethyl ammonium chloride 31.3g in the simulated oil after first time and second time remove phenol and cresols, is 70% of xylenol mole number, stirs 2min, and leave standstill 20min, system is divided into two-phase, and then separatory shifts out lower phase congruent melting solvent phase.Employing silver nitrate titration method is analyzed, and does not find that there is tetramethyl ammonium chloride in upper phase oil phase.Third time extraction obtains 47.4g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 5.4%.Under the condition of temperature 90 DEG C, pressure 0.06atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 20min, neutral oil mass content is reduced to 0.4%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the isopropyl ether of 6 times of volumes, leave standstill 5min, filtration drying after stirring 5min, reclaim tetramethyl ammonium chloride.To the above-mentioned isopropyl ether solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery isopropyl ether, and obtain product phenolic compound (being rich in xylenol), its quality is 13.6g, consists of phenol 2.8%, cresols 1.8%, xylenol 94.7%, neutral oil 0.7%.
Embodiment 11
Simulated oil is 80% toluene+20% normal hexane (volume ratio) solution containing different phenol, and wherein phenol content 100.1g/L, o-cresol content 99.2g/L, 2,6-xylenol content are 99.5g/L.Get simulated oil 500mL, under temperature 5 DEG C of conditions, with tetramethyl ammonium chloride extracting and separating phenolic compound.
First time adds tetramethyl ammonium chloride 29.1g in simulated oil, is 50% of phenol mole number, stirs 30min, and leave standstill 20min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and removes the simulated oil after phenol mutually with upper.First time extraction obtains 96.0g congruent melting solvent, and analyze composition, wherein neutral oil content is 11.1%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.4%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the n-butyl ether of 7 times of volumes, leave standstill 10min, filtration drying after stirring 10min, reclaim tetramethyl ammonium chloride.To the above-mentioned n-butyl ether solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery n-butyl ether, and obtain product phenolic compound (phenol-rich), its quality is 56.4g, consists of containing phenol 83.2%, cresols 11.5%, xylenol 4.8%, neutral oil 0.5%.
Second time adds tetramethyl ammonium chloride 30.2g to removing in the simulated oil after phenol through first time, for 60% of cresols mole number, stir 30min, leave standstill 20min, system is divided into two-phase, and then separatory obtains lower phase congruent melting solvent and the upper simulated oil removed mutually after phenol and ortho-cresol.Second time extraction obtains 79.5g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 9.9%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.6%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the n-butyl ether of 7 times of volumes, leave standstill 10min, filtration drying after stirring 10min, reclaim tetramethyl ammonium chloride.To the above-mentioned n-butyl ether solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery n-butyl ether, and obtain product phenolic compound (being rich in cresols), its quality is 41.5g, consists of phenol 3.5%, cresols 89.8%, xylenol 6.0%, neutral oil 0.7%.
Third time adds tetramethyl ammonium chloride 31.3g in the simulated oil after first time and second time remove phenol and cresols, is 70% of xylenol mole number, stirs 30min, and leave standstill 20min, system is divided into two-phase, and then separatory shifts out lower phase congruent melting solvent phase.Employing silver nitrate titration method is analyzed, and does not find that there is tetramethyl ammonium chloride in upper phase oil phase.Third time extraction obtains 47.7g congruent melting solvent, analyzes composition, wherein contains the neutral oil of 5.5%.Under the condition of temperature 80 DEG C, pressure 0.02atm, employing rotary evaporation mode removes the neutral oil in the congruent melting solvent of gained, and evaporation time 10min, neutral oil mass content is reduced to 0.4%.Under 20 DEG C of conditions, in the congruent melting solvent removing neutral oil, add the n-butyl ether of 7 times of volumes, leave standstill 10min, filtration drying after stirring 10min, reclaim tetramethyl ammonium chloride.To the above-mentioned n-butyl ether solution containing phenolic compound, 70 DEG C, under condition of negative pressure, carry out Distillation recovery n-butyl ether, and obtain product phenolic compound (being rich in xylenol), its quality is 13.8g, consists of phenol 2.9%, cresols 1.5%, xylenol 95.2%, neutral oil 0.4%.
Claims (7)
1. the method for phenol mixture in selective separation oil, is characterized in that comprising the steps:
(1) by the add-on of quaternary ammonium salt be 0.3 times-0.6 times of phenol mole number, quaternary ammonium salt is added in oil, at separation temperature is 0 DEG C-30 DEG C, after churning time 1min-30min, leave standstill 1min-20min, system is divided into two-phase, and the phenol that quaternary ammonium salt is optionally stronger with reactive force first forms congruent melting solvent, this congruent melting solvent and oil phase do not dissolve each other thus and separation of oil, obtain the congruent melting solvent of phenol-rich and the oil of de-phenol after separation;
(2) by the add-on of quaternary ammonium salt be 0.4 times-0.7 times of cresols mole number, quaternary ammonium salt is added in step (1) dephenolize oil, at separation temperature is 0 DEG C-30 DEG C, after churning time 1min-30min, leave standstill 1min-20min, the cresols that quaternary ammonium salt optionally takes second place with reactive force forms congruent melting solvent, this congruent melting solvent and oil phase do not dissolve each other and and separation of oil, obtain being rich in the congruent melting solvent of cresols and the oil of de-phenol and cresols after separation;
(3) by the add-on of quaternary ammonium salt be 0.5 times-0.9 times of xylenol mole number, quaternary ammonium salt is added again in step (2) dephenolize oil, at separation temperature is 0 DEG C-30 DEG C, after churning time 1min-30min, leave standstill 1min-20min, the xylenol that quaternary ammonium salt is optionally less with reactive force forms congruent melting solvent, this congruent melting solvent and oil phase do not dissolve each other and and separation of oil, obtain being rich in the congruent melting solvent of xylenol and the oil of de-phenol, cresols and xylenol after separation;
(4), after above-mentioned separation terminates, respectively under pressure 0.01 atm-0.06 atm, temperature 60 C-90 DEG C of conditions, underpressure distillation is carried out to three kinds of congruent melting solvents, remove the neutral oil wherein carried;
(5) be 4-7:1 by the volume ratio of solvent resistant and congruent melting solvent, remove in the congruent melting solvent of neutral oil respectively to above-mentioned three kinds and add solvent resistant, at separation temperature 0 DEG C-30 DEG C, quaternary ammonium salt recrystallization is separated out in solid form, filter, realize the regeneration of quaternary ammonium salt, obtain three kinds of solvent resistant solution containing phenol;
(6) distill the solvent resistant solution that three kinds contain phenol respectively, be separated by phenolic compound with solvent resistant, obtain phenol, cresols, xylenol and solvent resistant respectively, solvent resistant is reused.
2. the method for phenol mixture in a kind of selective separation oil as claimed in claim 1, it is characterized in that described oil is the mixture of aromatic hydrocarbons, aliphatic hydrocarbon and phenolic compound, wherein phenolic compound is phenol, cresols and xylenol.
3. the method for phenol mixture in a kind of selective separation oil as claimed in claim 2, is characterized in that in oil, phenolic compound concentration is 50 g/L-300g/L.
4. the method for phenol mixture in a kind of selective separation oil as claimed in claim 1, is characterized in that described neutral oil is the mixture of aromatic hydrocarbons and aliphatic hydrocarbon.
5. the method for phenol mixture in a kind of selective separation oil as claimed in claim 1, is characterized in that described quaternary ammonium salt is choline chloride 60, tetramethyl ammonium chloride, etamon chloride, methyl triethyl ammonium chloride, tetraethylammonium bromide or 4 bromide.
6. the method for phenol mixture in a kind of selective separation oil as claimed in claim 1, is characterized in that the quaternary ammonium salt that step (1)-(3) add is identical.
7. the method for phenol mixture in a kind of selective separation oil as claimed in claim 1, is characterized in that solvent resistant is ether, isopropyl ether, n-butyl ether, ethyl acetate or methyl-formiate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510254744.0A CN104946303B (en) | 2015-05-18 | 2015-05-18 | A kind of method of phenol mixture in Selective Separation oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510254744.0A CN104946303B (en) | 2015-05-18 | 2015-05-18 | A kind of method of phenol mixture in Selective Separation oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104946303A true CN104946303A (en) | 2015-09-30 |
| CN104946303B CN104946303B (en) | 2017-04-05 |
Family
ID=54161376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510254744.0A Active CN104946303B (en) | 2015-05-18 | 2015-05-18 | A kind of method of phenol mixture in Selective Separation oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104946303B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542969A (en) * | 2016-11-08 | 2017-03-29 | 北京化工大学 | A kind of method of use inner salt separating phenols compounds from carbolic oil |
| CN107399779A (en) * | 2017-08-09 | 2017-11-28 | 北京盖雅环境科技有限公司 | A kind of processing method of phenol wastewater |
| CN107501051A (en) * | 2017-09-14 | 2017-12-22 | 北京化工大学 | A kind of method that phenolic compound in oily phenol mixture is separated with quaternary ammonium dication liquid extraction |
| CN108913195A (en) * | 2018-07-12 | 2018-11-30 | 太原理工大学 | A kind of method of phenolic compound during direct conversion solution of Selective Separation coal is oily |
| CN110627624A (en) * | 2019-09-06 | 2019-12-31 | 陕西煤业化工集团神木天元化工有限公司 | Method for separating alkaline nitride from phenol products |
| CN113200869A (en) * | 2021-04-28 | 2021-08-03 | 南京长江江宇环保科技有限公司 | Method for recovering tetramethylammonium chloride from semiconductor development wastewater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209957A (en) * | 2007-12-25 | 2008-07-02 | 浙江工业大学 | Method for separating phenols compounds from phenol-containing waste water |
| CN102989196A (en) * | 2011-09-16 | 2013-03-27 | 北京化工大学 | Separation method for phenol compounds in oil |
| CN203683420U (en) * | 2013-09-06 | 2014-07-02 | 山西省国新能源发展集团有限公司 | Novel device for quickly separating phenol compounds in coal tar |
| CN104324519A (en) * | 2014-11-04 | 2015-02-04 | 中国科学院过程工程研究所 | Method for directly separating phenols from coal pyrolytic oil |
-
2015
- 2015-05-18 CN CN201510254744.0A patent/CN104946303B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209957A (en) * | 2007-12-25 | 2008-07-02 | 浙江工业大学 | Method for separating phenols compounds from phenol-containing waste water |
| CN102989196A (en) * | 2011-09-16 | 2013-03-27 | 北京化工大学 | Separation method for phenol compounds in oil |
| CN203683420U (en) * | 2013-09-06 | 2014-07-02 | 山西省国新能源发展集团有限公司 | Novel device for quickly separating phenol compounds in coal tar |
| CN104324519A (en) * | 2014-11-04 | 2015-02-04 | 中国科学院过程工程研究所 | Method for directly separating phenols from coal pyrolytic oil |
Non-Patent Citations (2)
| Title |
|---|
| 庞昆: "铜泡沫的制备和油酚混合物的共熔分离", 《中国优秀硕士学位论文全文数据库工程技术I辑》 * |
| 郭武杰: "季铵盐离子液体分离油酚混合物及机理", 《中国优秀硕士学位论文全文数据库工程技术I辑》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542969A (en) * | 2016-11-08 | 2017-03-29 | 北京化工大学 | A kind of method of use inner salt separating phenols compounds from carbolic oil |
| CN106542969B (en) * | 2016-11-08 | 2019-06-11 | 北京化工大学 | A method of with inner salt from carbolic oil separating phenols compounds |
| CN107399779A (en) * | 2017-08-09 | 2017-11-28 | 北京盖雅环境科技有限公司 | A kind of processing method of phenol wastewater |
| CN107501051A (en) * | 2017-09-14 | 2017-12-22 | 北京化工大学 | A kind of method that phenolic compound in oily phenol mixture is separated with quaternary ammonium dication liquid extraction |
| CN107501051B (en) * | 2017-09-14 | 2020-09-04 | 北京化工大学 | Method for extracting and separating phenolic compounds in oil-phenol mixture by using quaternary amino dicationic ionic liquid |
| CN108913195A (en) * | 2018-07-12 | 2018-11-30 | 太原理工大学 | A kind of method of phenolic compound during direct conversion solution of Selective Separation coal is oily |
| CN108913195B (en) * | 2018-07-12 | 2020-08-21 | 太原理工大学 | Method for selectively separating phenolic compounds in direct conversion liquid oil from coal |
| CN110627624A (en) * | 2019-09-06 | 2019-12-31 | 陕西煤业化工集团神木天元化工有限公司 | Method for separating alkaline nitride from phenol products |
| CN110627624B (en) * | 2019-09-06 | 2020-08-18 | 陕西煤业化工集团神木天元化工有限公司 | Method for separating alkaline nitride from phenol products |
| CN113200869A (en) * | 2021-04-28 | 2021-08-03 | 南京长江江宇环保科技有限公司 | Method for recovering tetramethylammonium chloride from semiconductor development wastewater |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104946303B (en) | 2017-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104946303A (en) | Method for selectively separating phenol mixture from oil | |
| CN102219649B (en) | Method of extracting phenolic compound from coal liquefied oil or coal tar | |
| CN108913195B (en) | Method for selectively separating phenolic compounds in direct conversion liquid oil from coal | |
| CN100412010C (en) | Treatment and reclaimation method of coal gasification wastewater contg. phenol | |
| CN100532280C (en) | Process for extracting phenol-containing aqueous solution | |
| CN106588579B (en) | A method of extracting phenolic compound from carbolic oil | |
| CN110128235B (en) | Eutectic solvent, preparation method thereof and application of eutectic solvent as extractant | |
| CN102989196B (en) | The separation method of phenolic compound in a kind of oil | |
| CN105176556A (en) | Method for separating phenol from coal tar phenol-containing distillate oil | |
| CN104324519A (en) | Method for directly separating phenols from coal pyrolytic oil | |
| CN105712427B (en) | Polyphenol has the extractant and extracting process of high distribution coefficient in a kind of pair of phenol wastewater | |
| CN106278827A (en) | A kind of method and device of extract and separate phenolic compound from coal derived oils | |
| CN107501051B (en) | Method for extracting and separating phenolic compounds in oil-phenol mixture by using quaternary amino dicationic ionic liquid | |
| CN103289717A (en) | Method for solvent extraction-column chromatography separation of coal tar, and apparatus thereof | |
| CN106865675B (en) | Extraction dephenolization method of phenol-containing wastewater | |
| CN105836835B (en) | The method that subcritical fluids multitple extraction handles high organic matter brine waste difficult to degrade | |
| CN105540969A (en) | High-phenol concentration waste water treatment method | |
| CN104310694A (en) | Method for treating semi-coke wastewater obtained by producing coal | |
| CN108395367B (en) | Method for separating phenolic compounds from coal tar | |
| CN107416936A (en) | A kind of composite extractant for extracting dihydric phenols material and its production and use | |
| CN102585870A (en) | Method for quickly separating chain hydrocarbon and phenols from medium and low temperature tar | |
| CN104707549B (en) | A kind of device and method reclaiming chromatographic grade organic reagent from organic reagent waste liquid | |
| CN113462466B (en) | Method for extracting and separating grease from seaweed | |
| CN110003939A (en) | A kind of efficient carbolic oil dephenolization method | |
| CN109776277A (en) | A method of from extraction phenolic substances in feedstock oil containing phenol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |