CN108002985B - Method for extracting and separating phenolic substances in coal tar by using polyethyleneimine - Google Patents

Method for extracting and separating phenolic substances in coal tar by using polyethyleneimine Download PDF

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CN108002985B
CN108002985B CN201711337578.6A CN201711337578A CN108002985B CN 108002985 B CN108002985 B CN 108002985B CN 201711337578 A CN201711337578 A CN 201711337578A CN 108002985 B CN108002985 B CN 108002985B
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coal tar
extractant
extracting
polyethyleneimine
extraction
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CN108002985A (en
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姜兴茂
朱爽
高家俊
戴亚芬
熊春艳
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Wuhan Institute of Technology
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Wuhan Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00—Working-up tar
    • C10C1/18—Working-up tar by extraction with selective solvents

Abstract

The invention relates to a method for extracting and separating phenols in coal tar by utilizing polyethyleneimine, which comprises the steps of firstly extracting phenols from coal tar by taking the polyethyleneimine as an extractant, then back-extracting the phenols from extract liquor obtained in the last step by taking low-boiling-point organic solvents such as diethyl ether, acetone, ethyl acetate, tetrahydrofuran and the like as back-extractants, finally distilling two liquid phases obtained by back-extraction, and obtaining crude phenols while separating and recovering the extractant and the back-extractants. The method has the advantages of simple and convenient operation, no generation of phenol-containing wastewater, insolubility of the extractant in the coal tar, no pollution to the coal tar, no corrosion to equipment, high-efficiency separation and extraction of the phenol substances, regeneration of the used raw material extractant and the back extractant, great reduction of the production cost and higher practical value.

Description

Method for extracting and separating phenolic substances in coal tar by using polyethyleneimine
Technical Field
The invention relates to the technical field of coal chemical industry, in particular to a method for extracting and separating phenolic substances in coal tar by using polyethyleneimine.
Background
The coal tar is a product in the coal dry distillation process, is black brown viscous liquid, and the annual output of China can reach more than 2000 million tons. According to the different carbonization temperatures and methods, the coal tar can be divided into low-temperature carbonization tar (450-. Besides hydrocarbons such as alkane, alkene and aromatic hydrocarbon, the coal tar also contains phenolic compounds with higher economic value, such as phenol, cresol, xylenol and the like. Generally speaking, the low-temperature coal tar contains more phenolic substances, and the phenolic content of the low-temperature coal tar can reach 10-20 wt%; the content of phenol in the high-temperature coal tar is relatively low, but the vacuum distillation products (phenol oil, naphthalene oil and wash oil) of the high-temperature coal tar contain more phenolic substances, for example, the content of phenol in the phenol oil reaches 20-30 wt%, the content of phenol in the naphthalene oil is 4-6 wt%, and the content of phenol in the wash oil is 3-5 wt%. At present, the price of crude phenol is about ten thousand yuan per ton, so that the phenolic substances in the coal tar are very necessary to be recovered.
The traditional separation method of phenolic substances is an alkali washing method, strong base NaOH is used as an alkali washing agent to react with phenolic substances in coal tar to generate sodium phenolate, and then the sodium phenolate is subjected to acid (such as H) treatment2SO4Or CO2) And (5) regenerating to obtain the phenolic substance. However, this method continuously consumes a large amount of alkali liquor and also produces phenol-containing wastewater which is difficult to treat, resulting in higher production cost and pollution control cost. In order to overcome the defects, some organic base solvents are used for separating phenolic substances in the coal tar, such as 1-methylimidazole, monoethanolamine, diethanolamine, triethanolamine, N-dimethylformamide and the like, and the organic bases can form hydrogen bonds with the phenolic substances so as to realize separation. In addition, the extraction agent can be used as an extraction agent, and the generation of phenol-containing waste water can be avoided. However, the organic bases have certain solubility in coal tar, not only pollute oil, but also cause loss of an extracting agent, and have low technical feasibility. In addition, some common quaternary ammonium salts are also used for separating and extracting phenol, such as choline chloride, triethylamine hydrochloride, tetramethylammonium chloride, tetraethylammonium chloride and the like. Although none of these quaternary ammonium salts is soluble in oil, there are some problems that limit their industrial application prospects. First, the quaternary ammonium salts all contain Cl-The paint is easy to absorb moisture and has strong corrosion to equipment; secondly, the quaternary ammonium salts are all solid, but the mixture after the quaternary ammonium salts react with phenols (such as phenol) is liquid, and the operation process is relatively complicated due to the change of physical properties.
In view of the above, it is important to develop an extractant which is insoluble in oil, non-corrosive and stable in physical properties for extracting phenols from coal tar.
Disclosure of Invention
The invention aims to overcome the defects of the existing extraction and separation technology of phenolic substances in coal tar, and provides a novel extracting agent, namely Polyethyleneimine (PEI), which is used for extracting and separating the phenolic substances in the coal tar. The extracting agent polyethyleneimine used in the invention has higher molecular weight, is immiscible with coal tar, cannot cause oil pollution, and hardly loses the extracting agent polyethyleneimine. In addition, the polyethyleneimine has no corrosion to equipment and stable physical properties, the separation of phenolic substances can be realized in the traditional extraction operation process, the phenolic substances in the coal tar can be efficiently separated and extracted through extraction, back extraction and distillation operations, and the used extractant and back extractant can be regenerated and are simple to operate. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the method for extracting and separating phenolic substances in coal tar by using polyethyleneimine comprises the following steps: (a) mixing polyethyleneimine and coal tar in proportion to make the polyethyleneimine and the coal tar fully contact with each other, so that phenolic substances enter an extracting agent, and performing liquid-liquid separation after extraction to obtain an extract phase; (b) mixing a low-boiling-point organic solvent serving as a back extractant with an extract phase in a ratio to ensure that the two phases are fully contacted, and performing liquid-liquid separation after back extraction to obtain a back extractant phase and an extractant phase; (c) distilling and recovering the low-boiling-point organic solvent in the back extraction agent phase to obtain a phenolic substance; distilling the low-boiling-point organic solvent in the extractant phase to obtain the regenerated polyethyleneimine extractant.
Further, the average molecular weight of the polyethyleneimine is 600-10000.
Furthermore, the mass ratio of the polyethyleneimine to the coal tar during mixed extraction is 0.1-3.
Furthermore, the content of phenolic substances in the coal tar is (1-20) wt%.
Further, the extraction temperature is 30-80 ℃, and the extraction time is 10-240 min.
Further, the low-boiling organic solvent is selected from one of diethyl ether, acetone, ethyl acetate and tetrahydrofuran.
Further, the mass ratio of the stripping agent phase to the stripping agent low-boiling-point organic solvent is 0.2-1, and the stripping is carried out for 10-240min at normal temperature.
Further, the operation conditions of the distillation, separation and recovery of the stripping agent phase and the extracting agent phase are as follows: the distillation temperature is 40-100 ℃, the distillation pressure is 0.01-0.1Mpa, and the distillation time is 0.5-6 h.
Compared with the prior art, the invention has the following beneficial effects: (1) the separation and extraction of the phenolic substances in the whole coal tar are divided into three steps, namely, firstly, the polyethyleneimine extraction process of the phenolic substances, then the back extraction process of the phenolic substances, and finally, the recovery and regeneration process of the phenolic substances and the extractant, so that the extraction agent and the back extractant are regenerated while the phenolic substances are efficiently separated and extracted; (2) the extractant polyethyleneimine has stable physical properties, has no corrosion to equipment, cannot cause oil pollution due to the insolubility of the extractant polyethyleneimine and coal tar, almost has no loss in the whole separation process, and can realize the separation of phenolic substances in the coal tar in the traditional extraction operation process; (3) the process is simple, the condition is mild, and the recovery rate of the phenolic substances in the coal tar can reach 10-60%.
Drawings
FIG. 1 is a schematic view of the process of the present invention.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following embodiments are further described.
Example 1
PEI with the average molecular weight of 10000 and coal tar (simulated oil formed by mixing phenol and toluene, wherein the content of phenol is 15 wt%) are mixed according to the mass ratio of 0.2, the PEI and the coal tar are fully contacted, extraction is carried out for 60min at the temperature of 30 ℃, so that phenolic substances enter an extracting agent from oil as much as possible, and an extraction phase and dephenolized oil are obtained. And (3) uniformly mixing the back extractant diethyl ether and the extract phase according to the mass ratio of 0.4, and back extracting for 60min at normal temperature to obtain a back extractant phase and an extract phase. Distilling the back extractant phase and the extractant phase at 50 deg.C and 0.01MPa for about 1 hr to obtain phenol substances, regenerated PEI and diethyl ether. The calculated recovery rate of the phenolic substances is 29.6 percent.
Example 2
PEI with the average molecular weight of 600 and coal tar (simulated oil formed by mixing phenol, toluene and n-octane, wherein the content of the toluene is 50 wt% and the content of the phenol is 15 wt%) are mixed according to the mass ratio of 0.5, the PEI and the coal tar are fully contacted, extraction is carried out for 60min at the temperature of 30 ℃, so that phenolic substances enter an extracting agent from oil as much as possible, and an extraction phase and dephenolized oil are obtained. And (3) uniformly mixing the back extractant diethyl ether and the extract phase according to the mass ratio of 0.4, and back extracting for 60min at normal temperature to obtain a back extractant phase and an extract phase. Distilling the back extractant phase and the extractant phase at 60 deg.C and 0.01MPa for about 0.5 hr to obtain phenol, regenerated PEI and diethyl ether. The calculated recovery rate of the phenolic substances is 36.5 percent.
Example 3
PEI with the average molecular weight of 600 and coal tar (simulated oil formed by mixing phenol, toluene and n-octane, wherein the content of toluene is 50 wt% and the content of phenol is 15 wt%) are mixed according to the mass ratio of 1:1, the PEI and the coal tar are fully contacted, extraction is carried out for 120min at the temperature of 30 ℃, so that phenolic substances enter an extracting agent from oil as much as possible, and an extraction phase and dephenolized oil are obtained. And (3) uniformly mixing the back extractant diethyl ether and the extract phase according to the mass ratio of 0.4:1, and back extracting for 30min at normal temperature to obtain a back extractant phase and an extract phase. Distilling the back extractant phase and the extractant phase at 60 deg.C and 0.01MPa for about 0.5 hr to obtain phenol, regenerated PEI and diethyl ether. The calculated recovery rate of the phenolic substances is 36.7%.
Example 4
PEI with the average molecular weight of 10000 and coal tar (simulated oil formed by mixing phenol, toluene and n-octane, wherein the content of toluene is 50 wt% and the content of phenol is 15 wt%) are mixed according to the mass ratio of 0.1:1, the PEI and the coal tar are fully contacted, extraction is carried out for 30min at the temperature of 30 ℃, so that phenolic substances enter an extracting agent from oil as much as possible, and an extraction phase and dephenolized oil are obtained. And (3) uniformly mixing the back extractant diethyl ether and the extract phase according to the mass ratio of 0.8:1, and back extracting for 30min at normal temperature to obtain a back extractant phase and an extract phase. Distilling the back extractant phase and the extractant phase at 80 deg.C and 0.1MPa for about 6 hr to obtain phenol, regenerated PEI and diethyl ether. The calculated recovery rate of the phenolic substances is 23.7%.
Example 5
PEI with the average molecular weight of 10000 and coal tar (simulated oil formed by mixing phenol and toluene, wherein the content of phenol is 15 wt%) are mixed according to the mass ratio of 1:1, the PEI and the coal tar are in full contact, extraction is carried out for 30min at the temperature of 30 ℃, so that phenolic substances enter an extracting agent from oil as much as possible, and an extraction phase and dephenolized oil are obtained. And (3) uniformly mixing the back extractant diethyl ether and the extract phase according to the mass ratio of 1:1, and back extracting for 120min at normal temperature to obtain a back extractant phase and an extract phase. Distilling the back extractant phase and the extractant phase at 70 deg.C and 0.01MPa for about 1 hr to obtain phenol substances, regenerated PEI and diethyl ether. The calculated recovery rate of the phenolic substances is 29.3 percent.
Example 6
PEI with an average molecular weight of 1800 and coal tar (simulated oil formed by mixing phenol and toluene, wherein the content of phenol is 15 wt%) are mixed according to the weight ratio of 0.2:1, fully contacting the two, extracting for 15min at 30 ℃ to ensure that phenolic substances enter an extracting agent from oil as much as possible to obtain an extract phase and dephenolized oil. And (3) uniformly mixing the back extractant diethyl ether and the extract phase according to the mass ratio of 0.4:1, and back extracting for 60min at normal temperature to obtain a back extractant phase and an extract phase. Distilling the back extractant phase and the extractant phase at 70 deg.C and 0.01MPa for about 2 hr to obtain phenol substances, regenerated PEI and diethyl ether. The calculated recovery rate of the phenolic substances is 18.3%.
Example 7
PEI with the average molecular weight of 1800 and coal tar (simulated oil formed by mixing phenol and toluene, wherein the content of phenol is 15 wt%) are mixed according to the mass ratio of 0.2:1, the PEI and the coal tar are fully contacted, extraction is carried out for 15min at the temperature of 30 ℃, so that phenolic substances enter an extracting agent from oil as much as possible, and an extract phase and dephenolized oil are obtained. And (3) uniformly mixing the back extractant diethyl ether and the extract phase according to the mass ratio of 0.4:1, and back extracting for 60min at normal temperature to obtain a back extractant phase and an extract phase. Distilling the back extractant phase and the extractant phase at 70 deg.C and 0.01MPa for about 2 hr to obtain phenol substances, regenerated PEI and diethyl ether. The calculated recovery rate of the phenolic substances is 13.8%.

Claims (3)

1. A method for extracting and separating phenolic substances in coal tar by using polyethyleneimine is characterized by comprising the following steps:
(a) mixing polyethyleneimine with the average molecular weight of 600-10000 and coal tar according to the mass ratio of 0.1-3 to ensure that the polyethyleneimine and the coal tar are fully contacted, so that phenolic substances enter an extracting agent, and performing liquid-liquid separation after extraction to obtain an extraction phase;
(b) mixing a low-boiling-point organic solvent serving as a back extractant with an extract phase according to a mass ratio of 0.2-1 to ensure that the two phases are fully contacted, and performing liquid-liquid separation after back extraction to obtain a back extractant phase and an extractant phase;
(c) distilling and recovering the low-boiling-point organic solvent in the back extraction agent phase to obtain a phenolic substance; distilling the low-boiling-point organic solvent in the extractant phase to obtain a regenerated polyethyleneimine extractant;
the low-boiling-point organic solvent is selected from one of diethyl ether, acetone, ethyl acetate and tetrahydrofuran, and the content of phenolic substances in the coal tar is 1-20 wt%; the operation conditions of the back extractant phase and the extractant phase distillation separation recovery are as follows: the distillation temperature is 40-100 ℃, the distillation pressure is 0.01-0.1Mpa, and the distillation time is 0.5-6 h.
2. The method for extracting and separating phenolic substances from coal tar by using polyethyleneimine according to claim 1, wherein the method comprises the following steps: the extraction temperature is 30-80 deg.C, and the extraction time is 10-240 min.
3. The method for extracting and separating phenolic substances from coal tar by using polyethyleneimine according to claim 1, wherein the method comprises the following steps: back-extracting at normal temperature for 10-240 min.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4256568A (en) * 1979-11-19 1981-03-17 Exxon Research & Engineering Co. Removal of phenols from phenol-containing streams
CN102219649A (en) * 2011-04-22 2011-10-19 煤炭科学研究总院 Method of extracting phenolic compound from coal liquefied oil or coal tar

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4256568A (en) * 1979-11-19 1981-03-17 Exxon Research & Engineering Co. Removal of phenols from phenol-containing streams
CN102219649A (en) * 2011-04-22 2011-10-19 煤炭科学研究总院 Method of extracting phenolic compound from coal liquefied oil or coal tar

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"武汉工程大学卢霞博士、周俊峰博士、沈陟博士、朱爽硕士为学生做学术报告";卢霞 等;《https://mep.wit.edu.cn/info/1065/4723.htm》;20171120 *

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