CN103601667A - Method for isolating carbazole from anthracene oil - Google Patents
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- C07—ORGANIC CHEMISTRY
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- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/84—Separation, e.g. from tar; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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Abstract
The invention discloses a method for isolating carbazole from anthracene oil and belongs to the field of deep processing technology of coal tar. The method employs countercurrent chromatography technology, and has the following advantages that: (1) the method is directly applicable to separation of carbazole from anthracene oil, crude anthraene, decrystalized anthracene oil and the like, isolated carbazole contains a little amount of aromatic nitrogen-containing compounds, and high-purity carbazole with purity of 98% or more can be obtained after the isolated carbazole is recrystallized with xylene; (2) a to-be isolated sample can be fully contacted with a liquid-state stationary phase, and the method has the advantages of being no loss in sample, efficient, rapid, large in isolating amount, high in recovery rate and the like; (3) the boiling point of a solvent system is medium, so that the toxicity is substantially reduced, also airtight operation can be performed in the chromatogram system, there is no pollution, the sample is recoverable almost completely, and the solvents of stationary phase and mobile phase are recoverable and reusable; and (4) the isolation process of carbazole is simplified substantially, and the separation technology of anthracene oil, crude anthracene and the like is simplified.
Description
Technical field
The present invention be specifically related to a kind of from carbolineum the method for separated carbazole, belong to coal tar deep processing technical field.
Background technology
Carbazole (C
12h
9n) being important dyestuff and Pigment Intermediates, is also the important source material of synthetic resins etc., and the carbazole of take is that the carbazole that the synthetic N-of base-material replaces is having special purposes aspect leaded light conduction speciality polymer material.The important source material that the stablizer of carbazole or precious metal ore flotation agent, water reducer, lubricating oil and thermal oil, tensio-active agent, fluorescence softening agent, biological activity matter are prepared etc.
Carbazole is one of important component in coal tar, in the coal tar distillation course of processing, be enriched in carbolineum cut together with luxuriant and rich with fragrance grade with anthracene, carbolineum crystallisation by cooling obtains crude anthracene, then obtains the products such as anthracene, phenanthrene and carbazole through separation, and most carbazole all comes from this in the world at present.The separation method of carbazole in research and development carbolineum, optimizes and simplifies technique, has good market outlook.
Solvent wash crystallization process is the main method of China's carbolineum and crude anthracene processing, its core technology is to utilize phenanthrene to have the first kind solvent (being mainly benzene kind solvent) of good solubility to carry out wash crystallization to isolate most of phenanthrene and fluorenes etc. to crude anthracene, then remaining solid (being mainly anthracene and carbazole) is used carbazole is had to the Equations of The Second Kind solvent of good solubility (as alcohol, aldehyde, ketone, pyridine or dimethyl sulfoxide (DMSO) etc.) wash crystallization to be to isolate carbazole, the anthracene of gained, luxuriant and rich with fragrance, the thick product of carbazole is used alternatingly above two kind solvents and obtains through repeated washing crystallization purifying repeatedly the anthracene that purity is higher, luxuriant and rich with fragrance and smart carbazole product (Zhao Zhenbo, solvent in < < crude anthracene separation and purification process is selected > >, hair peak, the research > > of the separated anthracene of < < solvent method, phenanthrene and carbazole).
The required solvent of solvent wash crystallization process source is easy to get, simple to operate, technology maturation.China's first kind solvent used is mainly benzene or toluene at present, and volatility is large, can cause neural spasm, has aberration inducing tendency; Equations of The Second Kind solvent is mainly acetone or dimethyl sulfoxide (DMSO), the two is all volatile, inflammable, explosive, and acetone has stronger anesthetic action to central nervous system, and DMSO and protein hydrophobic grouping are had an effect, cause protein denaturation, there is blood vessel toxicity and liver renal toxicity.Solvent method is because repeatedly used solvent extraction and recrystallization, and technical process is long, solvent load is large, solvent system toxicity is large, the carbazole rate of recovery is low, cost is higher, environmental pollution weight.The various replace solvents of research and development high-efficiency low-toxicity, introduce efficient separation method, and simplification of flowsheet is the direction of solvent method processing carbolineum.
Solvent-rectification method (or rectifying-solvent method) is the another class technology of crude anthracene processing.340.2 ℃ of 340.7 ℃ of the boiling points of anthracene, luxuriant and rich with fragrance boiling points, the boiling point of the two and carbazole (354.8 ℃ of boiling points) differs larger.Utilize this character, the separated carbazole of available continuous rectification under vacuum or azeotropic distillation, and anthracene separated with solvent method and phenanthrene combine (Zhou Weiguo etc., anthracene in < < coal tar, phenanthrene, carbazole refining and utilize > >; Ye Huang, < < produces anthracene-smart carbazole > > with crystallization-rectification method; Wang Huanyu etc., < < inquires into > > from coal tar separating-purifying anthracene and carbazole process modification; The preparation method of anthracene, phenanthrene, carbazole, CN1250768A).But rectifying exists equipment and complex process, energy consumption and high in cost of production problem.Additive method is if fractionation, emulsion liquid membrane, supercritical fluid method, zone melting process etc. are all at conceptual phase (He Xuanming etc., the processing of < < carbolineum and isolation technique progress > >).
High speed adverse current chromatogram (high-speed countercurrent chromatography, HSCCC) be the liquid luquid partition chromatography technology without solid carrier, its chromatographic column is the multi-layer helix-tube of one group of high speed rotating, in pipe, be two immiscible liquid phase solvent systems, lighter phase solvent is called phase, heavier phase solvent is called lower phase, and take one is stationary phase mutually, and another is moving phase mutually.HSCCC utilizes the synchronous planetary centrifugal motion of multi-layer helix-tube, make sample material carry out repeated dispensing extraction between immiscible two-phase (upper and lower phase) solvent, because the partition ratio of different components in two-phase is different, realize separated, in fields such as biology, medicine, natural product, organic synthesis, environmental analysis, food, geology, there is application (Cao Xueli, the high adverse current chromatogram isolation technique of < < and application > >).Different from other chromatographic techniques, this technology is because stationary phase supports without solid carrier, and loading capacity is large, thereby fractional dose is large, is easy to amplify, and has the prospect of industrial application.But because be subject to the impact of traditional hot-work pattern, this technology is applied less in coalification industry, there is no useful this technical point from the research of carbazole and application report.
Summary of the invention
The object of this invention is to provide a kind of from carbolineum the method for separated carbazole.
In order to realize above object, the technical solution adopted in the present invention is:
A method for separated carbazole from carbolineum, comprises the following steps:
(1) preparation solvent system
According to volume ratio, be normal heptane or hexanaphthene or normal hexane: benzene: acetone: ethanol or methyl alcohol or acetonitrile=(4.5～6): (1～2): (1～2): (4.5～6) get each solvent, mix rear degassedly, standing, be divided into upper and lower phase;
(2) when being stationary phase, lower mutually when the moving phase above mutually, sample to be separated is dissolved in moving phase, adopt positive rotary-die type; When being moving phase, lower mutually when the stationary phase above mutually, sample to be separated is dissolved in stationary phase, adopt reversing mode;
(3) receive carbazole cut, isolate carbazole.
In described step (1), adopt normal heptane/hexanaphthene/normal hexane and the ethanol/methyl alcohol/acetonitrile of higher to replace most of benzene and acetone, both retained the separating effect of benzene-acetone system to carbazole, reduced again the volatility of solvent system.Wherein, upper phenanthrene relatively has good solvability, and lower relative carbazole has good solvability.Compare the upper effect of playing mutually first kind solvent, the lower effect of playing mutually Equations of The Second Kind solvent with conventional solvent wash crystallization method.
In described step (2), working as upper is stationary phase mutually, lower while being moving phase mutually, two phase solvent system is set up a kind of special one-way fluid dynamic equilibrium in one group of multi-layer helix-tube of high speed rotating, in continuous rotation process, retain a large amount of stationary phase, sample adverse current under the drive of moving phase, through stationary phase, has formed special high speed adverse current chromatogram column system.The movement locus of spiral tube is synchronous planetary centrifugal motion, in the time of high speed rotation, around hollow shaft, do revolution at a high speed, its each site is moving phase and stationary phase short mix during side in orbit, sample component to be separated is at two alternate fast allocations, while moving to the outside of track, due to strong centrifugal action, two phase factor density are different and separate.Under the rotating speed of 800rpm, mix and can reach 13 times/second with separated frequency, be just equivalent to each time single extraction operation, finally make carbazole transfer to acquisition separation in moving phase.When upper be moving phase mutually, lower while being stationary phase mutually, separation principle is the same; But because phenanthrene is high at upper partition ratio in mutually, carbazole is high at lower partition ratio in mutually, and the partition ratio of anthracene in two-phase is placed in the middle, so be anthracene and luxuriant and rich with fragrance along with moving phase (lower phase) first flows out, after carbazole, flows out.For isolating quickly carbazole, so first-selected above, be mutually stationary phase, lower be moving phase mutually.Wherein, sample to be separated can be carbolineum, crude anthracene, de-brilliant carbolineum, or crude anthracene adopts solvent wash method to isolate luxuriant and rich with fragrance remaining sample (carbazole that separation is obtained is separated through carrying out with anthracene).
In described step (2), adverse current chromatogram is before startup, adopting cooling water circulation mode to control chromatographic system temperature is 20～50 ℃, stationary phase measures through volume pump, under static state, input in the chromatographic column of adverse current chromatogram, until chromatographic column exit end is collected stationary phase (termination of pumping after 20～50mL), make stationary phase be full of chromatographic column.Start chromatographic column, when upper, adopt positive rotary-die type during mutually for stationary phase, during instantly mutually for stationary phase, adopt reversing mode.Adjust rotating speed and mobile phase flow rate, to chromatographic column exit end outflow moving phase, the background signal of detection is stable, and system reaches balance.The control of circulating water temperature, a small amount of separation can be controlled in 20～25 ℃, and separation in enormous quantities can be controlled in 50 ℃.
Present stage, from 300ml～5000L not etc., along with the increase of column volume, sample size to be separated can correspondingly increase the spiral tube volume of adverse current chromatogram, and value is 0.2g～16kg.During separated carbazole, sample to be separated is dissolved in the moving phase or stationary phase of certain volume, the cumulative volume dissolving in looks sample size to be separated and column volume changes, and can be 20mL～200L; After ultrasonic dissolution is even, add in system, timing image data while opening, observe detection signal again.
In described step (2) when being mutually above stationary phase, lower mutually when the moving phase, the circulating water temperature of controlling adverse current chromatogram is 20～50 ℃, mobile phase flow rate is 3mL/min～30L/min, and stationary phase flow is 20mL/min～200L/min, and rotating speed is 500～900rpm; When being moving phase, lower mutually when the stationary phase above mutually, the circulating water temperature of controlling adverse current chromatogram is 20～25 ℃, and mobile phase flow rate is 3mL/min～30L/min, and stationary phase flow is 20mL/min～200L/min, and rotating speed is 500～900rpm.Moving phase/stationary phase flow and just/anti-pattern rotating speed are all relevant with spiral tube volume, and the larger flow of column volume is larger, for the rotating speed that lightens the load, can suitably turn down, and column volume more low discharge is lower, and rotating speed can suitably be heightened.
Preferably, in described step (2), when being stationary phase, lower mutually when the moving phase above mutually, the circulating water temperature of controlling adverse current chromatogram is 20～50 ℃, and mobile phase flow rate is 3mL/min～50mL/min, stationary phase flow is 20mL/min～300mL/min, and rotating speed is 500～900rpm; When being moving phase, lower mutually when the stationary phase above mutually, the circulating water temperature of controlling adverse current chromatogram is 20～25 ℃, and mobile phase flow rate is 3mL/min～30mL/min, and stationary phase flow is 20mL/min～200mL/min, and rotating speed is 500～900rpm.
In described step (3), working as upper is stationary phase mutually, lower while being moving phase mutually, the time that receives carbazole cut is 70～120min, the method of separated carbazole is for to steam solvent, and the solvent steaming is moving phase, can continue to use after modulation, stationary phase blows out with nitrogen, Distillation recovery stationary phase is reusable through overmodulation, and gained solid is anthracene, luxuriant and rich with fragrance mixture, can adopt conventional solvent extraction crystallizing and washing method separated; When upper be stationary phase mutually, lower while being moving phase mutually, the time that receives carbazole cut is 150～250min, other working method is the same.With the increase of separated scale, apparatus system rotating speed reduces, the collection time scope of fraction can broaden and after prolong.
In view of the object of separated carbazole, preferably above is stationary phase mutually, and lower is moving phase mutually.
Preferred, by the separated carbazole dimethylbenzene recrystallization of step (3), obtain high-purity carbazole.
Beneficial effect of the present invention:
The present invention adopts high-speed countercurrent chromatography separated carbazole from carbolineum, have the following advantages: (1) can be directly used in the separation of carbazole in carbolineum, crude anthracene, de-brilliant carbolineum etc., in the carbazole being separated to, contain a small amount of aromatic series nitrogenous compound, with dimethylbenzene recrystallization, obtain more than 98% high-purity carbazole; (2) between sample to be separated and liquid stationary phase, can fully contact, have sample nondestructive lose, efficient, fast, large, the rate of recovery advantages of higher of fractional dose; (3) boiling point of solvent system is medium, and toxicity reduces greatly, and chromatographic system can closed-loop operation, and pollution-free, sample almost can all reclaim, and stationary phase and mobile phase solvent are all recyclable; (4) sepn process of carbazole is simplified greatly, and the separating technology of carbolineum, crude anthracene etc. is simplified.
Accompanying drawing explanation
Fig. 1 is the Technology Roadmap of the embodiment of the present invention 1 separated carbazole from carbolineum;
Fig. 2 is the makings analysis of spectra of main ingredient in embodiment 1 crude anthracene;
Fig. 3 is the makings analysis of spectra of embodiment 1 carbazole;
Fig. 4 is the makings analysis of spectra of main ingredient in the de-brilliant carbolineum of embodiment 2;
Fig. 5 is the makings analysis of spectra of embodiment 2 carbazoles;
Fig. 6 is the makings analysis of spectra of main ingredient in embodiment 3 carbolineums;
Fig. 7 is the makings analysis of spectra of embodiment 3 carbazoles.
Embodiment
Following embodiment is only described in further detail the present invention, but does not form any limitation of the invention.
Embodiment 1
The method of the present embodiment separated carbazole from carbolineum, comprises the following steps:
(1) get crude anthracene 0.2655g, in crude anthracene, main ingredient makings analytical results refers to following table 1 and Fig. 2;
(2) preparation solvent system
According to volume ratio, be normal heptane: benzene: acetone: acetonitrile=4.5:1:1:4.5 gets each solvent, ultrasonicly mix rear degassed 20min, standing over night, makes two-phase solvent reach abundant balance, and the encloses container that is placed in mutually up and down of the solvent system separating is stored;
(3) check a whole set of each line interface of TBE-300B high-speed counter-current chromatograph, guarantee to connect errorless, upper as stationary phase using solvent system, by the spiral tube chromatographic column of constant flow pump input counter current chromatograph, until cylinder is full of, start counter current chromatograph, after operating steadily, with constant flow pump, pump into lower phase, in the situation of hole instrument high-speed rotation, two-phase solvent is realized contact efficiently in spiral tube, mix, distribute, transmit, when two phase solvent system reaches after balance, by sample introduction circle, the moving phase that is dissolved with sample crude anthracene to be separated is injected in spiral tube, sample to be separated passes through the equilibrium system in whole spiral tube with moving phase, dose volume is 20mL, because the distribution capability of each component in sample to be separated in two-phase is different, the difference that causes their translational speeds in spiral tube, thereby make each component in sample to be separated obtain separation, wherein circulator bath temperature is 25 ℃, mobile phase flow rate is 3mL/min, stationary phase flow is 20mL/min, adopt forward mode, engine speed is 900rpm,
(4) observe detection signal, between 75～84min, receive carbazole cut, steam separated from solvent and obtain carbazole 0.0338g, purity is 90%, impurity is nitrogenous aromatic polymer, makings is analyzed collection of illustrative plates and is seen Fig. 3, then with recrystallization of dimethylbenzene, to obtain purity be 98% carbazole 0.031g, and the rate of recovery is 95.3%.
The makings analytical results of main ingredient in table 1 crude anthracene
Embodiment 2
The method of the present embodiment separated carbazole from carbolineum, comprises the following steps:
(1) get de-brilliant carbolineum 0.5331g, main ingredient makings analytical results refers to following table 2 and Fig. 4;
(2) according to volume ratio, be hexanaphthene: benzene: acetone: ethanol=3:2:2:3 gets each solvent, ultrasonicly mix rear degassed 20min, standing over night, makes two-phase solvent reach abundant balance, and the encloses container that is placed in mutually up and down of the solvent system separating is stored;
(3) adverse current chromatogram device, with embodiment 1, takes off the lower phased soln of brilliant carbolineum, and dose volume is 30mL, controlled circulation bath temperature is 45 ℃, and flow rate of mobile phase is 3mL/min, and stationary phase flow velocity is 20mL/min, adopt forward mode, engine speed is 500rpm, and other operate with embodiment 1;
(4) observe detection signal, the time that receives carbazole cut is 110～120min, steams separated from solvent and obtains carbazole 0.0159g, purity is 39%, and the carbazole rate of recovery is 94.7%, and impurity is mainly nitrogen heterocyclic aromatics, also have a small amount of aromatic series oxygenatedchemicals, makings is analyzed collection of illustrative plates and is seen Fig. 5; With recrystallization of dimethylbenzene, obtaining purity is again 96% carbazole, and secondary recrystallization obtains 98% carbazole.
De-brilliant carbolineum is that carbolineum removes the part after crude anthracene (being anthracene, phenanthrene and click click), and wherein carbazole content is lower.The object of the present embodiment is to reclaim remaining carbazole in de-brilliant carbolineum, for improving the carbazole rate of recovery, has expanded collection time scope.This part carbazole can not carry out purifying when actual production, separated carbazole after can mixing with crude anthracene, and then purifying.
The makings analytical results of main ingredient in the de-brilliant carbolineum of table 2
Embodiment 3
The method of the present embodiment separated carbazole from carbolineum, comprises the following steps:
(1) get carbolineum 0.5508g, its main ingredient makings analytical results refers to following table 3 and Fig. 6;
(2) preparation solvent system
According to volume ratio, be normal hexane: benzene: acetone: methyl alcohol=7:2:2:7 gets each solvent, ultrasonicly mix rear degassed 20min, standing over night, makes two-phase solvent reach abundant balance, and the encloses container that is placed in mutually up and down of the solvent system separating is stored;
(3) adverse current chromatogram device is with embodiment 1, the lower phased soln of carbolineum, and dose volume is 30mL, controlled circulation bath temperature is 40 ℃, and flow rate of mobile phase is 3mL/min, and stationary phase flow velocity is 20mL/min, adopt forward mode, engine speed is 700rpm, and other operate with embodiment 1;
(4) observe detection signal, between 90～105min, receive carbazole cut, steam separated from solvent and obtain carbazole 0.0354g, purity is 88.7%, impurity is nitrogenous aromatic polymer, makings is analyzed collection of illustrative plates and is seen Fig. 7, then obtains 98% carbazole 0.032g with recrystallization of dimethylbenzene, and the rate of recovery is 94.86%.
The makings analytical results of main ingredient in table 3 carbolineum
Embodiment 4
(1) get anthracene and each 1g of smart carbazole, make biased sample;
(2) preparation solvent system
According to volume ratio, be hexanaphthene: benzene: acetone: acetonitrile=7:2:2:7 gets each solvent, ultrasonicly mix rear degassed 20min, standing over night, makes two-phase solvent reach abundant balance, and the encloses container that is placed in mutually up and down of the solvent system separating is stored;
(3) adopt TBE-5000A high-speed counter-current chromatograph, preparation sample solvent volume is 200mL, and circulator bath temperature is 45 ℃, and mobile phase flow rate is 30mL/min, and stationary phase flow is 200mL/min, adopts forward mode, and engine speed is 500rpm; Operation steps is with embodiment 1, and the carbazole fraction collection time is 100～120min, and flash liberation obtains carbazole, and it is 98% that makings detects purity, and the rate of recovery is 99%, and stationary phase blows out the separated anthracene that obtains of rear solvent wash crystallization process.
Claims (8)
1. a method for separated carbazole from carbolineum, is characterized in that: comprise the following steps:
(1) preparation solvent system
According to volume ratio, be normal heptane or hexanaphthene or normal hexane: benzene: acetone: ethanol or methyl alcohol or acetonitrile=(4.5～6): (1～2): (1～2): (4.5～6) get each solvent, mix rear degassedly, standing, be divided into upper and lower phase;
(2) when being stationary phase, lower mutually when the moving phase above mutually, sample to be separated is dissolved in moving phase, adopt positive rotary-die type; When being moving phase, lower mutually when the stationary phase above mutually, sample to be separated is dissolved in stationary phase, adopt reversing mode;
(3) receive carbazole cut, isolate carbazole.
According to claim 1 from carbolineum the method for separated carbazole, it is characterized in that: in described step (2), sample to be separated is that carbolineum, crude anthracene, de-brilliant carbolineum or crude anthracene are isolated the sample after phenanthrene.
According to claim 1 from carbolineum the method for separated carbazole, it is characterized in that: in described step (2), adopt ultrasonic method that sample to be separated is dissolved in moving phase or stationary phase.
According to claim 1 from carbolineum the method for separated carbazole, it is characterized in that: in described step (2) when being stationary phase, lower mutually when the moving phase above mutually, the circulating water temperature of controlling adverse current chromatogram is 20～50 ℃, mobile phase flow rate is 3mL/min～30L/min, stationary phase flow is 20mL/min～200L/min, and rotating speed is 500～900rpm; When being moving phase, lower mutually when the stationary phase above mutually, the circulating water temperature of controlling adverse current chromatogram is 20～25 ℃, and mobile phase flow rate is 3mL/min～30L/min, and stationary phase flow is 20mL/min～200L/min, and rotating speed is 500～900rpm.
According to claim 4 from carbolineum the method for separated carbazole, it is characterized in that: in described step (2) when being stationary phase, lower mutually when the moving phase above mutually, the circulating water temperature of controlling adverse current chromatogram is 20～50 ℃, mobile phase flow rate is 3mL/min～50mL/min, stationary phase flow is 20mL/min～300mL/min, and rotating speed is 500～900rpm; When being moving phase, lower mutually when the stationary phase above mutually, the circulating water temperature of controlling adverse current chromatogram is 20～25 ℃, and mobile phase flow rate is 3mL/min～30mL/min, and stationary phase flow is 20mL/min～200mL/min, and rotating speed is 500～900rpm.
According to claim 5 from carbolineum the method for separated carbazole, it is characterized in that: in described step (3) when upper be stationary phase, lower during mutually for moving phase mutually, the time that receives carbazole cut is 70～120min; When upper be moving phase, lower mutually when the stationary phase mutually, the time that receives carbazole cut is 150～250min.
According to claim 1 from carbolineum the method for separated carbazole, it is characterized in that: in described step (2), be stationary phase mutually, lower is moving phase mutually, and sample to be separated is dissolved in moving phase, adopts positive rotary-die type.
According to claim 1 from carbolineum the method for separated carbazole, it is characterized in that: by the separated carbazole dimethylbenzene recrystallization of step (3), obtain high-purity carbazole.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104165936A (en) * | 2014-06-03 | 2014-11-26 | 中国地质大学（武汉） | Detection method of nitrogen-containing compound from rock extract |
| CN109535063A (en) * | 2019-01-15 | 2019-03-29 | 中钢集团鞍山热能研究院有限公司 | A kind of technique that high-purity carbazole is extracted from carbolineum using integrated separation method |
| CN109806843A (en) * | 2019-03-21 | 2019-05-28 | 陕西延长石油（集团）有限责任公司 | The absorption resin and the preparation method and application thereof of polycyclic aromatic hydrocarbon in a kind of adsorbing separation coal tar |
| CN113307761A (en) * | 2021-06-02 | 2021-08-27 | 太原理工大学 | Method for separating carbazole from anthracene oil |
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| CN104165936A (en) * | 2014-06-03 | 2014-11-26 | 中国地质大学（武汉） | Detection method of nitrogen-containing compound from rock extract |
| CN104165936B (en) * | 2014-06-03 | 2016-03-16 | 中国地质大学（武汉） | The detection method of nitrogen-containing compound in a kind of rock extracts |
| CN109535063A (en) * | 2019-01-15 | 2019-03-29 | 中钢集团鞍山热能研究院有限公司 | A kind of technique that high-purity carbazole is extracted from carbolineum using integrated separation method |
| CN109806843A (en) * | 2019-03-21 | 2019-05-28 | 陕西延长石油（集团）有限责任公司 | The absorption resin and the preparation method and application thereof of polycyclic aromatic hydrocarbon in a kind of adsorbing separation coal tar |
| CN109806843B (en) * | 2019-03-21 | 2021-09-14 | 陕西延长石油（集团）有限责任公司 | Adsorption resin for adsorbing and separating polycyclic aromatic hydrocarbons in coal tar, and preparation method and application thereof |
| CN113307761A (en) * | 2021-06-02 | 2021-08-27 | 太原理工大学 | Method for separating carbazole from anthracene oil |
| CN113307761B (en) * | 2021-06-02 | 2023-01-24 | 太原理工大学 | Method for separating carbazole from anthracene oil |
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