CN101786935B - Method for extracting fluorene, anthracene and carbazole from mixed anthracene oil - Google Patents
Method for extracting fluorene, anthracene and carbazole from mixed anthracene oil Download PDFInfo
- Publication number
- CN101786935B CN101786935B CN 201010114548 CN201010114548A CN101786935B CN 101786935 B CN101786935 B CN 101786935B CN 201010114548 CN201010114548 CN 201010114548 CN 201010114548 A CN201010114548 A CN 201010114548A CN 101786935 B CN101786935 B CN 101786935B
- Authority
- CN
- China
- Prior art keywords
- anthracene
- tower
- fluorenes
- carbazole
- carbolineum
- 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.)
- Active
Links
Images
Landscapes
- Indole Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a method for extracting fluorene, anthracene and carbazole from mixed anthracene oil, comprising the steps of mixed anthracene oil rectifying, fluorene static crystallization, semi-refined anthracene extraction from first anthracene oil, semi-refined anthracene rectifying for extracting refined anthracene and carbazole, i.e. carrying out three-tower separation on the mixed anthracene oil, extracting components such as wash oil fraction, first anthracene oil fraction, second anthracene oil fraction, and the like. A crystallization method is adopted to remove impurities in the anthracene fraction, and the product has high purity and high yield. The separation of the refined anthracene and the carbazole adopts efficient rectification under vacuum for extracting anthracene and the carbazole. The invention is a novel process flow organically combined by a plurality of process equipment, has the advantages of convenience, high efficiency and stable work, achieves the purposes of extracting a plurality of precious industrial chemical raw materials such as fluorene, carbazole, refined anthracene, and the like from the mixed anthracene oil through a set of process, and greatly improves the utilization value of first anthracene oil fraction and second anthracene oil fraction in coal tar, wherein the integrated extraction rate of fluorene, anthracene and carbazole respectively reach 66%, 62% and 55% relative to the mixed anthracene oil as raw materials. Moreover, the invention also has the advantages of high production automation degree, environmental friendliness, energy saving, emission reduction, and obvious social and economical benefit.
Description
Technical field
The invention belongs to technical field of coal chemical industry, be specifically related to a kind of the utilization and mix the method that carbolineum extracts fluorenes, anthracene and carbazole
Background technology
The component that produces during the coal-tar heavy oil fractionation by distillation has components such as light oil, carbolic oil, naphtalene oil, washing oil, a carbolineum, anthracene oil, pitch; Wherein a carbolineum, anthracene oil are the main raw materials that extracts fluorenes, anthracene, carbazole; A classical group of mixing carbolineum becomes fluorenes 8.54%; Phenanthrene 24.52%, anthracene 7.39%, carbazole 4.14%.Traditional technology is with a carbolineum, anthracene oil separately, obtains crude anthracene or directly extracts anthracene, carbazole with a carbolineum with a carbolineum crystallization.And that the carbazole resource has is half the in the middle of anthracene oil, and traditional technology has been wasted fluorenes resource and the anthracene in the anthracene oil, the carbazole resource in the carbolineum.The solvent method anthracene process for refining that China generally adopts is general removes impurity such as phenanthrene, fluorenes earlier with benzene kind solvent, and then removes carbazole with aldehydes or alcoholic solvent, can obtain the anthracene of purity more than 90%.Certain factory adopts furfural and heavy aromatics (heavy benzene) to make solvent always; But there are problems; Coke-oven plant, Beijing institute has researched and developed single non-proton type solvent N (DMF) for this reason, can get purity greater than 90% anthracene, and yield is higher than former technology more than 20%; Though but higher as the anthracene purity of solvent gained with single DMF, the extraction yield of anthracene has only about 50% with respect to crude anthracene.For this reason, the inventor has developed a kind of method that can from mix carbolineum, extract fluorenes, anthracene and carbazole easily through great deal of experimental, and test effect is good, has the potentiality of industrial application.
Summary of the invention
The object of the present invention is to provide a kind of process stabilizing, simple flow is mixed the method that carbolineum extracts fluorenes, anthracene and carbazole efficiently.
The objective of the invention is to realize like this: comprise that the rectifying of mixing carbolineum, fluorenes stationary crystallization, a carbolineum extract half anthracene, anthracene, carbazole are extracted in half anthracene rectifying, specifically comprise following operation:
A, the rectifying of mixing carbolineum: raw materials mix carbolineum is heated to 130-150 ℃ through washing oil tower process furnace, gets into the washing oil tower; Washing oil column overhead pressure is 100-105kPa, and temperature is 260-265 ℃, and the extraction washing oil heats up in a steamer; The washing oil fraction gets into the fluorenes tower, and fluorenes column overhead pressure is 18-22kPa, and temperature is 145-150 ℃, naphthalene, methylnaphthalene fraction before the extraction dibenzofuran; Side stream temperature is 185-203 ℃ on the fluorenes tower, extraction dibenzofuran fraction; Side stream temperature is 198-203 ℃ under the fluorenes tower, extraction fluorenes fraction; At the bottom of the fluorenes Tata service temperature 210-212 ℃, extraction carbon black oil fraction; Washing oil Tata bottom pressure 103-105kPa, temperature 345-350 ℃, extraction carbolineum fraction; The carbolineum fraction gets into the carbolineum tower, and carbolineum top of tower pressure is 20-25kPa, and temperature is 260-280 ℃, extraction one carbolineum fraction; Carbolineum Tata bottom pressure is 20-25kPa, and temperature is 315-320 ℃, and the extraction carbazole is with after cut;
B, fluorenes crystallization: with the fluorenes fraction that obtains in the A operation after the mold heating unit is heated to 130 ℃ of fusions; Flowing automatically in the stationary crystallization device, is heat-conducting medium with 200 ℃ of thermal oils, slowly is cooled to 95 ℃; The fluorenes fraction forms crystallization, the not crystallization melt of draining on the heat pipe surface; Improve the temperature to 105 ℃ of heat-conducting medium, make the fluorenes impurity in the crystallizing layer melt, after raffinate is separated, improve the temperature of heat-conducting medium once again, crystallizing layer is all melted, repeat aforesaid operations and obtain the high-purity technical fluorenes;
C, extraction half anthracene: behind a carbolineum fraction of the carbolineum top of tower extraction process eluting solvent Pyatyi wash-out, impurity such as phenanthrene wherein, methyl dibenzofuran are by wash-out in the A operation, and the crystallization of gained is half anthracene that contains anthracene and carbazole, and half anthracene gets into and takes off luxuriant and rich with fragrance carbolineum groove; The mother liquor that comprises impurity such as phenanthrene, methyl first fluorenes gets into mother liquor tank, and mother liquor is through distillating recovering solvent, and the luxuriant and rich with fragrance slag of distillatory is as preparation carbon black oil raw material; Described eluting solvent is aromatic hydrocarbon solvent or alkane solvents; Described aromatic hydrocarbon solvent is refined heavy benzole, crude benzol, light oil, dephenolize oil, and described alkane solvents is solvent oil, diesel oil, kerosene;
D, refined anthracene and carbazole: will be pumped in the upgrading tower from half anthracene of C operation, tower top temperature is 155-160 ℃, at the most of solvent of upgrading tower cat head extraction; Column bottom temperature is 233-238 ℃, and fraction carries out underpressure distillation separation anthracene, carbazole by being pumped into anthracene carbazole tower at the bottom of the concentrated Tata, and tower top pressure is 15-21kPa; Temperature is 140-145 ℃; The last side line anthracene of gathering, anthracene extraction temperature is 257-260 ℃, pressure is 16-16.3kPa; The following side line carbazole of gathering, carbazole extraction temperature is 278-285 ℃, pressure is 18.9-19.3kPa; Collected raffinate can be used as preparation carbon black oil raw material at the bottom of the tower.
Mix carbolineum and mainly contain multiple compounds such as naphthalene, acenaphthene, dibenzofuran, fluorenes, anthracene, phenanthrene, carbazole, methyl first fluorenes, firefly anthracene, pyrene; Boiling point is from 200 ℃ to 500 ℃; Components such as washing oil, a carbolineum, anthracene oil have been comprised; Mix the first step of carbolineum processing various components are separated, and then make with extra care respectively.
The major impurity of fluorenes fraction is a dibenzofuran, methyl first fluorenes etc., and wherein the fusing point of fluorenes is higher than about 30 ℃ of the fusing point of other material, therefore can utilize its fusing point different characteristic separating impurity.
The technical process that kinds of processes of the present invention and equipment organic assembling form; Simple and effective; Working stability has realized that a cover technology separates multiple high added value composition---the purpose of fluorenes, anthracene and carbazole, has improved the utility value of a carbolineum fraction, anthracene oil fraction in the coal tar greatly.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention.
Among the figure: 1, washing oil tower; 2, carbolineum tower; 3, the washing oil tower returns sluice; 4, washing oil tower process furnace; 5, water cooler; 6, carbolineum tower process furnace; 7, carbolineum tower backflash; 8, a carbolineum groove; 9, rinse bath; 10, secondary cleaning groove; 11, three rinse baths; 12, four rinse baths; 13, five rinse baths; 14, take off luxuriant and rich with fragrance carbolineum groove; 15, mother liquor tank; 16, mixer; 17, heating tank; 18, novel solvent groove; 19, middle mother liquor tank; 20, upgrading tower; 21, anthracene carbazole tower; 22, anthracene extraction pump; 23, carbazole extraction pump; 24, stillage residue extraction pump; 25, water coolant backflash; 26, anthracene carbazole tower solvent recuperation groove; 27, upgrading tower solvent refluxing groove; 28, vacuum buffer tank; 29, fluorenes tower; 30, fluorenes tower backflash; 31, fluorenes tower process furnace; 32, rectifying feedstock pump; 33, solvent oil pump; 34, stationary crystallization device; 35, mold heating unit; 36, temperature regulating device; 37, heat-conducting medium container.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described, but never in any form the present invention is limited, any change or improvement based on training centre of the present invention is done all belong to protection scope of the present invention.
As shown in the figure, the present invention includes and mix that half anthracene is extracted in carbolineum rectifying, fluorenes stationary crystallization, a carbolineum, anthracene, carbazole are extracted in half anthracene rectifying, specifically comprise following operation:
A, the rectifying of mixing carbolineum: raw materials mix carbolineum is heated to 130-150 ℃ through washing oil tower process furnace, gets into washing oil tower 1; Washing oil tower 1 tower top pressure is 100-105kPa, and temperature is 260-265 ℃, and the extraction washing oil heats up in a steamer; The washing oil fraction gets into fluorenes tower 29, and fluorenes tower 29 tower top pressures are 18-22kPa, and temperature is 145-150 ℃, naphthalene, methylnaphthalene fraction before the extraction dibenzofuran; Side stream temperature is 185-203 ℃ on the fluorenes tower 29, extraction dibenzofuran fraction; 29 times side stream temperatures of fluorenes tower are 198-203 ℃, extraction fluorenes fraction; At the bottom of fluorenes tower 29 towers service temperature 210-212 ℃, extraction carbon black oil fraction; Washing oil tower 1 tower bottom pressure 103-105kPa, temperature 345-350 ℃, extraction carbolineum fraction; The carbolineum fraction gets into the carbolineum tower, and carbolineum tower 2 top pressures are 20-25kPa, and temperature is 260-280 ℃, extraction one carbolineum fraction; Carbolineum tower 2 tower bottom pressures are 20-25kPa, and temperature is 315-320 ℃, and the extraction carbazole is with after cut;
B, fluorenes crystallization: with the fluorenes fraction that obtains in the A operation after mold heating unit 35 is heated to 130 ℃ of fusions; Flowing automatically in the stationary crystallization device, is heat-conducting medium with 200 ℃ of thermal oils, slowly is cooled to 95 ℃; The fluorenes fraction forms crystallization, the not crystallization melt of draining on the heat pipe surface; Improve the temperature to 105 ℃ of heat-conducting medium, make the fluorenes impurity in the crystallizing layer melt, after raffinate is separated, improve the temperature of heat-conducting medium once again, crystallizing layer is all melted, repeat aforesaid operations and obtain the high-purity technical fluorenes;
C, extraction half anthracene: after a carbolineum fraction of carbolineum tower 2 top extraction passes through eluting solvent Pyatyi wash-out in the A operation; Impurity such as phenanthrene wherein, methyl dibenzofuran are by wash-out; The crystallization of gained is half anthracene that contains anthracene and carbazole, and half anthracene gets into and takes off luxuriant and rich with fragrance carbolineum groove 14; The mother liquor that comprises impurity such as phenanthrene, methyl first fluorenes gets into mother liquor tank 15, and mother liquor is through distillating recovering solvent, and the luxuriant and rich with fragrance slag of distillatory is as preparation carbon black oil raw material;
D, refined anthracene and carbazole: will be pumped into from half anthracene of C operation in the upgrading tower 20, tower top temperature is 155-160 ℃, at the most of solvent of upgrading tower 20 cat head extraction; Column bottom temperature is 233-238 ℃, and fraction carries out underpressure distillation separation anthracene, carbazole by being pumped into anthracene carbazole tower 21 at the bottom of upgrading tower 20 towers, and tower top pressure is 15-21kPa; Temperature is 140-145 ℃; The last side line anthracene of gathering, anthracene extraction temperature is 257-260 ℃, pressure is 16-16.3kPa; The following side line carbazole of gathering, carbazole extraction temperature is 278-285 ℃, pressure is 18.9-19.3kPa; Collected raffinate can be used as preparation carbon black oil raw material at the bottom of the tower.
Described stationary crystallization device is board-like or tubular structure, is heat-transfer medium in the pipe, is the fluorenes melt between pipe.
Described intraductal heat transfer medium is a thermal oil.
Eluting solvent in the described C operation is aromatic hydrocarbon solvent or alkane solvents.
Described aromatic hydrocarbon solvent is refined heavy benzole, crude benzol, light oil, dephenolize oil.
Described alkane solvents is solvent oil, diesel oil, kerosene.
Embodiment 1
A, the rectifying of mixing carbolineum: consisting of of raw materials mix carbolineum contains acenaphthene 6%, dibenzofuran 4%, and fluorenes 9%, phenanthrene 25%, anthracene 6%, carbazole 3%, material flow are 6253kg/h.Be heated to 150 ℃ through washing oil tower process furnace, get into the washing oil tower; Washing oil column overhead pressure is 100kPa, and temperature is 260 ℃, and the flow of extraction washing oil fraction is 1630kg/h, consists of acenaphthene 22%, dibenzofuran 14%, fluorenes 32%; The washing oil fraction gets into the fluorenes tower, and fluorenes column overhead pressure is 20kPa, and temperature is 145 ℃; Naphthalene before the extraction dibenzofuran, the flow of methylnaphthalene fraction are 455kg/h, and side stream temperature is 185 ℃ on the fluorenes tower, and the flow of extraction dibenzofuran fraction is 507kg/h; Side stream temperature is 200 ℃ under the fluorenes tower, and the flow of extraction fluorenes fraction is 514kg/h, and it is 89% that fraction contains fluorenes; Service temperature is 210 ℃ at the bottom of the fluorenes Tata, and the flow of extraction carbon black oil fraction is 155kg/h; Washing oil Tata bottom pressure 105kPa, 350 ℃ of temperature, the flow of extraction carbolineum fraction is 4623kg/h, consists of phenanthrene 33%, anthracene 10%, carbazole 6%; The carbolineum fraction gets into the carbolineum tower, and carbolineum top of tower pressure is 20kPa, and temperature is 260 ℃, extraction one carbolineum fraction; Flow is 2450kg/h, consists of phenanthrene 51.5%, anthracene 13.6%, carbazole 6.5%; Carbolineum Tata bottom pressure is 25kPa, and temperature is 315 ℃, and flow is 2172kg/h.
B, fluorenes crystallization: after the fluorenes fraction that the A operation is obtained is heated to 130 ℃ of fusions, flowing automatically in the stationary crystallization device, is heat-conducting medium with 200 ℃ of thermal oils, slowly is cooled to 95 ℃, and the fluorenes fraction forms crystallization, the not crystallization melt of draining on the heat pipe surface; Improve the temperature to 105 ℃ of heat-conducting medium, make the fluorenes impurity in the crystallizing layer melt, after raffinate is separated, improve the temperature of heat-conducting medium once again, crystallizing layer is all melted, obtain purity and be 95% industrial fluorenes, the extraction yield of this operation fluorenes is 81%.
C, extraction half anthracene: the A operation obtains a carbolineum fraction, consists of phenanthrene 51.5%, anthracene 13.6%; Carbazole 6.5%, through obtaining taking off half luxuriant and rich with fragrance anthracene behind the refined heavy benzole solvent Pyatyi wash-out, it consists of and contains luxuriant and rich with fragrance 1.0%; Anthracene 27.5%, carbazole 12.9%, solvent 57.9%; The extraction yield of this operation anthracene is 82.9%, and the extraction yield of carbazole is 81.3%.
D, refined anthracene and carbazole: will be pumped in the upgrading tower from half anthracene of C operation, tower top temperature is 155 ℃, and column bottom temperature is 238 ℃, and fractional composition is anthracene 48% at the bottom of the tower, carbazole 30%, and phenanthrene 2%, solvent 15%, other is 2% years old; Fraction is by being pumped into anthracene carbazole tower at the bottom of concentrating Tata, and this tower is a vacuum still, and tower top pressure is 15kPa, and temperature is 140 ℃, and anthracene extraction temperature is 257 ℃, and pressure is 16.3kPa, and the purity of anthracene is 96%, the extraction rate reached 98% of anthracene; Carbazole extraction temperature is 279 ℃, and pressure is 19.2kPa, and carbazole purity is 97%, and the carbazole extraction yield is 95%.
Embodiment 2
A, mix carbolineum rectifying: the raw materials mix carbolineum identical with embodiment 1, flow is 6350kg/h.Through being preheated to 140 ℃, get into the washing oil tower, washing oil column overhead pressure is 105kPa, and temperature is 265 ℃, and the flow of extraction washing oil fraction is 1550kg/h; The washing oil fraction gets into the fluorenes tower, and fluorenes column overhead pressure-controlling is 148 ℃ for the 22kPa temperature, and flow is 428kg/h, and side stream temperature is 189 ℃ on the fluorenes tower, and extraction dibenzofuran fraction flow is 404kg/h; Side stream temperature is 203 ℃ under the fluorenes tower, and extraction fluorenes fraction flow is 412kg/h; Service temperature is 212 ℃ at the bottom of the fluorenes Tata, and extraction carbon black oil fraction flow is 306kg/h; Washing oil Tata bottom pressure 103kPa, 345 ℃ of temperature, the flow of extraction carbolineum fraction is 4800kg/h; The carbolineum fraction gets into the carbolineum tower, and carbolineum top of tower pressure is 20kPa, and temperature is 260 ℃, and flow is 2420kg/h, extraction one carbolineum fraction; Controlled temperature is 320 ℃ at the bottom of the tower, and pressure is 23kPa, and flow is 2380kg/h.
B, fluorenes crystallization: after the fluorenes fraction that the A operation is obtained is heated to 130 ℃ of fusions, flowing automatically in the stationary crystallization device, is heat-conducting medium with 200 ℃ of thermal oils, slowly is cooled to 95 ℃, the not crystallization melt of draining; Improve the temperature to 110 ℃ of heat-conducting medium thermal oil, make the fluorenes impurity in the crystallizing layer melt, after raffinate is separated, improve the temperature of heat-transfer fluid again, crystallizing layer all melts, and obtains purity and be 96% industrial fluorenes, and the extraction yield of this operation fluorenes is 84%.
C, extraction half anthracene: the A operation obtains a carbolineum fraction, and through half anthracene that obtains behind the light oil solvent Pyatyi wash-out, the extraction yield of this operation anthracene is 82%, and the extraction yield of carbazole is 81%.
D, refined anthracene and carbazole: will be pumped in the concentrating under reduced pressure tower from half anthracene of C operation, the upgrading tower tower top temperature is 158 ℃; Column bottom temperature is 233 ℃: fraction is by being pumped into anthracene carbazole tower at the bottom of concentrating Tata, and this tower is a vacuum still, and tower top pressure is 21kPa; Temperature is 145 ℃, and anthracene extraction temperature is 260 ℃, and pressure is 16kPa; The purity of anthracene is 94%, the extraction rate reached 97% of anthracene; Carbazole extraction temperature is 285 ℃, and pressure is 18.9kPa, and carbazole purity is 97%, and the carbazole extraction yield is 98%.
Embodiment 3
A, mix carbolineum rectifying: the raw materials mix carbolineum identical with embodiment 1, flow is 5050kg/h.Through being preheated to 130 ℃, get into the washing oil tower, tower top pressure is 100kPa, and tower top temperature is 260 ℃, and the flow of extraction washing oil fraction is 1200kg/h; The washing oil fraction gets into the fluorenes tower, and fluorenes column overhead pressure-controlling is 18kPa, and service temperature is 150 ℃, and flow is 235kg/h, and side stream temperature is 190 ℃ on the fluorenes tower, and dibenzofuran fraction flow is 351kg/h; Side stream temperature is 198 ℃ under the fluorenes tower, and extraction fluorenes fraction flow is 429kg/h; Service temperature is 210 ℃ at the bottom of the fluorenes Tata, and flow is 185kg/h, extraction carbon black oil oil fraction; Washing oil Tata bottom pressure 105kPa, 350 ℃ of temperature, the flow of extraction carbolineum fraction is 3850kg/h; The carbolineum fraction gets into the carbolineum tower, and carbolineum top of tower pressure is 25kPa, and temperature is 280 ℃, and flow is 2080kg/h, extraction one carbolineum fraction; Controlled temperature is 320 ℃ at the bottom of the tower, and pressure is 25kPa, and flow is 1770kg/h.
B, fluorenes crystallization: after the fluorenes fraction that the A operation is obtained is heated to 130 ℃, flowing automatically in the mold, is heat-conducting medium with 200 ℃ of thermal oils, slowly is cooled to 95 ℃, the not crystallization melt of draining; Improve the temperature to 110 ℃ of heat-transfer medium thermal oil, the fluorenes impurity in the crystallizing layer melts, and after raffinate is separated, improves the temperature of heat-conducting medium again, and crystallizing layer all melts, and obtains purity and be 95% industrial fluorenes, and the extraction yield of this operation fluorenes is 80%.
C, extraction half anthracene: the A operation obtains a carbolineum fraction, and through half anthracene that obtains behind the dephenolize Oil solvent Pyatyi wash-out, the extraction yield of this operation anthracene is 81%, and the extraction yield of carbazole is 83%.
D, refined anthracene and carbazole: will be pumped in the upgrading tower from half anthracene of C operation, the upgrading tower tower top temperature is 160 ℃, and column bottom temperature is 235 ℃; Fraction is by being pumped into anthracene carbazole tower at the bottom of concentrating Tata, and this tower is a vacuum still, and tower top pressure is 20kPa, and temperature is 140 ℃, and anthracene extraction temperature is 260 ℃, and pressure is 16kPa, and the purity of anthracene is 95%, the extraction rate reached 98% of anthracene; Carbazole extraction temperature is 278 ℃, and pressure is 19.3kPa, and carbazole purity is 96%, and the carbazole extraction yield is 95%.
Embodiment 4
Other operations are identical with embodiment 1.In the C operation, obtain a carbolineum fraction, through thick from the A operation
Obtain behind the benzene solvent Pyatyi wash-out taking off half luxuriant and rich with fragrance anthracene, the extraction yield of this operation anthracene is 81.1%, and the extraction yield of carbazole is 82.6%.
Other operations are identical with embodiment 2.In the C operation, obtain a carbolineum fraction from the A operation, through obtaining taking off half luxuriant and rich with fragrance anthracene behind the solvent oil Pyatyi wash-out, the extraction yield of this operation anthracene is 79.8%, and the extraction yield of carbazole is 81.9%.
Embodiment 6
Other operations are identical with embodiment 3.In the C operation, obtain a carbolineum fraction from the A operation, through obtaining taking off half luxuriant and rich with fragrance anthracene behind the diesel oil Pyatyi wash-out, the extraction yield of this operation anthracene is 80.3%, and the extraction yield of carbazole is 82.1%.。
Embodiment 7
Other operations are identical with embodiment 1.In the C operation, obtain a carbolineum fraction from the A operation, through obtaining taking off half luxuriant and rich with fragrance anthracene behind the kerosene solvent Pyatyi wash-out, the extraction yield of this operation anthracene is 80.9%, and the extraction yield of carbazole is 82.5%.
Characteristics of the present invention:
1, be raw material to mix carbolineum, extracted valuable industrial chemicals such as fluorenes, carbazole, anthracene, reasonable use the fluorenes in one carbolineum, the resources such as carbazole in the anthracene oil.
2, the present invention utilizes highly efficient distilling technology, and the yield of fluorenes, carbazole, anthracene improves greatly, and the extraction yield of fluorenes is 81% in the rectifying, and the extraction yield of anthracene is 88.8%, and the extraction yield of carbazole is 84.9%.
3, the present invention is with stationary crystallization method purification fluorenes, and the extraction yield of fluorenes is up to 81%.
4, the present invention removes the impurity such as phenanthrene in the carbolineum fraction with the continuous washing mode, the extraction rate reached 81.3% of this step anthracene, the extraction rate reached to 82.9% of carbazole.
5, the present invention separates anthracene and carbazole with the method for highly efficient distilling, and the extraction yield of anthracene is up to 98%, and the carbazole extraction yield is up to 97%.
6, the present invention adopts the three-tower type high efficiency packing tower to carry out pre-treatment to mixing carbolineum, respectively fluorenes and the carbolineum fraction that is rich in anthracene, phenanthrene, carbazole is carried out enrichment, separates respectively then, extracts; Level of automation is high; Production environment is friendly, energy-saving and emission-reduction, society and remarkable in economical benefits.
Claims (3)
1. one kind is mixed the method that carbolineum extracts fluorenes, anthracene and carbazole, comprises that the rectifying of mixing carbolineum, fluorenes stationary crystallization, a carbolineum extract half anthracene, anthracene, carbazole are extracted in half anthracene rectifying, specifically comprise following operation:
A, the rectifying of mixing carbolineum: raw materials mix carbolineum is heated to 130-150 ℃ through washing oil tower process furnace, gets into washing oil tower (1); Washing oil tower (1) tower top pressure is 100-105kPa, and temperature is 260-265 ℃, and the extraction washing oil heats up in a steamer; The washing oil fraction gets into fluorenes tower (29), and fluorenes tower (29) tower top pressure is 18-22kPa, and temperature is 145-150 ℃, naphthalene, methylnaphthalene fraction before the extraction dibenzofuran; It is 185-203 ℃ that fluorenes tower (29) is gone up side stream temperature, extraction dibenzofuran fraction; Fluorenes tower (29) side stream temperature down is 198-203 ℃, extraction fluorenes fraction; At the bottom of fluorenes tower (29) tower service temperature 210-212 ℃, extraction carbon black oil fraction; Washing oil tower (1) tower bottom pressure 103-105kPa, temperature 345-350 ℃, extraction carbolineum fraction; The carbolineum fraction gets into the carbolineum tower, and carbolineum tower (2) top pressure is 20-25kPa, and temperature is 260-280 ℃, extraction one carbolineum fraction; Carbolineum tower (2) tower bottom pressure is 20-25kPa, and temperature is 315-320 ℃, and the extraction carbazole is with after cut;
B, fluorenes crystallization: with the fluorenes fraction that obtains in the A operation after mold heating unit (35) is heated to 130 ℃ of fusions; Flowing automatically in the stationary crystallization device, is heat-conducting medium with 200 ℃ of thermal oils, slowly is cooled to 95 ℃; The fluorenes fraction forms crystallization, the not crystallization melt of draining on the heat pipe surface; Improve the temperature to 105 ℃ of heat-conducting medium, make the fluorenes impurity in the crystallizing layer melt, after raffinate is separated, improve the temperature of heat-conducting medium once again, crystallizing layer is all melted, repeat aforesaid operations and obtain the high-purity technical fluorenes;
C, extraction half anthracene: after a carbolineum fraction of carbolineum tower (2) top extraction passes through eluting solvent Pyatyi wash-out in the A operation; Impurity such as phenanthrene wherein, methyl dibenzofuran are by wash-out; The crystallization of gained is half anthracene that contains anthracene and carbazole, and half anthracene gets into and takes off luxuriant and rich with fragrance carbolineum groove (14); The mother liquor that comprises impurity such as phenanthrene, methyl first fluorenes gets into mother liquor tank (15), and mother liquor is through distillating recovering solvent, and the luxuriant and rich with fragrance slag of distillatory is as preparation carbon black oil raw material; Described eluting solvent is aromatic hydrocarbon solvent or alkane solvents; Described aromatic hydrocarbon solvent is refined heavy benzole, crude benzol, light oil, dephenolize oil, and described alkane solvents is solvent oil, diesel oil, kerosene;
D, refined anthracene and carbazole: will be pumped into from half anthracene of C operation in the upgrading tower (20), tower top temperature is 155-160 ℃, at the most of solvent of upgrading tower (20) cat head extraction; Column bottom temperature is 233-238 ℃, and fraction carries out underpressure distillation separation anthracene, carbazole by being pumped into anthracene carbazole tower (21) at the bottom of upgrading tower (20) tower, and tower top pressure is 15-21kPa; Temperature is 140-145 ℃; The last side line anthracene of gathering, anthracene extraction temperature is 257-260 ℃, pressure is 16-16.3kPa; The following side line carbazole of gathering, carbazole extraction temperature is 278-285 ℃, pressure is 18.9-19.3kPa; Collected raffinate can be used as preparation carbon black oil raw material at the bottom of the tower.
2. mixing carbolineum as claimed in claim 1 extracts the method for fluorenes, anthracene and carbazole, and it is characterized in that: described stationary crystallization device is board-like or tubular structure, is heat-transfer medium in the pipe, is the fluorenes melt between pipe.
3. mixing carbolineum as claimed in claim 2 extracts the method for fluorenes, anthracene and carbazole, and its thing is levied and is: described intraductal heat transfer medium is a thermal oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010114548 CN101786935B (en) | 2010-02-26 | 2010-02-26 | Method for extracting fluorene, anthracene and carbazole from mixed anthracene oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010114548 CN101786935B (en) | 2010-02-26 | 2010-02-26 | Method for extracting fluorene, anthracene and carbazole from mixed anthracene oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101786935A CN101786935A (en) | 2010-07-28 |
| CN101786935B true CN101786935B (en) | 2012-12-12 |
Family
ID=42530334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010114548 Active CN101786935B (en) | 2010-02-26 | 2010-02-26 | Method for extracting fluorene, anthracene and carbazole from mixed anthracene oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101786935B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516015A (en) * | 2011-12-12 | 2012-06-27 | 宝钢工程技术集团有限公司 | Production method and system for extracting refined anthracene and carbazole by using crystallization distillation method |
| CN103232318B (en) * | 2013-04-16 | 2016-04-06 | 中冶焦耐工程技术有限公司 | With a carbolineum be raw material production anthracene, the method for smart carbazole and luxuriant and rich with fragrance product and device |
| CN103601667B (en) * | 2013-11-30 | 2015-11-18 | 河南城建学院 | A kind of method being separated carbazole from carbolineum |
| CN103739439B (en) * | 2014-01-22 | 2015-06-17 | 鞍山兴德工程技术有限公司 | Device for preparing refined anthracene and refined carbazole by taking anthracene oil as raw material |
| CN104045506B (en) * | 2014-06-30 | 2015-07-08 | 李信成 | Device and process for extracting phenanthrene, fluoranthene and pyrene products in anthracene oil |
| CN112933633B (en) * | 2021-04-12 | 2023-03-24 | 孝义市金精化工有限公司 | Negative-pressure continuous distillation and separation device for coal tar washing oil and coal tar washing oil separation and refining method |
| CN115193081A (en) * | 2022-07-28 | 2022-10-18 | 武汉宝聚炭材料有限公司 | System and method for efficiently and environmentally extracting crude anthracene |
| CN116217328A (en) * | 2023-03-15 | 2023-06-06 | 盐城汇百实业有限公司 | Method for preparing high-purity anthracene and carbazole by rectifying crude anthracene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164647A (en) * | 1996-09-01 | 1997-11-12 | 武汉钢铁(集团)公司 | Chromatographic column for analysising anthracene oil in tar and using method |
| CN1172791A (en) * | 1996-04-04 | 1998-02-11 | Vft股份公司 | Distillation process for improving yield of pure products from crude anthracene |
| CN1487910A (en) * | 2001-01-24 | 2004-04-07 | ���ظ�˹��ѧ�����ɷ�����˾ | Obtaining anthracene and carbazole by melt-crystallization |
| CN101130517A (en) * | 2006-08-24 | 2008-02-27 | 宝山钢铁股份有限公司 | Process for refining carbazole |
-
2010
- 2010-02-26 CN CN 201010114548 patent/CN101786935B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172791A (en) * | 1996-04-04 | 1998-02-11 | Vft股份公司 | Distillation process for improving yield of pure products from crude anthracene |
| CN1164647A (en) * | 1996-09-01 | 1997-11-12 | 武汉钢铁(集团)公司 | Chromatographic column for analysising anthracene oil in tar and using method |
| CN1487910A (en) * | 2001-01-24 | 2004-04-07 | ���ظ�˹��ѧ�����ɷ�����˾ | Obtaining anthracene and carbazole by melt-crystallization |
| CN101130517A (en) * | 2006-08-24 | 2008-02-27 | 宝山钢铁股份有限公司 | Process for refining carbazole |
Non-Patent Citations (1)
| Title |
|---|
| 华东化工学院燃料教研组.从粗蒽中分离精制蒽、菲、咔唑.《化工学报》.1960,(第02期),138-149. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101786935A (en) | 2010-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101786935B (en) | Method for extracting fluorene, anthracene and carbazole from mixed anthracene oil | |
| CN102304013B (en) | Novel process for producing refined anthracene and refined carbazole by taking crude anthracene as raw material | |
| CN106916044A (en) | A kind of method for refining carbonization crude benzole | |
| CN101898947A (en) | Method for producing 2,4-dichloroacetophenone by using solid waste chlorobenzene tar as raw material | |
| CN103664480A (en) | Method for refining petrobenzene and thiophene by using ionic liquid complex solvent | |
| CN102452886A (en) | Method for purifying 1-octylene from Fischer-Tropsch synthetic oil products | |
| CN103073383A (en) | Method and device for separating isohexane, n-hexane and benzene | |
| CN106943764A (en) | The rectifier unit and method of a kind of cyclohexanone | |
| CN103232318B (en) | With a carbolineum be raw material production anthracene, the method for smart carbazole and luxuriant and rich with fragrance product and device | |
| CN102516015A (en) | Production method and system for extracting refined anthracene and carbazole by using crystallization distillation method | |
| CN102336622B (en) | Reclaiming device and separation method for heavy component residue of coked crude benzene hydrogenation process | |
| CN101250079A (en) | Heat-exchange network device for refining crude benzene and method of operation | |
| CN103351887A (en) | Process for preparing high temperature heat transfer oil base oil by using C10 heavy aromatic residual oil | |
| CN104860797A (en) | Isopropyl ether-isopropyl alcohol azeotrope distillation separation method based on choline chloride deep eutectic solvent | |
| CN102268273B (en) | Deep processing technology for coking wash oil | |
| CN104591952A (en) | Method for refining mesitylene by virtue of differential pressure thermal coupling rectification | |
| CN110668910B (en) | Benzene distillation residue recovery device, recovery method and application | |
| CN101245044B (en) | Method for extracting biphenyl and indole from coal tar recovered wash oil | |
| CN101270026B (en) | Abstraction distillation system special for carbonization benezene or sulfureous containing benezene, and fine purification method | |
| CN105348046B (en) | Method for recovering 4-cumylphenol from phenol tar | |
| CN202337739U (en) | C10 heavy aromatics recycling technology system | |
| CN115093326A (en) | Method for separating ethyl acetate-ethanol-butanone mixture by extraction pressure swing distillation | |
| CN100336788C (en) | Method of extracting high purity acenaphthene from coat tar scrubbing oil | |
| CN210419808U (en) | Fusel recovery system in BDO device waste liquid | |
| CN102807466B (en) | Process for purifying industrial fluorene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170524 Address after: Qujing City, Yunnan Province, 655003 areas of the state to the town of kylin Guangxi Village Patentee after: The many synthesis Chemical Co., Ltd.s in Qujing Address before: Qujing City, Yunnan Province, 655003 areas of the state to the town of kylin Guangxi Village Patentee before: Qujin Zhongyi Finechemical Co., Ltd. |
|
| TR01 | Transfer of patent right |