CN102746089A - Method for extracting fluorene from wash oil of coal tar - Google Patents
Method for extracting fluorene from wash oil of coal tar Download PDFInfo
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- CN102746089A CN102746089A CN2012102417104A CN201210241710A CN102746089A CN 102746089 A CN102746089 A CN 102746089A CN 2012102417104 A CN2012102417104 A CN 2012102417104A CN 201210241710 A CN201210241710 A CN 201210241710A CN 102746089 A CN102746089 A CN 102746089A
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Abstract
The invention discloses a method for extracting fluorene from wash oil of coal tar, belonging to the field of chemical separation. The method comprises the following steps of: carrying out primary normal pressure rectification on the wash oil as a raw material by adopting a proper reflux ratio; intercepting fractions at different temperature sections; dividing the fractions into a high fluorene content fraction section (a fluorene content is larger than 65 percent) and a low fluorene fraction content section; carrying out secondary rectification on low fluorene content fractions; intercepting a proper fraction section to be combined with high fluorene content fractions; adding a recrystallization solvent into the high fluorene content fractions with certain quality according to a certain proportion, and carrying out recrystallization to obtain crude fluorene; and washing the crude fluorene to obtain refined fluorene. According to a process for extracting the fluorene from the wash oil of the coal tar, crude fluorene fractions with the fluorene content larger than 65 percent are obtained through secondary rectification, and the fluorene content can reach above 99.5 percent after another twice recrystallization, so that the solvent consumption is low, the production time is short, and an organic solvent can be repeatedly used after extraction; and in addition, the whole process is convenient to operate, the pollution and the cost are low, and the raw material recovery rate of a product can reach above 25 percent.
Description
Technical field
The present invention relates to the process for extracting of fluorenes, particularly relate to a kind of method of from coal tar wash oil, extracting fluorenes.Belong to the chemical separating field.
Background technology
The 230-300 that cuts when wash oil fraction is coal tar distillation ℃ of cut section is one of important cut in the coal tar distillation process, is rich in valuable Organic Chemicals such as beta-methylnaphthalene, alpha-methyl-naphthalene, acenaphthene, fluorenes.Domestic washing oil is mainly used in the coal stove coal gas and washes benzene, and price is very cheap.Along with the development of fine chemistry industry, Chemicals ranges of application such as technical methylnaphthalene, beta-methylnaphthalene, alpha-methyl-naphthalene, industrial acenaphthylene constantly enlarge, and market demand constantly increases, for the development and use of washing oil are laid a good foundation.Washing oil not only can obtain the pure article of high added value after processing treatment, and matter washing oil in can obtaining.Because heavy constituent content such as acenaphthene, dibenzofuran and fluorenes obviously reduce in the middle matter washing oil, it is washed the benzene effect and is superior to traditional washing oil.Therefore Components of Wash Oil is carried out separation and purification has far-reaching economic benefit.
Fluorenes is mainly used in medicine as raw material, agricultural chemicals, synthetic dyestuff, fields such as engineering plastics.As make tranquilizer, anodyne, hypotensor, control spasm medicine; But synthetic pesticide, weedicide, indanthrene dye; Can make fluorenes urea formaldehyde, washing composition, sterilizing agent, wetting agent, flash liquid agent etc.As the organic synthesis raw material, can synthesize TNF, aryl transparent nylon etc., be used for xerox, pharmacy, sterilizing agent, agricultural chemicals and sterilant; Fluorenes still is the raw material of thermoplastic resin, as is used for fluorochrome, shock resistance synthetic glass and fluorenes urea formaldehyde etc.At present, these utilisation technologies of fluorenes have only few countries such as Japan, the U.S. to grasp, and China still is in the laboratory development stage, and present domestic washing oil separation and purification technology is gone back imperfection, and its key technical index is still waiting further raising.
The separation and purification of fluorenes is a raw material with washing oil rectifying Residual oil, heavy wash oil or low naphthalene washing oil usually, rectifying intercepting high-content fluorenes cut, and then with crystallisation by cooling method or solvent crystallization purification.The fusion-crystallization method that comprises commonly used, (Jia Chunyan, Yin Qiu rings, Zhang Meijing etc. and utilize the fusion-crystallization method to carry out the purification of fluorenes. the chemical industry journal; 2007,58 (9): 2266-2269) through crystallisation by cooling and two stages of sweating, the industrial fluorenes with 95% is a raw material; Through regulating rate of temperature fall, crystallization gentle sweating temperature eventually, prepare the smart fluorenes of purity 97.4%, this method complicated steps; Whole process time is long, is applicable to refining to a small amount of thick fluorenes, suitable suitability for industrialized production.Perfectly crystallization process, (Zhou Tianhang, Yang Keshan. the experimental study of fluorenes cut Crystallization Separation. Coal Chemical Industry, 2002, (3): 40-44) use strict controlled chilling speed of crystallizer and crystallization terminal temperature in the crystallisation process, after spinning obtains containing the thick fluorenes of fluorenes 63%.Though this technology cost is lower, the thick fluorenes product purity of gained is lower.Another kind is a solvent crystallization, (Jia Chunyan. the technical study of the mensuration of fluorenes solubleness and solution crystal process purification fluorenes. Coal Chemical Industry, 2007 (04): 35-38).The wash oil fraction of coal tar or carbolineum cut are separated earlier making industrial fluorenes, adopt crystallization process that industrial fluorenes is made with extra care again, obtain the higher smart fluorenes of purity through batch distillation.But solvent for use methyl alcohol, ethanol, toluene, o-Xylol and propyl carbinol are lower to the separating power of major impurities such as the dibenzofuran in the industrial fluorenes, methyl diphenyl, methyl dibenzofuran; Must pass through repeatedly recrystallization; Just can obtain purity and be higher than 99.5% smart fluorenes; The loss of fluorenes is bigger, and whole process time is long.Also has the method for extracting fluorenes in the washing oil in addition; (Chen Xin. from heavy wash oil, extract the technical study of industrial fluorenes. the Anshan iron and steel plant technology; 2000, (10): be raw material 6-8.), obtain the industrial fluorenes of two quality grades of purity＞93% and＞95% with the wash oil fraction that contains fluorenes 20%～30%; But its product is merely 12% to the yield of raw material, and productive rate remains further to be improved.
Summary of the invention
To the present invention seeks in order addressing the above problem, a kind of method of from coal tar wash oil, extracting fluorenes to be provided.
Technical scheme of the present invention realizes through following method:
A kind of method of from coal tar wash oil, extracting fluorenes comprises the following steps:
Step 1, in container, add coal tar wash oil after, receive container on the rectifier unit, setting reflux ratio is 10～20: 1; Heating can produce steam after the coal tar wash oil boiling, and steam becomes liquid to flow in the container in the rectifier unit through condenser condenses, promptly obtains the rectifying front-end volatiles; When treating that the rectifying front-end volatiles come to life, the constant boiling temperature of controlled temperature at the rectifying front-end volatiles, this moment, the rectifier unit top had cut to reflux; After treating that the rectifier unit tip temperature is stable, the beginning collecting temperature is 270～280 ℃ a cut, and 275～277 ℃ the cut and the cut of other temperature that collect are sub-packed in the different containers; Temperature between 275～277 ℃ is a high-content fluorenes cut section, and other temperature is the fluorenes cut section of low levels;
The fluorenes cut of the low levels of step 2, step 1 gained carries out secondary rectifying according to the method for step 1, and collecting temperature is after 275～277 ℃ the cut section, merges with the high-content fluorenes cut of step 1 gained, is cooled to room temperature, obtains thick fluorenes cut;
Step 3, in the thick fluorenes cut of step 2 gained, add organic solvent and carry out recrystallization and obtain thick fluorenes; The mass ratio of wherein thick fluorenes cut and organic solvent is 1: 4～6; The whole temperature of crystallization is 30～50 ℃, and rate of temperature fall is 0.1～0.3 ℃/min;
Step 4, with the thick fluorenes of organic solvent and step 3 gained according to mass ratio be 2～5: 1 mix after, adopt the 0 usefulness recrystallization condition identical with step 3, carry out the recrystallization second time, refiningly obtain smart fluorenes;
Step 3, the described organic solvent of step 4 are a kind of or any two kinds mixing solutions in toluene, ethanol, methyl alcohol, the ETHYLE ACETATE
Beneficial effect
1, a kind of technology of from coal tar wash oil, extracting fluorenes of the present invention; Obtain containing the thick fluorenes cut of fluorenes amount＞65% through secondary rectifying, the content through fluorenes behind twice recrystallization just can reach more than 99.5% again, and solvent consumption is few; PT is short, and organic solvent is reusable through extracting the back;
2, a kind of technology of from coal tar wash oil, extracting fluorenes of the present invention, convenient, the low pollution of whole process operation, low cost, product can reach more than 25% the yield of raw material, has industrial prospect.
Embodiment
Embodiment 1
Step 1, in the 2000ml there-necked flask, add the coal tar wash oil of 1600g; Receive there-necked flask on the rectifier unit; Open electric mantle and begin heating; Note observing the intelligent controller temperature, when treating that the rectifying front-end volatiles come to life, through the temperature of adjustment transformer efficiency control rectifier unit heating.When rectifier unit has cut to reflux; After total reflux treated that tower top temperature is stable about half a hour, setting reflux ratio was 10: 1, and the beginning collecting temperature is 270～280 ℃ a cut; Collect the high-content fluorenes cut section 390g between 275～277 ℃, other is the fluorenes cut section 280g of low levels;
Step 2, the fluorenes cut of the low levels of step 1 gained is carried out secondary rectifying according to the method for step 1, collecting temperature is after 275～277 ℃ the cut section, merges with the high-content fluorenes cut of step 1 gained, is cooled to room temperature, obtains thick fluorenes cut 520g;
Step 3, in the thick fluorenes cut of step 2 gained, add 2100g toluene and carry out recrystallization, rate of temperature fall is 0.1/min, and the whole temperature of crystallization is 30 ℃, obtains the thick fluorenes of 490g;
Step 4, with 1000g toluene with after the thick fluorenes of step 3 gained mixes; Adopt the recrystallization condition identical, carry out the recrystallization second time, the refining smart fluorenes of 470g that obtains with step 3; Contain fluorenes amount＞99.7% through the performance liquid chromatography detection, product is 29.3% to the yield of raw material.
Embodiment 2
Step 1, in the 2000ml there-necked flask, add the coal tar wash oil of 1600g; Receive there-necked flask on the rectifier unit; Open electric mantle and begin heating; Note observing the intelligent controller temperature, when treating that the rectifying front-end volatiles come to life, through the temperature of adjustment transformer efficiency control rectifier unit heating.When rectifier unit has cut to reflux; After total reflux treated that tower top temperature is stable about half a hour, setting reflux ratio was 20: 1, and the beginning collecting temperature is 270～280 ℃ a cut; Collect the high-content fluorenes cut section 405g between 275～277 ℃, other is the fluorenes cut section 290g of low levels;
Step 2, the fluorenes cut of the low levels of step 1 gained is carried out secondary rectifying according to the method for step 1, collecting temperature is after 275～277 ℃ the cut section, merges with the high-content fluorenes cut of step 1 gained, is cooled to room temperature, obtains thick fluorenes cut 535g;
Step 3, in the thick fluorenes cut of step 2 gained, add 2500g ethanol and carry out recrystallization, rate of temperature fall is 0.2/min, and the whole temperature of crystallization is 40 ℃, obtains thick fluorenes 500g;
Step 4, with 1500g ethanol with after the thick fluorenes of step 3 gained mixes; Adopt the recrystallization condition identical, carry out the recrystallization second time, the refining smart fluorenes of 478g that obtains with step 3; Contain fluorenes amount＞99.5% through the performance liquid chromatography detection, product is 29.8% to the yield of raw material.
Embodiment 3
Step 1, in the 2000ml there-necked flask, add the coal tar wash oil of 1600g; Receive there-necked flask on the rectifier unit; Open electric mantle and begin heating; Note observing the intelligent controller temperature, when treating that the rectifying front-end volatiles come to life, through the temperature of adjustment transformer efficiency control rectifier unit heating.When rectifier unit has cut to reflux; After total reflux treated that tower top temperature is stable about half a hour, setting reflux ratio was 15: 1, and the beginning collecting temperature is 270～280 ℃ a cut; Collect the high-content fluorenes cut section 395g between 275～277 ℃, other is the fluorenes cut section 270g of low levels;
Step 2, the fluorenes cut of the low levels of step 1 gained is carried out secondary rectifying according to the method for step 1, collecting temperature is after 275～277 ℃ the cut section, merges with the high-content fluorenes cut of step 1 gained, is cooled to room temperature, obtains thick fluorenes cut 480g;
Step 3, in the thick fluorenes cut of step 2 gained, add 2400g methyl alcohol and carry out recrystallization, rate of temperature fall is 0.3/min, and the whole temperature of crystallization is 50 ℃, obtains thick fluorenes 460g;
Step 4, with 1850g methyl alcohol with after the thick fluorenes of step 3 gained mixes; Adopt the recrystallization condition identical, carry out the recrystallization second time, make with extra care and obtain smart fluorenes 435g with step 3; Contain fluorenes amount＞99.8% through the performance liquid chromatography detection, product is 27.1% to the yield of raw material.
Embodiment 4
Step 1, in the 2000ml there-necked flask, add the coal tar wash oil of 1600g; Receive there-necked flask on the rectifier unit; Open electric mantle and begin heating; Note observing the intelligent controller temperature, when treating that the rectifying front-end volatiles come to life, through the temperature of adjustment transformer efficiency control rectifier unit heating.When rectifier unit has cut to reflux; After total reflux treated that tower top temperature is stable about half a hour, setting reflux ratio was 13: 1, and the beginning collecting temperature is 270～280 ℃ a cut; Collect the high-content fluorenes cut section 395g between 275～277 ℃, other is the fluorenes cut section 270g of low levels;
Step 2, the fluorenes cut of the low levels of step 1 gained is carried out secondary rectifying according to the method for step 1, collecting temperature is after 275～277 ℃ the cut section, merges with the high-content fluorenes cut of step 1 gained, is cooled to room temperature, obtains thick fluorenes cut 475g;
Step 3, in the thick fluorenes cut of step 2 gained, add 1500g ETHYLE ACETATE and carry out recrystallization, rate of temperature fall is 0.2 ℃/min, and the whole temperature of crystallization is 40 ℃, obtains thick fluorenes 450g;
Step 4, with 1800g ETHYLE ACETATE with after the thick fluorenes of step 3 gained mixes; Adopt the recrystallization condition identical, carry out the recrystallization second time, make with extra care and obtain smart fluorenes 415g with step 3; Contain fluorenes amount＞99.5% through the performance liquid chromatography detection, product is 25.9% to the yield of raw material.
Embodiment 5
Step 1, in the 2000ml there-necked flask, add the coal tar wash oil of 1600g; Receive there-necked flask on the rectifier unit; Open electric mantle and begin heating; Note observing the intelligent controller temperature, when treating that the rectifying front-end volatiles come to life, through the temperature of adjustment transformer efficiency control rectifier unit heating.When rectifier unit has cut to reflux; After total reflux treated that tower top temperature is stable about half a hour, setting reflux ratio was 13: 1, and the beginning collecting temperature is 270～280 ℃ a cut; Collect the high-content fluorenes cut section 400g between 275～277 ℃, other is the fluorenes cut section 280g of low levels;
Step 2, the fluorenes cut of the low levels of step 1 gained is carried out secondary rectifying according to the method for step 1, collecting temperature is after 275～277 ℃ the cut section, merges with the high-content fluorenes cut of step 1 gained, is cooled to room temperature, obtains thick fluorenes cut 490g;
Step 3, in the thick fluorenes cut of step 2 gained, add 2000g toluene and carry out recrystallization, rate of temperature fall is 0.3 ℃/min, and the whole temperature of crystallization is 30 ℃, obtains thick fluorenes 460g;
Step 4, with 2300g ETHYLE ACETATE with after the thick fluorenes of step 3 gained mixes; Adopt the recrystallization condition identical, carry out the recrystallization second time, make with extra care and obtain smart fluorenes 440g with step 3; Contain fluorenes amount＞99.7% through the performance liquid chromatography detection, product is 27.5% to the yield of raw material.
Claims (2)
1. a method of from coal tar wash oil, extracting fluorenes is characterized in that: comprise the following steps:
Step 1, in container, add coal tar wash oil after, receive container on the rectifier unit, setting reflux ratio is 10～20: 1; Heating can produce steam after the coal tar wash oil boiling, and steam becomes liquid to flow in the container in the rectifier unit through condenser condenses, promptly obtains the rectifying front-end volatiles; When treating that the rectifying front-end volatiles come to life, the rectifier unit top has cut to reflux; After treating that the rectifier unit tip temperature is stable, the beginning collecting temperature is 270～280 ℃ a cut, and 275～277 ℃ the cut and the cut of other temperature that collect are sub-packed in the different containers; Temperature between 275～277 ℃ is a high-content fluorenes cut section, and other temperature is the fluorenes cut section of low levels;
The fluorenes cut of the low levels of step 2, step 1 gained carries out secondary rectifying according to the method for step 1, and collecting temperature is after 275～277 ℃ the cut section, merges with the high-content fluorenes cut of step 1 gained, is cooled to room temperature, obtains thick fluorenes cut;
Step 3, in the thick fluorenes cut of step 2 gained, add organic solvent and carry out recrystallization and obtain thick fluorenes; The mass ratio of wherein thick fluorenes cut and organic solvent is 1: 4～6; The whole temperature of crystallization is 30～50 ℃, and rate of temperature fall is 0.1～0.3 ℃/min;
Step 4, with the thick fluorenes of organic solvent and step 3 gained according to mass ratio be 2～5: 1 mix after, adopt the recrystallization condition identical with step 3, carry out the recrystallization second time, refiningly obtain smart fluorenes.
2. a kind of method of from coal tar wash oil, extracting fluorenes as claimed in claim 1, it is characterized in that: step 3, the described organic solvent of step 4 are a kind of or any two kinds mixing solutions in toluene, ethanol, methyl alcohol, the ETHYLE ACETATE.
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| CN2012102417104A CN102746089A (en) | 2012-07-13 | 2012-07-13 | Method for extracting fluorene from wash oil of coal tar |
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| CN2012102417104A CN102746089A (en) | 2012-07-13 | 2012-07-13 | Method for extracting fluorene from wash oil of coal tar |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304365A (en) * | 2013-06-28 | 2013-09-18 | 江西理工大学 | New process for purifying and refining coarse fluorene |
| CN109232524A (en) * | 2018-10-21 | 2019-01-18 | 辽宁科技学院 | A method of the separation and purification dibenzothiophen from coal tar |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH072706A (en) * | 1993-06-16 | 1995-01-06 | Osaka Gas Co Ltd | Production of fluorene |
| CN1884234A (en) * | 2005-06-22 | 2006-12-27 | 上海宝钢化工有限公司 | Method for purifying fluorene crystals |
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2012
- 2012-07-13 CN CN2012102417104A patent/CN102746089A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH072706A (en) * | 1993-06-16 | 1995-01-06 | Osaka Gas Co Ltd | Production of fluorene |
| CN1884234A (en) * | 2005-06-22 | 2006-12-27 | 上海宝钢化工有限公司 | Method for purifying fluorene crystals |
Non-Patent Citations (3)
| Title |
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| 李素梅等: "芴的提取精制研究进展", 《河北化工》 * |
| 梁晓强: "洗油中芴和氧芴的提取", 《中国优秀硕士学位论文全文数据库》 * |
| 陈新: "从重质洗油中提取工业芴的工艺研究", 《鞍钢技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304365A (en) * | 2013-06-28 | 2013-09-18 | 江西理工大学 | New process for purifying and refining coarse fluorene |
| CN103304365B (en) * | 2013-06-28 | 2016-02-03 | 江西理工大学 | A kind of thick fluorenes purification novel process |
| CN109232524A (en) * | 2018-10-21 | 2019-01-18 | 辽宁科技学院 | A method of the separation and purification dibenzothiophen from coal tar |
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Application publication date: 20121024 |