CN102731282B - Method for extracting dibenzofuran from absorber oil of coal tar - Google Patents
Method for extracting dibenzofuran from absorber oil of coal tar Download PDFInfo
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Abstract
The invention relates to a method for extracting dibenzofuran from an absorber oil of coal tar, belonging to the field of chemical separation. The method comprises the steps of performing first constant pressure rectification for the raw material absorber oil by using an appropriate reflux ratio; capturing fractions of different temperature sections; dividing the fractions into a high-content dibenzofuran fraction section (content of dibenzofuran is greater than 5%) and a low-content dibenzofuran fraction section; performing secondary rectification for the low-content dibenzofuran fraction, capturing the appropriate fraction sections, combining the fraction sections with the high-content dibenzofuran fraction; adding a recrystallization solvent into the high-content dibenzofuran fraction of certain mass according to a certain proportion for recrystallization to obtain coarse fluorene; and then performing secondary recrystallization for the coarse fluorene to obtain refined fluorene. The method provided by the invention obtains coarse dibenzofuran with dibenzofuran content greater than 60% through rectification for two times, and then the dibenzofuran is extracted by the organic solvent in a supercritical state. Equipment used in the whole process is simple, energy consumption is low, the operation is convenient, and yield is high. The separation method is simple, the product is free from loss, the solvent is easy to recycle and can be recycled for many times. Substantially no pollution is generated, the cost is low and the method provided by the invention has industrialization prospect.
Description
Technical field
The present invention relates to the extracting method of dibenzofuran, particularly relate to a kind of method of extracting dibenzofuran from coal tar wash oil.Belong to chemical separating field.
Background technology
230～300 ℃ of cut sections that cut when wash oil fraction is coal tar distillation, are one of important cuts in coal tar distillation process, are rich in the valuable Organic Chemicals such as β～methylnaphthalene, α～methylnaphthalene, acenaphthene, fluorenes.Dibenzofuran is the important component that in washing oil, content is higher, value is large, purposes is larger.Separated dibenzofuran from washing oil, can avoid other materials in dibenzofuran and washing oil to form azeotrope, is conducive to the extraction of other components, can also reduce the polymerizability of washing oil, improves washing oil mobility and washing effect.Therefore, from washing oil, extract dibenzofuran, have important practical significance and wide application prospect.
Dibenzofuran (dibenzofuran) has another name called diphenylene oxide, diphenylene-oxide, molecular formula C
12h
8o, molecular weight 168, dibenzofuran is white or colourless needle-like or lobate crystal, band blue-fluorescence, slightly has a distinctive odor, water insoluble, can be dissolved in most of organic solvents, as methyl alcohol, ethanol, benzene, acetic acid etc., can volatilize with water vapor, can distil.Dibenzofuran is of many uses, is mainly used in following aspect: (1) produces dyestuff dibenzofuran and generates 3-bromine dibenzofuran through bromination, saponification and carboxylated after obtain dibenzofuran-2,3-acid, can be used for producing dyestuff.(2) produce the acetylize of medicine dibenzofuran and generate 3-acetyl dibenzofuran, reduction and aminoalkyl group obtain 3-aminoalkyl group dibenzofuran, can be used as convulsion relieving agent and anodyne.Dibenzofuran alkali-melting can obtain 2,2-'-biphenyl diphenol, is sterilizing agent and deinsectization sterilant; Also can produce veterinary drug nitroclofene (Bayer 9015), be used for the treatment of liver's trematodiasis of ox, sheep etc.(3) produce the sulfonation polycondensation together with lipid acid, fat, alcohols, phenols or alkyl halide of various auxiliary agent dibenzofuran, can obtain the chlorination dibenzofuran that wetting agent, textile auxiliary agent, chlorination obtain is electrically insulating material additive, and sulfonated polycondensate can be used as textile auxiliary agent and wetting agent etc.(4) other dibenzofuran also can be used as thermal barrier, and food and wood preservative etc.
US Patent No. 460812 has been introduced a kind of separation and refining method of dibenzofuran, take heavy wash oil as raw material, by rectifying washing oil, obtain the dibenzofuran cut containing dibenzofuran massfraction > 30%, again this dibenzofuran cut is put into second rectifying tower, then the cut of specific range of temperatures is purified in continuous crystallisation machine, obtain high purity dibenzofuran.This kind of method productive rate is low, and needed plant and instrument is huge, and cost of investment is higher.
Another kind method is to adopt 60 valve tray rectifying tower, intercepts the dibenzofuran cut of 280～286 ℃, and dibenzofuran content is 55%～65%.Wide fraction is at N～40 rectifying tower rectifying intercepting dibenzofuran narrow fraction again, and its dibenzofuran content can reach 80%.By high-content dibenzofuran cut, adopted the dibenzofuran of solvent crystallization purifying high-purity.(Xiao Ruihua. coal tar chemical science. Beijing: metallurgical industry press, 2002:170) this method adopts a large amount of solvents just can obtain purity higher oxygen fluorenes through recrystallization repeatedly, and in recrystallization process, the loss amount of dibenzofuran is larger.
Summary of the invention
To the present invention seeks to that equipment requirements is high in order solving in prior art, to be subject to loss in dibenzofuran purification process, and the higher problem of cost, a kind of method of extracting dibenzofuran from coal tar wash oil is provided.
The object of the invention is to be achieved through the following technical solutions.
A method of extracting dibenzofuran from coal tar wash oil, comprises the following steps:
Step 1, in container, add after coal tar wash oil, container is received on rectifier unit, setting reflux ratio is 10～20: 1; Heating, can produce steam after coal tar wash oil boiling, and steam becomes liquid to flow in the container in rectifier unit by condenser condenses, obtains rectifying front-end volatiles; When rectifying front-end volatiles come to life, control homo(io)thermism at the boiling temperature of rectifying front-end volatiles, now rectifier unit top has cut to reflux; After rectifier unit tip temperature is stable, beginning collecting temperature is the cut of 280～290 ℃, and the cut of 285～287 ℃ and the cut of other temperature that collect are sub-packed in different containers; Temperature between 285～287 ℃ is high-content dibenzofuran cut section, the dibenzofuran cut section that other temperature is low levels;
The dibenzofuran 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 the cut section of 285～287 ℃, merges with the high-content dibenzofuran cut of step 1 gained, is cooled to room temperature, obtains thick dibenzofuran cut;
Step 3, in the thick dibenzofuran cut of step 2 system, add extraction agent, join high pressure and divide and answer in still after mixing, the pressure of controlling in autoclave is 7～9MPa; Be heated to 230 ℃～250 ℃, after reaction 1～5h, be cooled to room temperature, filter and collect filtrate;
Step 4, the filtrate of step 3 gained is put into decompression evaporator, control pressure is between vacuum 10MPa～1MPa, until absence of liquid steams, the solid obtaining in vaporizer is smart dibenzofuran.
Extraction agent described in step 3 is any one in ethanol, methyl alcohol, toluene; The mass ratio of extraction agent and thick dibenzofuran is: 1～3: 1
Beneficial effect
1, a kind of method of extracting dibenzofuran from coal tar wash oil of the present invention, by twice rectifying, obtain the thick dibenzofuran containing dibenzofuran amount > 60%, with organic solvent, under supercritical state, extract dibenzofuran again, whole process is used equipment simple, energy expenditure is low, easy to operate, productive rate is high;
2, a kind of method of extracting dibenzofuran from coal tar wash oil of the present invention, supercritical extraction dibenzofuran with an organic solvent, underpressure distillation steams solvent and obtains smart dibenzofuran again, separation method is simple, and product is loss not, and solvent recuperation is easy, can repeatedly recycle, basic not pollution, cost is low, has industrial prospect.
Embodiment
Embodiment 1
Step 1, in 2000ml there-necked flask, add the coal tar wash oil of 1000g, there-necked flask is received on rectifier unit, setting reflux ratio is 10: 1; Heating, can produce steam after coal tar wash oil boiling, and steam becomes liquid to flow in the flask in rectifier unit by condenser condenses, obtains rectifying front-end volatiles; When rectifying front-end volatiles come to life, control homo(io)thermism at the boiling temperature of rectifying front-end volatiles, now rectifier unit top has cut to reflux; Total reflux about half an hour, after rectifier unit tip temperature is stable, starts collecting temperature and is the cut of 280～290 ℃, and the cut of 285～287 ℃ and the cut of other temperature that collect are sub-packed in different containers; Collect the high-content dibenzofuran cut section 315g between 285～287 ℃, the dibenzofuran cut section 210g that other is low levels;
The dibenzofuran cut of the low levels of step 2, step 1 gained carries out secondary rectifying according to the method for step 1, collecting temperature is after the cut section of 285～287 ℃, merge with the high-content dibenzofuran cut of step 1 gained, be cooled to room temperature, obtain thick dibenzofuran cut 400g;
Step 3, in the thick dibenzofuran cut of step 2 system, add 400g ethanol, join high pressure and divide and answer in still after mixing, the pressure of controlling in autoclave is 7MPa; Be heated to 230 ℃, after reaction 1h, be cooled to room temperature, filter and collect filtrate;
Step 4, the filtrate of step 3 gained is put into decompression evaporator, control pressure is at vacuum 10MPa, until absence of liquid steams, the 250g solid obtaining in vaporizer is smart dibenzofuran.Through gas chromatographic detection, containing dibenzofuran amount > 99.5%, product is 25% to the yield of raw material.
Embodiment 2
Step 1, in 2000ml there-necked flask, add the coal tar wash oil of 1000g, there-necked flask is received on rectifier unit, setting reflux ratio is 20: 1; Heating, can produce steam after coal tar wash oil boiling, and steam becomes liquid to flow in the flask in rectifier unit by condenser condenses, obtains rectifying front-end volatiles; When rectifying front-end volatiles come to life, control homo(io)thermism at the boiling temperature of rectifying front-end volatiles, now rectifier unit top has cut to reflux; Total reflux about half an hour, after rectifier unit tip temperature is stable, starts collecting temperature and is the cut of 280～290 ℃, collects the high-content dibenzofuran cut section 305g between 285～287 ℃, the dibenzofuran cut section 200g that other is low levels;
The dibenzofuran 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 the cut section of 285～287 ℃, merges with the high-content dibenzofuran cut of step 1 gained, is cooled to room temperature, obtains thick dibenzofuran cut 385;
Step 3, in the thick dibenzofuran cut of step 2 system, add 800g methyl alcohol, join high pressure and divide and answer in still after mixing, the pressure of controlling in autoclave is 9MPa; Be heated to 250 ℃, after reaction 5h, be cooled to room temperature, filter and collect filtrate;
Step 4, the filtrate of step 3 gained is put into decompression evaporator, control pressure is at vacuum 1MPa, until absence of liquid steams, the 220g solid obtaining in vaporizer is smart dibenzofuran.Through gas chromatographic detection, containing dibenzofuran amount > 99.4%, product is 22% to the yield of raw material.
Embodiment 3
Step 1, in 2000ml there-necked flask, add the coal tar wash oil of 1000g, there-necked flask is received on rectifier unit, setting reflux ratio is 15: 1; Heating, can produce steam after coal tar wash oil boiling, and steam becomes liquid to flow in the flask in rectifier unit by condenser condenses, obtains rectifying front-end volatiles; When rectifying front-end volatiles come to life, control homo(io)thermism at the boiling temperature of rectifying front-end volatiles, now rectifier unit top has cut to reflux; Total reflux about half an hour, after rectifier unit tip temperature is stable, starts collecting temperature and is the cut of 280～290 ℃, collects the high-content dibenzofuran cut section 335g between 285～287 ℃, the dibenzofuran cut section 200g that other is low levels;
The dibenzofuran cut of the low levels of step 2, step 1 gained carries out secondary rectifying according to the method for step 1, collecting temperature is after the cut section of 285～287 ℃, merge with the high-content dibenzofuran cut of step 1 gained, be cooled to room temperature, obtain thick dibenzofuran cut 410g;
Step 3, in the thick dibenzofuran cut of step 2 system, add 1200g toluene, join high pressure and divide and answer in still after mixing, the pressure of controlling in autoclave is 8MPa; Be heated to 240 ℃, after reaction 3h, be cooled to room temperature, filter and collect filtrate;
Step 4, the filtrate of step 3 gained is put into decompression evaporator, control pressure is at vacuum 5MPa, until absence of liquid steams, the 260g solid obtaining in vaporizer is smart dibenzofuran.Through gas chromatographic detection, containing dibenzofuran amount > 99.7%, product is 26% to the yield of raw material.
Embodiment 4
Step 1, in 2000ml there-necked flask, add the coal tar wash oil of 1000g, there-necked flask is received on rectifier unit, setting reflux ratio is 13: 1; Heating, can produce steam after coal tar wash oil boiling, and steam becomes liquid to flow in the flask in rectifier unit by condenser condenses, obtains rectifying front-end volatiles; When rectifying front-end volatiles come to life, control homo(io)thermism at the boiling temperature of rectifying front-end volatiles, now rectifier unit top has cut to reflux; Total reflux about half an hour, after rectifier unit tip temperature is stable, starts collecting temperature and is the cut of 280～290 ℃, collects the high-content dibenzofuran cut section 305g between 285～287 ℃, the dibenzofuran cut section 200g that other is low levels;
The dibenzofuran cut of the low levels of step 2, step 1 gained carries out secondary rectifying according to the method for step 1, collecting temperature is after the cut section of 285～287 ℃, merge with the high-content dibenzofuran cut of step 1 gained, be cooled to room temperature, obtain thick dibenzofuran cut 390g;
Step 3, in the thick dibenzofuran cut of step 2 system, add 1600g methyl alcohol, join high pressure and divide and answer in still after mixing, the pressure of controlling in autoclave is 7MPa; Be heated to 235 ℃, after reaction 2h, be cooled to room temperature, filter and collect filtrate;
Step 4, the filtrate of step 3 gained is put into decompression evaporator, control pressure is at vacuum 3MPa, until absence of liquid steams, the 235g solid obtaining in vaporizer is smart dibenzofuran.Through gas chromatographic detection, containing dibenzofuran amount > 99.2%, product is 23.5% to the yield of raw material.
Embodiment 5
Step 1, in 2000ml there-necked flask, add the coal tar wash oil of 1000g, there-necked flask is received on rectifier unit, setting reflux ratio is 18: 1; Heating, can produce steam after coal tar wash oil boiling, and steam becomes liquid to flow in the flask in rectifier unit by condenser condenses, obtains rectifying front-end volatiles; When rectifying front-end volatiles come to life, control homo(io)thermism at the boiling temperature of rectifying front-end volatiles, now rectifier unit top has cut to reflux; Total reflux about half an hour, after rectifier unit tip temperature is stable, starts collecting temperature and is the cut of 280～290 ℃, collects the high-content dibenzofuran cut section 295g between 285～287 ℃, the dibenzofuran cut section 190g that other is low levels;
The dibenzofuran cut of the low levels of step 2, step 1 gained carries out secondary rectifying according to the method for step 1, collecting temperature is after the cut section of 285～287 ℃, merge with the high-content dibenzofuran cut of step 1 gained, be cooled to room temperature, obtain thick dibenzofuran cut 385g;
Step 3, in the thick dibenzofuran cut of step 2 system, add 1900g toluene, join high pressure and divide and answer in still after mixing, the pressure of controlling in autoclave is 9MPa; Be heated to 245 ℃, after reaction 4h, be cooled to room temperature, filter and collect filtrate;
Step 4, the filtrate of step 3 gained is put into decompression evaporator, control pressure is at vacuum 8MPa, until absence of liquid steams, the 270g solid obtaining in vaporizer is smart dibenzofuran.Through gas chromatographic detection, containing dibenzofuran amount > 99.5%, product is 27% to the yield of raw material.
Claims (1)
1. from coal tar wash oil, extract a method for dibenzofuran, it is characterized in that: comprise the following steps:
Step 1, in 2000ml there-necked flask, add the coal tar wash oil of 1000g, there-necked flask is received on rectifier unit, setting reflux ratio is 13: 1; Heating, can produce steam after coal tar wash oil boiling, and steam becomes liquid to flow in the flask in rectifier unit by condenser condenses, obtains rectifying front-end volatiles; When rectifying front-end volatiles come to life, control homo(io)thermism at the boiling temperature of rectifying front-end volatiles, now rectifier unit top has cut to reflux; Total reflux about half an hour, after rectifier unit tip temperature is stable, starts collecting temperature and is the cut of 280～290 ℃, collects the high-content dibenzofuran cut section 305g between 285～287 ℃, the dibenzofuran cut section 200g that other is low levels;
The dibenzofuran cut of the low levels of step 2, step 1 gained carries out secondary rectifying according to the method for step 1, collecting temperature is after the cut section of 285～287 ℃, merge with the high-content dibenzofuran cut of step 1 gained, be cooled to room temperature, obtain thick dibenzofuran cut 390g;
Step 3, in the thick dibenzofuran cut of step 2 system, add 1600g methyl alcohol, join high pressure and divide and answer in still after mixing, the pressure of controlling in autoclave is 7MPa; Be heated to 235 ℃, after reaction 2h, be cooled to room temperature, filter and collect filtrate;
Step 4, the filtrate of step 3 gained is put into decompression evaporator, control pressure is at vacuum 3MPa, until absence of liquid steams, the 235g solid obtaining in vaporizer is smart dibenzofuran.Through gas chromatographic detection, containing dibenzofuran amount >99.2%, product is 23.5% to the yield of raw material.
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| CN201210239739.9A CN102731282B (en) | 2012-07-12 | 2012-07-12 | Method for extracting dibenzofuran from absorber oil of coal tar |
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| CN201210239739.9A CN102731282B (en) | 2012-07-12 | 2012-07-12 | Method for extracting dibenzofuran from absorber oil of coal tar |
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| WO1982002047A1 (en) * | 1980-12-10 | 1982-06-24 | Sakuma Kiyoshi | Process for producing dibenzofuran |
| CN1208727A (en) * | 1997-08-14 | 1999-02-24 | 攀钢集团煤化工公司 | Continuous distillation technology for coking naphthalene oil fraction |
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