CN106928172B - A kind of process for refining of dibenzofuran - Google Patents
A kind of process for refining of dibenzofuran Download PDFInfo
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- CN106928172B CN106928172B CN201710125235.7A CN201710125235A CN106928172B CN 106928172 B CN106928172 B CN 106928172B CN 201710125235 A CN201710125235 A CN 201710125235A CN 106928172 B CN106928172 B CN 106928172B
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- dibenzofuran
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
Abstract
The present invention relates to a kind of process for refining of dibenzofuran, the dibenzofuran fraction containing dibenzofuran 55%~65% that it is obtained using washing oil Residual oil or heavy wash oil rectifying is raw material, direct crystallisation by cooling is centrifuged to obtain the thick dibenzofuran containing dibenzofuran 85% or so, 95% ethyl alcohol and DMF(N is added in thick dibenzofuran, dinethylformamide) mixed solvent rising temperature for dissolving, then a certain amount of water is added dropwise as precipitating reagent, impurity fluorenes is precipitated, solution crystallisation by cooling after heat filtering is centrifugally separating to obtain the dibenzofuran that content is greater than 98%, and yield is greater than 85%.Mixed solvent and precipitating reagent, two-step method refine dibenzofuran, avoid secondary rectifying, reduce energy consumption, and entire technique is made to have the multiple advantages such as easy to operate, good product quality, product yield height, the few, safety and environmental protection of solvent usage.
Description
Technical field
Dibenzofuran in the present invention is coal tar deep processing product, belongs to chemical technology field, especially a kind of from coal tar
The technique of middle purification dibenzofuran.
Background technique
Contain dibenzofuran 1%~2% in coal tar, belongs to that content is higher, the biggish component of purposes.Dibenzofuran can be used as heat carrier and food
Product and the preservation of timber against decay agent etc..Its deep processing product, such as dibenzofuran 2,3- acid can be used for producing dyestuff, 3- aminoalkyl dibenzofuran
It can be used as convulsion relieving agent and anodyne, chlorination dibenzofuran can be used as the additive of electrically insulating material, and sulfonated polycondensate can be used as weaving
Auxiliary agent and wetting agent etc..
" purifications and utilization of coke chemicals " one that separation and refining method about dibenzofuran is write in Wang Zhaoxiong, Gao Jinsheng etc.
More detailed (P313~315) introduced in book, cut dibenzofuran long distillate (dibenzofuran content by rectifying of raw material of heavy wash oil
55%~65%), secondary rectifying cuts narrow fraction (dibenzofuran content 80.8%), then makees solvent crystallisation by cooling with alpha-methyl-naphthalene and obtains
Content is greater than 95% dibenzofuran product.Have many advantages, such as with alpha-methyl-naphthalene as solvent, but there are still two problems, first is that solvent
Alpha-methyl-naphthalene itself requires height, and alpha-methyl-naphthalene content is greater than 80%, beta-methylnaphthalene since the fewer crystalline temperature high-content the better, and
Alpha-methyl-naphthalene and beta-methylnaphthalene boiling point only differ 3.5 DEG C, and intersolubility is again especially good, so either rectification method or crystallisation is wanted
Obtain that the seldom alpha-methyl-naphthalene fraction of beta-methylnaphthalene content is extremely difficult, and cost is very high, economically infeasible；Second is that alpha-methyl-naphthalene
Fraction is poor to the removal ability of impurity fluorenes, it requires that dibenzofuran narrow fraction does not allow fluorenes to be mixed into as far as possible, and the impurity of dibenzofuran is mainly
It is acenaphthene and fluorenes, does not allow fluorenes to be mixed into extremely difficult, the reflux ratio that when rectifying will be very big, such energy consumption can be very high, while in cutting oxygen
The appearance of fluorenes one will be changed to other fractions when fluorenes narrow fraction, and at this moment dibenzofuran content is also very high, this can largely have lost
The yield of dibenzofuran.Another method is dibenzofuran narrow fraction crystallisation by cooling, and centrifugal filtration obtains thick dibenzofuran, is then tied again with alcohol
Crystalline substance obtains dibenzofuran product twice, and thick dibenzofuran and Alcohol by weight are than 1: 1.5~2.The problem of this method is that rectifying twice could obtain
To narrow fraction, energy consumption height；Alcohol is poor to the solvability of dibenzofuran, and solvent consumption is big；Alcohol is very poor to the solvability of impurity fluorenes,
It needs strictly to limit the fluorenes content in dibenzofuran narrow fraction, difficulty is big when rectifying secondary in this way obtains narrow fraction, energy consumption is high, yield is low.
In Institutes Of Technology Of Taiyuan's Liang Xiaoqiang Master's thesis " extraction of fluorenes and dibenzofuran in washing oil " be also use alpha-methyl-naphthalene fraction make it is molten
Agent crystallization, equally exists problem above.
102731282 B proposition methanol of patent CN, ethyl alcohol and toluene carry out the side of supercritical extract dibenzofuran as solvent
Method, the quality and yield of product are all fine, but supercritical extract needs high temperature (235 DEG C) and high pressure (7MPa), equipment requirement is high,
Investment is big, is not appropriate for industrialized production at present.102898269 A of patent CN is also to carry out by extractant of Supercritical Ethanol
Supercritical extract cools down to obtain the acenaphthene, fluorenes and dibenzofuran of high concentration through cooling system, it is last it is purified, crystallize, be obtained by filtration it is high-purity
The finished product of degree equally exists the problem of equipment requirement is high, investment is big, current unsuitable industrialized production.
103012341 A of patent CN discloses a kind of method of industrial continuous production high-purity technical dibenzofuran.It with
Heavy wash oil is raw material, first prepares the dibenzofuran fraction that fluorenes content is less than 1% and dibenzofuran content is 70%~75%, then made with n-butanol
Dibenzofuran fraction solvent obtains the industrial dibenzofuran product that purity is greater than 96% by once recrystallizing.Dibenzofuran and fluorenes boiling point difference are only
Have 10 DEG C, to prepare fluorenes content less than 1% and dibenzofuran content 70%~75% dibenzofuran fraction be substantially exactly obtain it is above-mentioned
Dibenzofuran narrow fraction needs big reflux ratio, and energy consumption is high, yield is low.
Technique of the invention is exactly a kind of new dibenzofuran purification work developed on the basis of summarizing the above technology advantage and disadvantage
Skill, this technique using the dibenzofuran fraction containing dibenzofuran 55%~65% as raw material, without limitation dibenzofuran fraction in impurity fluorenes content and
The content of acenaphthene, there is raw material to obtain, and easy, equipment investment is few, easy to operate, good product quality, product yield are high, solvent usage
Less, the multiple advantages such as safety and environmental protection.
Summary of the invention
The purpose of the present invention is intended to provide a kind of process for refining of dibenzofuran, it is with the dibenzofuran fraction containing dibenzofuran 55%~65%
Raw material removes impurity fluorenes with precipitating reagent water after obtaining thick dibenzofuran, solvent dissolution by fraction crystallisation by cooling and recrystallization goes to clean
Matter acenaphthene obtains the dibenzofuran that content is greater than 98%, and yield is 85% or so.There is this technique raw material to obtain, and easy, equipment investment is few, behaviour
Make the multiple advantages such as simple, good product quality, product yield height, the few, safety and environmental protection of solvent usage.
Technical solution of the present invention comprises the steps of, and process flow diagram is shown in Fig. 1:
Step 1: the crystallizer with stirring is added after the dibenzofuran fraction containing dibenzofuran 55%~65% is heated to 90 DEG C of dissolutions
Interior, control mixing speed is 15r/min~20r/min, and material is then dropped to 20 DEG C~25 DEG C with the rate of temperature fall of 10 DEG C/h,
The thick dibenzofuran of content 85% or so is obtained after centrifuge separation；
Step 2: by containing dibenzofuran 85% or so thick dibenzofuran and mixed solvent be in mass ratio 1:0.5 ratio addition have
In the crystallizer of stirring, it is warming up to 60 DEG C under stirring condition and is completely dissolved, constant temperature stirring condition lower is equivalent to solvent quality 20%
Water droplet add in crystallizer, 30min is dripped off, then heat filtering, obtain filtrate and a small amount of filter cake, mixed solvent here be by
95% ethyl alcohol and DMF(N, dinethylformamide) ratio of 4:1 in mass ratio mixes；
Step 3: the filtrate after step 2 heat filtering is extracted into another crystallizer under agitation with the speed of 10 DEG C/h
Degree cools to 20 DEG C, and centrifuge separation obtains the dibenzofuran product of filtrate and content greater than 98%；
Step 4: will be used to produce Industrial fluorene after a small amount of filtration cakes torrefaction that step 2 obtains；
Step 5: step 3 being obtained into filtrate and passes through solvent recovery kettle vacuum distillation recovered solvent, adds 5 meters of Kosé on kettle
The rectifying column of net filler controls the initial gross separation that tower top temperature realizes ethyl alcohol, water and DMF by flowing back, and ethyl alcohol and DMF press 4:
1 ratio mixing circulation utilizes, and water is reused as dropwise addition with water, and the Residual oil after recycling design returns and is fitted on washing oil Residual oil or heavy
Continue to produce dibenzofuran fraction in washing oil.
In coal tar wash oil, the front and back component of dibenzofuran is respectively acenaphthene and fluorenes, thus the thick dibenzofuran after the crystallization of dibenzofuran fraction
In impurity be mainly exactly acenaphthene and fluorenes, obtain the dibenzofuran fraction containing dibenzofuran 55%~65% and be easy to, but to obtain very low containing fluorenes
Dibenzofuran narrow fraction is then very difficult, but since generally solubility is lower than dibenzofuran in a solvent for fluorenes, recrystallization not can be removed, so existing
There is technique to have to remove impurity fluorenes in such a way that rectifying obtains narrow fraction mostly, thus the production cycle is long, energy consumption is high, product
Yield is low.Due to acenaphthene, dibenzofuran and fluorenes the difference of in the mixed solvent solubility cause be added water sedimentation agent after be precipitated it is successive suitable
Sequence is different, and fluorenes is first precipitated, is precipitated after dibenzofuran, and acenaphthene is not precipitated, and using this principle, present invention process is targetedly selected compound
Solvent and precipitating reagent take the operating procedure of two-step method, first the impurity fluorenes of precipitation are removed, and then crystallisation by cooling obtains dibenzofuran,
Impurity acenaphthene has then stayed in solution, to obtain the dibenzofuran product of high quality and high yield.
The technological improvement that the present invention is done is mainly by two o'clock: first is that the mixed solvent for selecting ethyl alcohol and DMF to form is as thick
The recrystallization solvent of dibenzofuran removes impurity acenaphthene；Second is that selection water first removes the impurity fluorenes of indissoluble as precipitating reagent.This two o'clock is improved
Have the advantages that the present invention in process of production following prominent:
1. due to can first remove impurity fluorenes, it is possible to select the dibenzofuran fraction containing dibenzofuran 55%~65% to make raw material, no
With the content for limiting impurity fluorenes by secondary rectifying, raw material is easy, and low energy consumption, while decreasing setting for secondary rectifying
Standby investment；
2. can remove during solubilizer direct crystallization does not obtain the thick dibenzofuran of 85% content in addition to acenaphthene in dibenzofuran fraction and
Other impurity except fluorenes, keep recrystallization process solvent consumption few, product yield height and safety and environmental protection；
3. appropriate DMF is added in ethanol can promote the dissolution of thick dibenzofuran, the usage amount of recrystallization process solvent is reduced,
The yield of dibenzofuran is in turn ensured simultaneously；
4. water dissolves each other with ethyl alcohol and DMF, the dissolving power of mixed solvent can be reduced after addition, thus plays the work of precipitating reagent
With making the fluorenes of most indissoluble crystallize precipitation first, the amount and crystallization temperature of control addition water can guarantee the quality and yield of dibenzofuran.
5. two-step method operates, a step heat filtering removes impurity fluorenes, step recrystallization removal impurity acenaphthene, entire technological operation letter
Single, process is short.
6. solvent recovery kettle vacuum distillation recovered solvent and waste water, mixing circulation utilizes solvent in proportion, and waste water is as drop
Add and is reused with water, whole process safety and environmental protection.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Specific embodiment
The present invention is further illustrated by the following examples:
Embodiment 1
As shown in Figure 1, the dibenzofuran fraction containing dibenzofuran 58.26% is heated to 90 DEG C of fusings in storage tank, being then added to volume is
In the dibenzofuran crystallizer of 8m3,6000kg is added, 25 DEG C, then constant temperature are cooled at the uniform velocity with the rate of 10 DEG C/h under agitation
1h is centrifugally separating to obtain thick dibenzofuran 3770kg later, contains dibenzofuran 84.11%, and the yield of this process is 90.71%.
The de- brilliant oil being centrifuged out can be blended into washing oil for washing benzene.
Thick dibenzofuran obtained above is added in the dibenzofuran crystallizer of volume 8m3 with strip machine, mixed solvent is added
1885kg(mixed solvent is mixed by 95% ethyl alcohol and the DMF ratio of 4:1 in mass ratio), stirring be warming up to 60 DEG C completely it is molten
It solves, water 377kg is added dropwise under stirring condition, 30min is dripped off, and what cannot be dripped is too fast, is led in filter while hot, is filtered by vacuum, filter
Liquid is directly pumped in another dibenzofuran crystallizer, at the uniform velocity cools to 20 DEG C with the rate of 10 DEG C/h, constant temperature 1h is centrifugated later
Dibenzofuran 3030kg is obtained, dibenzofuran 98.12% is contained, the yield of this process is 93.76%, total recovery 85.05%.
Filter cake after vacuum filtration is for producing Industrial fluorene.
Filtrate is equipped with the rectifying column of 5 meters of high wire packings, passes through into solvent recovery kettle rectification under vacuum recycling design on kettle
It flows back to control the initial gross separation that tower top temperature realizes ethyl alcohol, water and DMF, ethyl alcohol and DMF 4:1 mixing circulation benefit in mass ratio
With water is reused as dropwise addition with water, and the Residual oil after recycling design, which returns to be fitted in washing oil Residual oil or heavy wash oil, to be continued to produce
Dibenzofuran fraction.
Embodiment 2
Dibenzofuran fraction 6000kg containing dibenzofuran 60.38% is added in dibenzofuran crystallizer, under agitation with the speed of 10 DEG C/h
Rate at the uniform velocity cools to 23 DEG C, then constant temperature 1h, is centrifugally separating to obtain thick dibenzofuran 3860kg later, contains dibenzofuran 85.26%, this process
Yield be 90.84%.
Thick dibenzofuran obtained above strip machine is added in dibenzofuran crystallizer, mixed solvent 1930kg is added, stirring rises
Temperature is completely dissolved to 60 DEG C, and water 386kg is added dropwise under stirring condition, and 30min is dripped off, led in filter while hot, is filtered by vacuum, filter
Liquid is extracted into another dibenzofuran crystallizer, at the uniform velocity cools to 20 DEG C with the rate of 10 DEG C/h, constant temperature 1h is centrifugally separating to obtain dibenzofuran
3150kg contains dibenzofuran 98.25%, and the yield of this process is 94.04%, total recovery 85.43%.
Filtrate recycles two kinds of solvents and waste water into solvent recovery kettle rectification under vacuum, and mixing circulation is sharp in proportion for two kinds of solvents
With waste water is reused as dropwise addition with water.
Embodiment 3
Dibenzofuran fraction 6000kg containing dibenzofuran 62.56% is added in dibenzofuran crystallizer, under agitation with the speed of 10 DEG C/h
Rate at the uniform velocity cools to 20 DEG C, then constant temperature 1h, is centrifugally separating to obtain thick dibenzofuran 3990kg later, contains dibenzofuran 85.72%, this process
Yield be 91.12%.
Thick dibenzofuran obtained above strip machine is added in dibenzofuran crystallizer, mixed solvent 1995kg is added, stirring rises
Water 399kg is added dropwise to 60 DEG C in temperature under stirring condition, 30min is dripped off, led in filter while hot, is filtered by vacuum, and filtrate is extracted into separately
In one dibenzofuran crystallizer, 20 DEG C are at the uniform velocity cooled to the rate of 10 DEG C/h, constant temperature 1h is centrifugally separating to obtain dibenzofuran 3280kg,
Containing dibenzofuran 98.56%, the yield of this process is 94.52%, total recovery 86.12%.
Filtrate recycles two kinds of solvents and waste water into solvent recovery kettle rectification under vacuum, and mixing circulation is sharp in proportion for two kinds of solvents
With waste water is reused as dropwise addition with water.
Claims (1)
1. a kind of process for refining of dibenzofuran, it is characterised in that comprise the steps of:
Step 1: the dibenzofuran fraction containing dibenzofuran 55%~65% being heated to control in the crystallizer with stirring is added after 90 DEG C of dissolutions
Mixing speed processed is 15r/min~20r/min, material is then dropped to 20 DEG C~25 DEG C with the rate of temperature fall of 10 DEG C/h, centrifugation
The thick dibenzofuran of content 85% or so is obtained after separation；
Step 2: by containing dibenzofuran 85% or so thick dibenzofuran and mixed solvent be in mass ratio 1:0.5 ratio be added with stirring
Crystallizer in, 60 DEG C are warming up under stirring condition and is completely dissolved, the water for being equivalent to solvent quality 20% under constant temperature stirring condition
It is added dropwise into crystallizer, 30min is dripped off, then heat filtering, obtains filtrate and a small amount of filter cake, and mixed solvent here is by 95%
Ethyl alcohol and DMF(N, dinethylformamide) ratio of 4:1 in mass ratio mixes；
Step 3: the filtrate after step 2 heat filtering being extracted into another crystallizer and is dropped under agitation with the speed of 10 DEG C/h
Temperature is to 20 DEG C, centrifuge separation, obtains the dibenzofuran product of filtrate and content greater than 98%；
Step 4: will be used to produce Industrial fluorene after a small amount of filtration cakes torrefaction that step 2 obtains；
Step 5: step 3 being obtained into filtrate and passes through solvent recovery kettle vacuum distillation recovered solvent, 5 meters of high silk screens is added on kettle and fills out
The rectifying column of material, the initial gross separation that tower top temperature realizes ethyl alcohol, water and DMF is controlled by flowing back, and ethyl alcohol and DMF press 4:1 ratio
Example mixing circulation utilizes, and water is reused as dropwise addition with water, and the Residual oil after recycling design time is fitted on washing oil Residual oil or heavy is washed
Continue to produce dibenzofuran fraction in oil.
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| CN109232524B (en) * | 2018-10-21 | 2020-07-28 | 辽宁科技学院 | Method for separating and refining dibenzothiophene from coal tar |
| CN114181180B (en) * | 2021-12-22 | 2022-11-22 | 河北海力香料股份有限公司 | Method for treating 3,3',4,4' -diphenyl ether dianhydride mother liquor residue |
| CN115850221A (en) * | 2022-12-07 | 2023-03-28 | 天津大学 | Method for separating fluorenone and dibenzofuran |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN203833849U (en) * | 2014-05-19 | 2014-09-17 | 孝义市金精化工有限公司 | Dibenzofuran crystallization refining device |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203833849U (en) * | 2014-05-19 | 2014-09-17 | 孝义市金精化工有限公司 | Dibenzofuran crystallization refining device |
Non-Patent Citations (2)
| Title |
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| 氧芴溶解度参数的模拟计算及氧芴的提纯工艺研究;王庚亮，等;《现代化工》;20140731;第34卷(第7期);第153-156页 |
| 芴及氧芴的精制工艺研究;陈玉娟;《江西理工大学硕士学位论文》;20150731;第55-61页 |
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