CN100473631C - Process for purifying biphenyl - Google Patents
Process for purifying biphenyl Download PDFInfo
- Publication number
- CN100473631C CN100473631C CNB2006100251984A CN200610025198A CN100473631C CN 100473631 C CN100473631 C CN 100473631C CN B2006100251984 A CNB2006100251984 A CN B2006100251984A CN 200610025198 A CN200610025198 A CN 200610025198A CN 100473631 C CN100473631 C CN 100473631C
- Authority
- CN
- China
- Prior art keywords
- biphenyl
- crystallization
- purification process
- washings
- thick
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a purification method of biphenyl, which adopts a single-tower vacuum rectification and a secondary solution crystallization process to purify recovered wash oil. Firstly, rectifying recovered wash oil by using a single-tower vacuum rectification process to obtain 55-75% of crude biphenyl fraction, then dissolving the crude biphenyl fraction by using an alcohol solvent, crystallizing according to a set cooling curve under the stirring condition, collecting purified biphenyl after reaching the crystallization end point temperature, and carrying out solution crystallization on the collected biphenyl again to obtain a biphenyl product with the purity of more than 99%. The method has the advantages of simple process flow, convenient operation, full utilization of raw materials, recycling of solvent, low energy consumption, low production cost and the like, and expands the application of the recovered wash oil and the biphenyl product purified from the intermediate product of coal tar processing.
Description
Technical field
The present invention relates to the purification process of biphenyl, more specifically relate to from reclaim washing oil, extract the method for high purity biphenyl.
Background technology
Biphenyl is a kind of broad-spectrum important organic raw material, can mix with biphenyl ether as thermal barrier, also can prepare such as multiple important derivative products such as emulsifying agent, white dyes, dye for fabrics, synthetic resins, liquid crystal material, agricultural chemicals and medicine.The massfraction of biphenyl in coal tar is about 0.2～0.4%, and the overwhelming majority concentrates in the wash oil fraction, and the cut in washing oil is about 8%.Washing oil is one of main fraction in the coal tar course of processing, the boiling spread 230-270 of tar washing oil ℃, is rich in Organic Chemicals such as 2-methylnaphthalene, biphenyl, acenaphthene, indoles and fluorenes.Washing oil is widely used in the washing and recycling that coal gas is washed benzene and various organic gass because of its satisfactory stability and dissolving power.Reclaiming washing oil (WO-R) is the intermediates that utilize coal tar wash oil processing beta-methylnaphthalene, and the content of its biphenyl is about about 21%, is mainly used in to be made into to wash the benzene washing oil.The method of utilizing washing oil to extract high purity biphenyl that adopts at present comprises highly efficient distilling-crystallization process and lightweight washing oil azeotropic distillation.The shortcoming of highly efficient distilling-crystallization process is that must remove indoles to the washing oil raw material earlier handles technology and equipment complexity, production cost height; The limitation of azeotropic distillation is that selected feedstock fraction is narrower, the biphenyl loss is more in the leaching process, yield is lower, and reclaim entrainer and need consume a large amount of energy, the biphenyl purity of utilizing prior art to obtain is up to about 95% (Gu Guangjuan etc., fuel and chemical industry, 1988 (4): 46-50).Have not yet to see the relevant report that extracts biphenyl that from reclaim washing oil, reclaims.Do not see relevant from the intermediates of coal tar processing, the extraction yet and obtain the report that purity reaches the biphenyl more than 99%.
Summary of the invention
The purpose of this invention is to provide a kind of method of from reclaim washing oil, extracting high purity biphenyl.Utilize the inventive method can obtain high purity biphenyl more than 99%.
The handled raw material of the inventive method is to utilize the intermediates of coal tar wash oil processing beta-methylnaphthalene to reclaim washing oil (WO-R), and wherein biphenyl content is about 21%.
The characteristics of the inventive method are successively to adopt single tower rectification under vacuum and second aqueous crystallization processes to purify to reclaiming washing oil.According to the inventive method, at first utilize single tower rectification under vacuum technology to carry out rectifying to reclaiming washing oil, obtain the thick biphenyl cut of 55-75%.After dissolving thick biphenyl cut with alcoholic solvent then, under agitation condition, carry out crystallization according to the temperature lowering curve of setting, collect purified biphenyl after reaching the crystallization terminal temperature, the biphenyl of collecting is carried out solution crystallization once more, obtain purity and reach biphenyl product more than 99%.The inventive method may further comprise the steps:
(1) will reclaim washing oil and add in the stuffing rectification column, under the vacuum pressure of 0.07-0.09MPa, reflux 1-2 hour, extraction cut, control of reflux ratio were 5-15, collected 175-213 ℃ cut, and obtaining biphenyl content is the thick biphenyl of 55-75%;
(2) in crystallizer, add thick biphenyl and the alcoholic solvent that step (1) obtains, under 40-55 ℃ starting temperature,, be cooled to warm 0-15 ℃ eventually of crystallization while stirring with the constant speed of cooling of 2-20K/hr, the biphenyl crystallization is separated with impure mother liquor, obtain the biphenyl of primary crystallization;
(3) in crystallizer, add biphenyl crystallization and the alcoholic solvent that step (2) obtains, under 50-60 ℃ starting temperature,, be cooled to warm 0-15 ℃ eventually of crystallization while stirring with the constant speed of cooling of 2-20K/hr, the biphenyl crystallization is separated with impure mother liquor, obtain the biphenyl crystallization of purifying.
The theoretical plate number of stuffing rectification column is the 38-50 piece in the inventive method, preferred stainless steel dumped packing of filler or stainless steel ripple filler.
Solution crystallization can carry out also can carrying out off and on continuously, and used equipment all should have good hot-swap feature, preferably has the equipment of heating and cooling circulatory function simultaneously.Crystallizer can be selected stirred type crystallizer for use, as has the discontinuous crystallizer of anchor stirrer.
Alcoholic solvent particular methanol, ethanol, propyl alcohol, butanols, Virahol or their mixture in step (2) and (3), the effect that the wherein independent effect of using is better than mixing use.By weight, the biphenyl raw material is 1:1.3-3.5 with the preferable amount ratio of alcoholic solvent, wherein preferred 1:2-3; Stirring velocity is 50-250rpm, and best stirring velocity is 100-200rpm; Preferred speed of cooling is 5-15K/hr, and preferred the continuation stirred 1-2 hour under the whole temperature of crystallization, thereby made crystallization more full and uniform.
Can the beta-methylnaphthalene crystallization be separated with impure mother liquor by ordinary method, for example can adopt extrude, filtration or mode such as centrifugal realize in the beta-methylnaphthalene crystallization and the separating of impure mother liquor.
A preferred embodiment of the present invention is step (3) to be separated the biphenyl crystallization that obtains wash, and to remove residual adhesion impurity, can further improve biphenyl crystalline purity by carrying out washing treatment.The alcohol solution of alcoholic solvent that washings employing crystallization is used or saturated biphenyl, the wherein alcohol solution of preferred saturated biphenyl.The use temperature of washings is 0-15 ℃, and preferred 5-10 ℃, temperature is identical eventually with crystallization for most preferred washings use temperature.The consumption of washings is the 6-120% of thick biphenyl weight, wherein the 24-60% of preferred thick biphenyl weight.Mode of washing can be single wash or washing several times, and wherein preferably repeatedly washing for example, with 30% washing biphenyl crystallization of the total consumption of washings, is used remaining 70% repeated washing once earlier then.
In order to improve the yield of biphenyl, another preferred embodiment of the present invention is that recycling step (2) separates the mother liquor that obtains with (3) and reprocesses and recycle.Preferred mode is that recycling step (2) separates the residual washings of mother liquor and washing back that obtains with (3), merges this two kinds of solution, reprocesses and recycles.
Beneficial effect
1, the inventive method adopts single tower rectification under vacuum technology, and it is lower that theoretical plate number requires, economization use equipment;
Advantages such as it is simple, easy to operate that 2, the treating process of the inventive method employing secondary crystallisation by cooling has technical process, makes full use of raw material, recycles solvent, and energy consumption is low, and production cost is low.Gained biphenyl purity is up to more than 99%, thus the application of having expanded the biphenyl product that reclaims washing oil and from the intermediates of coal tar processing, purify.
Embodiment
Below by embodiment the inventive method is further elaborated, but does not limit the present invention:
Employed crystallizer is the stirred type crystallizer that has anchor stirrer (German JULABO company produce model F32-HP) among the following embodiment, and this crystallizer is provided with the refrigeration heating controller.
The raw material of the purified processing of following embodiment is for reclaiming washing oil (WO-R), and its biphenyl content is 21.52wt%.The rectification under vacuum device is the stuffing rectification column of φ 30 * 1350mm, adopts Stainless Steel Helices, and still kettle is the 2000ml there-necked flask.
Vapor-phase chromatography is adopted in the analysis of thick biphenyl, smart biphenyl and mother liquor, uses GC-2010 type gas chromatograph (day island proper Tianjin company).Chromatographic column is SE-54 capillary column (30m * φ 0.25mm * 0.2 μ m); Column temperature is 80 ℃ of initial temperature, stops 1min, is warming up to 180 ℃ with 5 ℃/min, keeps 20min; Flame ionization ditector; Detector temperature is 280 ℃; Carrier gas is N
2, flow velocity is 6mL/min; Sample size 1 μ L; Adopt the area normalization method of band correction factor to calculate mensuration.
Embodiment 1
The rectification under vacuum device adopts the stainless steel dumped packing, and stage number is 40, takes by weighing 983gWO-R and adds in the still kettle, the adjusting vacuum pressure is 0.075MPa, begins to be heated to backflow, wait to reflux stablize 1-2hr after, beginning extraction cut, reflux ratio is 10, when recovered temperature reaches 209 ℃, begin to collect the biphenyl cut, when temperature reaches 213 ℃, stop extraction, obtain the thick biphenyl crystallization of 272.0g, by analysis, biphenyl content is 71.36wt% in the thick biphenyl.
Take by weighing the thick biphenyl crystallization of 41.3g cut, 66.08g dehydrated alcohol, add and have in the stirred type crystallizer of anchor stirrer, be heated to 55 ℃, under 100rpm speed stirs, speed of cooling with 10K/h is cooled to warm 5 ℃ eventually of crystallizations, filter out the biphenyl crystallization, amount ratio by 1:1.6 has biphenyl crystallization and the dehydrated alcohol adding that leaches in the stirred type crystallizer of anchor stirrer, be heated to 60 ℃, under 100rpm speed stirs, be cooled to crystallization 5 ℃ of temperature eventually with the speed of cooling of 10K/h, filter out crystal, be the saturated ethanolic soln washing of 5 ℃ thick biphenyl subsequently with the 7.5g temperature, the crystallization of dry acquisition 18.7g biphenyl.By analysis: the purity of biphenyl is 99.15wt%.
Embodiment 2
The rectification under vacuum device adopts the stainless steel dumped packing, and stage number is 40, takes by weighing 983gWO-R and adds in the still kettle, the adjusting vacuum pressure is 0.075MPa, begins to be heated to backflow, wait to reflux stablize 1-2hr after, beginning extraction cut, reflux ratio is 10, when recovered temperature reaches 209 ℃, begin to collect the biphenyl cut, when temperature reaches 213 ℃, stop extraction, obtain the thick biphenyl crystallization of 272.0g, by analysis, biphenyl content is 71.36wt% in the thick biphenyl.
Take by weighing the thick biphenyl crystallization of 51.6g cut, 103.2g dehydrated alcohol, add and have in the stirred type crystallizer of anchor stirrer, be heated to 50 ℃, under 120rpm speed stirs, be cooled to crystallization 10 ℃ of temperature eventually with the speed of cooling of 10K/h, filter out the biphenyl crystallization, by the amount ratio of 1:2 the biphenyl crystallization that leaches and dehydrated alcohol are added and have in the stirred type crystallizer of anchor stirrer, carry out crystallization once more according to the aforementioned operation condition, filtration, the crystallization of dry acquisition 19.1g biphenyl.By analysis: the purity of biphenyl is 99.83wt%.
Embodiment 3
The rectification under vacuum device adopts the stainless steel dumped packing, and stage number is 50, takes by weighing 983gWO-R and adds in the still kettle, the adjusting vacuum pressure is 0.09MPa, begins to be heated to backflow, wait to reflux stablize 1-2hr after, beginning extraction cut, reflux ratio is 8, when recovered temperature reaches 175 ℃, begin to collect the biphenyl cut, when temperature reaches 187 ℃, stop extraction, obtain the thick biphenyl crystallization of 268.0g, by analysis, biphenyl content is 67.1wt% in the thick biphenyl.
Take by weighing the thick biphenyl crystallization of 40.0g cut, the 120g Virahol, add and have in the stirred type crystallizer of anchor stirrer, be heated to 40 ℃, under 120rpm speed stirs, speed of cooling with 5K/h is cooled to warm 0 ℃ eventually of crystallization, filter out the biphenyl crystallization, amount ratio by 1:3 has biphenyl crystallization and the Virahol adding that leaches in the stirred type crystallizer of anchor stirrer, be heated to 53 ℃, under 120rpm speed stirs, be cooled to crystallization 0 ℃ of temperature eventually with the speed of cooling of 5K/h, filter out crystal, be 0 ℃ washed with isopropyl alcohol subsequently with the 9.6g temperature, the crystallization of dry acquisition 13.5g biphenyl.By analysis: the purity of biphenyl is 99.40wt%.Merging filtrate and washings as solvent, take by weighing the amalgamation liquid of the thick biphenyl crystallization of 20g and 32g filtrate and washings, add in the stirred type crystallizer, carry out secondary crystal according to the aforementioned operation condition, the crystallization of dry acquisition 7.5g biphenyl.By analysis: the purity of biphenyl is 99.35wt%.
Embodiment 4
The rectification under vacuum device adopts stainless steel ripple filler, and stage number is 40, takes by weighing 983gWO-R and adds in the still kettle, the adjusting vacuum pressure is 0.07MPa, begins to be heated to backflow, wait to reflux stablize 1-2hr after, beginning extraction cut, reflux ratio is 5, when recovered temperature reaches 206 ℃, begin to collect the biphenyl cut, when temperature reaches 214 ℃, stop extraction, obtain the thick biphenyl crystallization of 225.4g, by analysis, biphenyl content is 65.7wt% in the thick biphenyl.
Take by weighing the thick biphenyl crystallization of 40.0g cut, 80g Virahol, add and have in the stirred type crystallizer of anchor stirrer, be heated to 50 ℃, under 120rpm speed stirs, speed of cooling with 15K/h is cooled to warm 15 ℃ eventually of crystallizations, filter out the biphenyl crystallization, amount ratio by 1:2 adds biphenyl crystallization and the Virahol that leaches in the stirred type crystallizer, be heated to 55 ℃, under 120rpm speed stirs, be cooled to crystallization 15 ℃ of temperature eventually with the speed of cooling of 15K/h, filter out crystal, be 15 ℃ washed with isopropyl alcohol subsequently with the 40g temperature, the crystallization of dry acquisition 12.7g biphenyl.By analysis: the purity of biphenyl is 99.11wt%.
Claims (10)
1. the purification process of a biphenyl is characterized in that successively adopting single tower rectification under vacuum and second aqueous crystallization processes to purifying as the recovery washing oil of the intermediates that utilize coal tar wash oil processing beta-methylnaphthalene, may further comprise the steps:
(1) will reclaim washing oil and add in the stuffing rectification column, under the vacuum pressure of 0.07-0.09MPa, reflux 1-2 hour, extraction cut, control of reflux ratio were 5-15, collected 175-213 ℃ cut, and obtaining biphenyl content is the thick biphenyl of 55-75%;
(2) in crystallizer, add thick biphenyl and the alcoholic solvent that step (1) obtains, under 40-55 ℃ starting temperature,, be cooled to warm 0-15 ℃ eventually of crystallization while stirring with the constant speed of cooling of 2-20K/hr, the biphenyl crystallization is separated with impure mother liquor, obtain the biphenyl of primary crystallization;
(3) in crystallizer, add biphenyl crystallization and the alcoholic solvent that step (2) obtains, under 50-60 ℃ starting temperature,, be cooled to warm 0-15 ℃ eventually of crystallization while stirring with the constant speed of cooling of 2-20K/hr, the biphenyl crystallization is separated with impure mother liquor, obtain the biphenyl crystallization of purifying;
Wherein in step (2) and (3), by weight, the amount ratio of biphenyl raw material and alcoholic solvent is 1: 1.3-3.5.
2. the purification process of biphenyl according to claim 1, the theoretical plate number that it is characterized in that described stuffing rectification column is the 38-50 piece.
3. the purification process of biphenyl according to claim 1 is characterized in that described alcoholic solvent is methyl alcohol, ethanol, propyl alcohol, butanols, Virahol or their mixture.
4. according to the purification process of claim 1 or 3 described biphenyl, it is characterized in that by weight that the amount ratio of biphenyl raw material and alcoholic solvent is 1:2-3.
5. the purification process of biphenyl according to claim 1 is characterized in that stirring velocity is 50-250rpm.
6. the purification process of biphenyl according to claim 1 is characterized in that speed of cooling is 5-15K/hr.
7. the purification process of biphenyl according to claim 1, it is characterized in that step (3) is separated the biphenyl crystallization that obtains washs, the alcohol solution of alcoholic solvent that washings employing crystallization is used or saturated biphenyl, the use temperature of washings is 0-15 ℃, the consumption of washings is the 6-120% of thick biphenyl weight, and mode of washing is single wash or washing several times.
8. the purification process of biphenyl according to claim 7, the use temperature that it is characterized in that washings is 5-10 ℃, the consumption of washings is the 24-60% of thick biphenyl weight.
9. the purification process of biphenyl according to claim 1 is characterized in that recycling step (2) separates the mother liquor that obtains with (3) and reprocesses and recycle.
10. the purification process of biphenyl according to claim 7 is characterized in that recycling step (2) separates the residual washings of mother liquor and washing back that obtains with (3), merges this two kinds of solution, reprocesses and recycles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100251984A CN100473631C (en) | 2006-03-29 | 2006-03-29 | Process for purifying biphenyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100251984A CN100473631C (en) | 2006-03-29 | 2006-03-29 | Process for purifying biphenyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101045670A CN101045670A (en) | 2007-10-03 |
| CN100473631C true CN100473631C (en) | 2009-04-01 |
Family
ID=38770616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100251984A Active CN100473631C (en) | 2006-03-29 | 2006-03-29 | Process for purifying biphenyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100473631C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731238B (en) * | 2012-07-12 | 2014-08-20 | 韩钊武 | Environment-friendly method for extracting biphenyl from washed oil of coal tar |
| CN108395362A (en) * | 2017-02-08 | 2018-08-14 | 鞍钢股份有限公司 | Method for extracting biphenyl by heating heat carrier and performing negative pressure rectification |
| CN109053355B (en) * | 2018-09-29 | 2020-12-25 | 上海化工研究院有限公司 | Method for purifying biphenyl by continuous rectification |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651367A (en) * | 2004-12-07 | 2005-08-10 | 哈尔滨工程大学 | Method of extracting high purity acenaphthene from coat tar scrubbing oil |
| CN1680226A (en) * | 2004-04-05 | 2005-10-12 | 上海宝钢化工有限公司 | Method for preparing high-purity biphenyl from crude biphenyl |
-
2006
- 2006-03-29 CN CNB2006100251984A patent/CN100473631C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1680226A (en) * | 2004-04-05 | 2005-10-12 | 上海宝钢化工有限公司 | Method for preparing high-purity biphenyl from crude biphenyl |
| CN1651367A (en) * | 2004-12-07 | 2005-08-10 | 哈尔滨工程大学 | Method of extracting high purity acenaphthene from coat tar scrubbing oil |
Non-Patent Citations (2)
| Title |
|---|
| 从苯塔残液中提取联苯的研究. 侯文杰.燃料与化工，第35卷第4期. 2004 * |
| 煤焦油洗油组分提取及其在精细化工中的应用. 王凤武.煤化工，第2期. 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101045670A (en) | 2007-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105037162A (en) | Method for continuous extraction distillation separation of dimethyl carbonate-methanol azeotropic mixture | |
| CN105111079A (en) | Method and device for separating acetic acid sec-butyl ester and sec-butyl alcohol | |
| CN115894229B (en) | Selective synthesis process of adipic acid monoethyl ester | |
| CN100473631C (en) | Process for purifying biphenyl | |
| CN101229988B (en) | Method for refining high-purity anthracene and carbazole from crude anthracene | |
| CN112047883A (en) | Preparation method of cisatracurium besylate | |
| CN107522614B (en) | Method for separating and purifying glutaric acid in mixed dibasic acid by using low-carbon halogenated alkane | |
| CN100336788C (en) | Method of extracting high purity acenaphthene from coat tar scrubbing oil | |
| CN111848400A (en) | Device and process for preparing dimethyl carbonate by reactive distillation coupled extraction distillation | |
| CN113549026A (en) | Synthesis process of N-vinyl oxazolidinone compound | |
| CN207537372U (en) | Continuous reaction rectification production cyanoacetate compound, malonate compound device | |
| CN114213208A (en) | Method for extracting, rectifying and purifying mesitylene by using efficient composite solvent | |
| CN109646977B (en) | Reactive distillation coupling tower and application thereof in preparation of formic acid | |
| CN100506763C (en) | Method for purifying biphenyl by elution crystallization | |
| CN107445927A (en) | The technique that a kind of xylose dehydration prepares furfural | |
| CN101912693B (en) | Equipment and method for separating indole and biphenyl from wash oil fraction | |
| CN101328105B (en) | Process for purifying biphenyl by rectification-emulsification crystallization method | |
| CN115093317B (en) | Continuous process for preparing butenone by acid resin catalysis | |
| CN105315156A (en) | Synthesis method for 2-methylcyclohexyl acetate | |
| CN115124417B (en) | Refining method and equipment for lactic acid monomer | |
| CN101092358B (en) | Method for intermittent preparing diisopropyl ester amber acid | |
| CN219050363U (en) | Acetic acid separation device in process of preparing lactic acid by straw and system for preparing lactic acid | |
| CN113045417B (en) | Process for producing acetoacetic ester by catalytic method | |
| CN212293375U (en) | Device for preparing dimethyl carbonate by reactive distillation coupled with extractive distillation | |
| CN219963992U (en) | Methyl acrylate extraction, rectification, purification and separation process device |
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: 20210128 Address after: 201900 chemical office building, Weisan Road, Baoshan District, Shanghai Patentee after: BAOWU CARBON MATERIAL TECHNOLOGY Co.,Ltd. Address before: 201900, Fujin Road, Shanghai, Baoshan District orchard Patentee before: BAOSHAN IRON & STEEL Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 201900 chemical office building, Weisan Road, Baoshan District, Shanghai Patentee after: Baowu Carbon Technology Co.,Ltd. Address before: 201900 chemical office building, Weisan Road, Baoshan District, Shanghai Patentee before: BAOWU CARBON MATERIAL TECHNOLOGY Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |