CN101182277A - Method for extracting biphenyl from middle washing oil - Google Patents
Method for extracting biphenyl from middle washing oil Download PDFInfo
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- CN101182277A CN101182277A CN 200710158910 CN200710158910A CN101182277A CN 101182277 A CN101182277 A CN 101182277A CN 200710158910 CN200710158910 CN 200710158910 CN 200710158910 A CN200710158910 A CN 200710158910A CN 101182277 A CN101182277 A CN 101182277A
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Abstract
The invention discloses a method of extracting biphenyl from medium wash oil. The medium wash oil containing 15 percent of biphenyl is used as the raw material to be processed for three times of batch distillations inside a rectifying still and a distillation column with the theoretical plate number of 50 to 80 pieces to obtain the biphenyl product, the purity of which is more than 95 percent, and at the same time, industrial methylnaphthalene, mixed dimethyl naphthalene fraction and acenaphthene fraction are obtained. The technology of the invention is simple and is easy for grasping. Under the technical condition that the devices for the three times distillations, the theoretical plate number of the distillation column, the pressure of the rectifying still, the reflux ration and the temperature of the rectifying still are same, the required products can be produced just by slightly adjusting the temperature of the rectifying still and the top temperature of the distillation column. The extraction rate of the biphenyl can be more than 70 percent. A coking plant which produces 4000t medium wash oil yearly can produce 400t biphenyl product yearly, the biphenyl content of which is more than 95 percent, and the coking plant can obtain 1000t industrial methylnaphthalene, 1300t mixed dimethyl naphthalene fraction and 1200t acenaphthene fraction at the same time, so the comprehensive economic benefit is very considerable.
Description
Technical field
The invention belongs to coal chemical technology, be specifically related to the method that the matter washing oil is produced biphenyl in a kind of the utilization.
Background technology
The production method of biphenyl mainly is to produce chemical synthesiss such as biphenyl by the benzene pyrolysis and the method for separation and Extraction biphenyl from coal tar fraction, the biphenyl of China all takes the synthetic mode to produce at present, the method of extracting biphenyl from coal tar still is in laboratory stage, and the industrialization of being unrealized.
The method of separating biphenyl from coal tar mainly contains potassium and melts two kinds of method and azeotropic distillations.
Potassium melts method: be with washing oil rectifying, cut 240 ℃～260 ℃ cuts, remove indoles with potassium hydroxide, tell neutral oil as the raw material that extracts biphenyl, cut 252 ℃～262 ℃ biphenyl cuts with rectifying tower again, crystallisation by cooling obtains biphenyl crude product, again with the crude product ethyl alcohol recrystallization, obtains purity greater than 90% industrial biphenyl.
Azeotropic distillation: first rectifying cuts 245 ℃～260 ℃ cuts, utilize ethylene glycol to make entrainer, the azeotrope boiling point that biphenyl and ethanol form is 230.4 ℃, the azeotropic point that indoles and ethylene glycol form is 242.6 ℃, the two differs 12.2 ℃, and the indoles boiling point is 253 ℃, and is approaching with the biphenyl boiling point, so separablely go out biphenyl.
More than two kinds of extracting method relative merits are respectively arranged, the potassium method of melting is used highly basic, to the equipment requirements height, and pollute big, so should not adopt.Azeotropic distillation need adopt entrainer, exists entrainer Separation and Recovery problem; Azeotropic distillation is removed indoles only in addition, but can not remove the neutral impurity approaching with the biphenyl boiling point.
By retrieval, domestic relevant for the report that from coal tar, obtains naphthalene and acenaphthene cut through rectifying and solvent-extracted method.As Chinese patent publication number CN1651367A, a kind of " extracting the method for high purity acenaphthene from coal tar " is provided, be to adopt single tower rectification under vacuum technology, pressure-controlling is at 0.05-0.06MPa, control of reflux ratio is at 10-20, acenaphthene cut extraction temperature is at 235 ℃-245 ℃, the acenaphthene cut that obtains mixed with organic solvent again, reaches acenaphthene product more than 99% by recrystallization acquisition purity.Chinese patent application numbers 97107637.5 then discloses one " coking naphtalene oil cut continuous rectification technology ", be to adopt so-called " three stoves, three towers " promptly continuous three rectifying of deep fat to be processed in washing oil, make NAPTHALENE FLAKES. (INDUSTRIAL GRADE, technical methylnaphthalene or acenaphthene cut and dibenzofuran cut through rectifying tubular oven and rectifying tower.But do not see and the inventive method and the identical or akin bibliographical information of product that makes.
Summary of the invention
It is raw material with middle matter washing oil that purpose of the present invention aims to provide a kind of, through three batch fractionatings, and when acquisition purity is greater than 95% biphenyl product, the method for obtain technical methylnaphthalene, mixing dimethylnaphthalene cut and acenaphthene cut.
For this reason, the present invention has taked following technical solution:
The present invention therefrom extracts the method for biphenyl in the matter washing oil, and the matter washing oil is a raw material in the employing, through three batch fractionatings, obtains purity greater than 95% biphenyl product in rectifying still and rectifying tower, obtains technical methylnaphthalene, mixing dimethylnaphthalene cut and acenaphthene cut simultaneously.The technological process of its extraction is:
1, rectifying for the first time: matter washing oil in the raw material packed into heat rectifying in rectifying tower in the rectifying still.Rectifying still still temperature is at 250 ℃～310 ℃, and still is pressed and remained on 5～20KPa, and the rectifying tower top temperature is at 240 ℃～270 ℃, is cut respectively under 10～30 the condition in reflux ratio; Successively recovered water, technical methylnaphthalene cut, biphenyl content stop extraction then greater than 50% biphenyl cut and mix the dimethylnaphthalene cut.Treat to extract the still raffinate out when the rectifying still temperature drops to 150 ℃, be the acenaphthene cut.
2, rectifying for the second time: the biphenyl content that rectifying is for the first time obtained is packed into greater than 50% biphenyl cut and is heated rectifying in rectifying tower in the rectifying still.Rectifying still still temperature is at 260 ℃～310 ℃, and still is pressed and remained on 5～20KPa, and the rectifying tower top temperature is at 240 ℃～260 ℃, is cut respectively under 10～30 the condition in reflux ratio; Successively extraction technical methylnaphthalene cut, biphenyl content greater than 80% biphenyl main distillate fraction, stop extraction greater than 50% biphenyl cut and biphenyl content then.Treat to extract the still raffinate out when the rectifying still temperature drops to 150 ℃, be the dimethylnaphthalene cut.
3, rectifying for the third time: the biphenyl content that rectifying is for the second time obtained is packed into greater than 80% biphenyl cut and is heated rectifying in rectifying tower in the rectifying still.Rectifying still still temperature is at 260 ℃～310 ℃, and still is pressed and remained on 5～20KPa, and the rectifying tower top temperature is at 240 ℃～260 ℃, is cut respectively under 10～30 the condition in reflux ratio; Successively extraction biphenyl content greater than 50% biphenyl cut, biphenyl content greater than 80% biphenyl main distillate fraction and biphenyl content greater than 95% biphenyl finished product, stop extraction then.Extract the still raffinate when treating that the rectifying still temperature drops to 150 ℃ out, promptly biphenyl content is greater than 50% biphenyl cut.
Described raw material is a biphenyl content greater than 15% middle matter washing oil.The rectifying tower number of theoretical plate is the 50-80 piece.
The invention has the beneficial effects as follows that technology is simple, be easy to grasp.The equipment used three rectifying is constant, under rectifying tower number of theoretical plate, rectifying still still pressure, the processing condition that when the rectifying still temperature drop is identical that reflux, only the gentle rectifying tower top temperature of rectifying still still is adjusted a little, just can be produced desired product, proved the scientific rationality of this method.The extraction yield height of biphenyl can reach more than 70%.For matter washing oil in the annual output is the coke-oven plant of 4000t, by biphenyl content in the middle matter washing oil be 15%, extraction yield is 70% to calculate, the biphenyl stock number is 600t, can produce biphenyl content greater than 95% biphenyl product 400t; Can also obtain simultaneously technical methylnaphthalene 1000t, mix dimethylnaphthalene cut 1300t, acenaphthene cut 1200t, overall economic efficiency is very considerable.
Embodiment
It is that 15% middle matter washing oil is a raw material that the present invention adopts biphenyl content, at rectifying still and number of theoretical plate is to carry out batch fractionating three times in the rectifying tower of 50-80 piece, obtain purity greater than 95% biphenyl product, obtain technical methylnaphthalene simultaneously, mix dimethylnaphthalene cut and acenaphthene cut.The technological process that embodiment extracts is:
Embodiment 1:
Rectifying for the first time: will contain in the raw material of 15% biphenyl the matter washing oil and pack into and carry out heat temperature raising in the rectifying still, rectifying still still temperature is warming up to 310 ℃ by 250 ℃, and still is pressed and remained on 20KPa.Put into rectifying tower rectifying then, the rectifying tower top temperature rises to 270 ℃ by 240 ℃, is cut respectively under 10 the condition in reflux ratio; Successively recovered water, technical methylnaphthalene cut, biphenyl content stop extraction then greater than 50% biphenyl cut and mix the dimethylnaphthalene cut.Treat to extract the still raffinate out when the rectifying still temperature drops to 150 ℃, be the acenaphthene cut.
Rectifying for the second time: the biphenyl content that rectifying is for the first time obtained is packed into greater than 50% biphenyl cut and is heated in the rectifying still, and the still temperature rises to 310 ℃ by 260 ℃, and still is pressed and remained on 5 KPa.Put into rectifying tower rectifying then, smart rectifying tower top temperature is warming up to 260 ℃ by 240 ℃, is cut respectively under 20 the condition in reflux ratio; Successively extraction technical methylnaphthalene cut, biphenyl content greater than 80% biphenyl main distillate fraction, stop extraction greater than 50% biphenyl cut and biphenyl content then.Treat to extract the still raffinate out when the rectifying still temperature drops to 150 ℃, be the dimethylnaphthalene cut.
Rectifying for the third time: the biphenyl content that rectifying is for the second time obtained is packed into greater than 80% biphenyl cut and is heated in the rectifying still, and the still temperature control rises to 310 ℃ by 260 ℃, and still is pressed and remained on 10KPa.Put into rectifying tower rectifying then.The rectifying tower top temperature rises to 260 ℃ by 240 ℃, is cut respectively under 25 the condition in reflux ratio; Successively extraction biphenyl content greater than 50% biphenyl cut, biphenyl content greater than 80% biphenyl main distillate fraction and biphenyl content greater than 95% biphenyl finished product, stop extraction then.Extract the still raffinate when treating that the rectifying still temperature drops to 150 ℃ out, be biphenyl content greater than 50% biphenyl cut.
Embodiment 2:
Rectifying for the first time: will contain in the raw material of 15% biphenyl the matter washing oil and pack into and carry out heat temperature raising in the rectifying still, rectifying still still temperature rises to 310 ℃ by 250 ℃, and still is pressed and remained on 5KPa.Put into rectifying tower rectifying then, the rectifying tower top temperature rises to 260 ℃ by 240 ℃, is cut respectively under 30 the condition in reflux ratio; Successively recovered water, technical methylnaphthalene cut, biphenyl content stop extraction then greater than 50% biphenyl cut and mix the dimethylnaphthalene cut.Treat to extract the still raffinate out when the rectifying still temperature drops to 150 ℃, be the acenaphthene cut.
Rectifying for the second time: the biphenyl content that rectifying is for the first time obtained is packed into greater than 50% biphenyl cut and is heated in the rectifying still, and the still temperature rises to 310 ℃ by 260 ℃, and still is pressed and remained on 20KPa.Put into rectifying tower rectifying then, smart rectifying tower top temperature rises to 260 ℃ by 240 ℃, is cut respectively under 10 the condition in reflux ratio; Successively extraction technical methylnaphthalene cut, biphenyl content greater than 80% biphenyl main distillate fraction, stop extraction greater than 50% biphenyl cut and biphenyl content then.Treat to extract the still raffinate out when the rectifying still temperature drops to 150 ℃, be the dimethylnaphthalene cut.
Rectifying for the third time: the biphenyl content that rectifying is for the second time obtained is packed into greater than 80% biphenyl cut and is heated in the rectifying still, and the still temperature rises to 310 ℃ by 260 ℃, and still is pressed and remained on 17KPa.Put into rectifying tower rectifying then.The rectifying tower top temperature rises to 260 ℃ by 240 ℃, is cut respectively under 10 the condition in reflux ratio; Successively extraction biphenyl content greater than 50% biphenyl cut, biphenyl content greater than 80% biphenyl main distillate fraction and biphenyl content greater than 95% biphenyl finished product, stop extraction then.Extract the still raffinate when treating that the rectifying still temperature drops to 150 ℃ out, be biphenyl content greater than 50% biphenyl cut.
Claims (3)
1. method of therefrom extracting biphenyl in the matter washing oil, it is characterized in that the matter washing oil is a raw material in the employing, in rectifying still and rectifying tower through three batch fractionatings, obtain purity greater than 95% biphenyl product, obtain technical methylnaphthalene simultaneously, mix dimethylnaphthalene cut and acenaphthene cut; Its leaching process is:
(1), rectifying for the first time: matter washing oil in the raw material packed into heat rectifying in rectifying tower in the rectifying still; The temperature control of rectifying still still is at 250 ℃～310 ℃, and still is pressed and remained on 5～20KPa, and the rectifying tower top temperature is at 240 ℃～270 ℃, is cut respectively under 10～30 the condition in reflux ratio; Successively recovered water, technical methylnaphthalene cut, biphenyl content stop extraction then greater than 50% biphenyl cut and mix the dimethylnaphthalene cut; Treat to extract the still raffinate out when the rectifying still temperature drops to 150 ℃, be the acenaphthene cut;
(2), rectifying for the second time: the biphenyl content that rectifying is for the first time obtained is packed into greater than 50% biphenyl cut and is heated rectifying in rectifying tower in the rectifying still; The temperature control of rectifying still still is at 260 ℃～310 ℃, and still is pressed and remained on 5～20KPa, and the rectifying tower top temperature is at 240 ℃～260 ℃, is cut respectively under 10～30 the condition in reflux ratio; Successively extraction technical methylnaphthalene cut, biphenyl content greater than 80% biphenyl main distillate fraction, stop extraction greater than 50% biphenyl cut and biphenyl content then; Treat to extract the still raffinate out when the rectifying still temperature drops to 150 ℃, be the dimethylnaphthalene cut;
(3), rectifying for the third time: the biphenyl content that rectifying is for the second time obtained is packed into greater than 80% biphenyl cut and is heated rectifying in rectifying tower in the rectifying still; The temperature control of rectifying still still is at 260 ℃～310 ℃, and still is pressed and remained on 5～20KPa, and the rectifying tower top temperature is at 240 ℃～260 ℃, is cut respectively under 10～30 the condition in reflux ratio; Successively extraction biphenyl content greater than 50% biphenyl cut, biphenyl content greater than 80% biphenyl main distillate fraction and biphenyl content greater than 95% biphenyl finished product, stop extraction then; Extract the still raffinate when treating that the rectifying still temperature drops to 150 ℃ out, promptly biphenyl content is greater than 50% biphenyl cut.
2. extract the method for biphenyl in the therefrom matter washing oil according to claim 1, it is characterized in that the biphenyl content in the described raw material in the matter washing oil is greater than 15%.
3. extract the method for biphenyl in the therefrom matter washing oil according to claim 1, it is characterized in that described rectifying tower number of theoretical plate is the 50-80 piece.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101589102A CN101182277B (en) | 2007-12-14 | 2007-12-14 | Method for extracting biphenyl from middle washing oil |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007101589102A CN101182277B (en) | 2007-12-14 | 2007-12-14 | Method for extracting biphenyl from middle washing oil |
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| CN101182277A true CN101182277A (en) | 2008-05-21 |
| CN101182277B CN101182277B (en) | 2010-04-14 |
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| CN2007101589102A Expired - Fee Related CN101182277B (en) | 2007-12-14 | 2007-12-14 | Method for extracting biphenyl from middle washing oil |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101912693A (en) * | 2010-07-29 | 2010-12-15 | 河南宝硕焦油化工有限公司 | Equipment and method for separating indole and biphenyl from wash oil fraction |
| CN103804117A (en) * | 2013-12-05 | 2014-05-21 | 安徽奥瑞化工有限公司 | Preparation method of biphenyl |
| CN108395362A (en) * | 2017-02-08 | 2018-08-14 | 鞍钢股份有限公司 | A method of extracting biphenyl using heat carrier heating negative pressure rectifying |
| CN108395400A (en) * | 2017-02-08 | 2018-08-14 | 鞍钢股份有限公司 | A kind of technique of industrialized production 2- methylquinoline fractions |
| CN109053355A (en) * | 2018-09-29 | 2018-12-21 | 上海化工研究院有限公司 | A kind of method of continuous rectification biphenyl purification |
| CN109438164A (en) * | 2018-12-06 | 2019-03-08 | 南京师范大学 | The device and method for extracting acenaphthene and acenaphthylene in LCO double ring arene |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3700566A (en) * | 1969-10-13 | 1972-10-24 | Phillips Petroleum Co | Biphenyl purification process by plural stage fractional distillation |
| CN100336788C (en) * | 2004-12-07 | 2007-09-12 | 哈尔滨工程大学 | Method of extracting high purity acenaphthene from coat tar scrubbing oil |
-
2007
- 2007-12-14 CN CN2007101589102A patent/CN101182277B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101912693A (en) * | 2010-07-29 | 2010-12-15 | 河南宝硕焦油化工有限公司 | Equipment and method for separating indole and biphenyl from wash oil fraction |
| CN101912693B (en) * | 2010-07-29 | 2012-08-22 | 河南宝硕焦油化工有限公司 | Equipment and method for separating indole and biphenyl from wash oil fraction |
| CN103804117A (en) * | 2013-12-05 | 2014-05-21 | 安徽奥瑞化工有限公司 | Preparation method of biphenyl |
| CN108395362A (en) * | 2017-02-08 | 2018-08-14 | 鞍钢股份有限公司 | A method of extracting biphenyl using heat carrier heating negative pressure rectifying |
| CN108395400A (en) * | 2017-02-08 | 2018-08-14 | 鞍钢股份有限公司 | A kind of technique of industrialized production 2- methylquinoline fractions |
| CN109053355A (en) * | 2018-09-29 | 2018-12-21 | 上海化工研究院有限公司 | A kind of method of continuous rectification biphenyl purification |
| CN109438164A (en) * | 2018-12-06 | 2019-03-08 | 南京师范大学 | The device and method for extracting acenaphthene and acenaphthylene in LCO double ring arene |
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| CN101182277B (en) | 2010-04-14 |
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