CN1552682A - Method for preparing purified petroleum benzine and concentrating thiofuran by cruden benzol - Google Patents
Method for preparing purified petroleum benzine and concentrating thiofuran by cruden benzol Download PDFInfo
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- CN1552682A CN1552682A CNA031405452A CN03140545A CN1552682A CN 1552682 A CN1552682 A CN 1552682A CN A031405452 A CNA031405452 A CN A031405452A CN 03140545 A CN03140545 A CN 03140545A CN 1552682 A CN1552682 A CN 1552682A
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- thiophene
- benzene
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Abstract
A process for preparing high-purity benzene and concentrated thiophene from crude benzene features use of two-class extracting and rectification. Its advantages are simple process, low corrosion to equipment, low cost and high output rate.
Description
Technical field
The present invention relates to the deep processing and the utilization of iron and steel enterprise and the coking enterprise byproduct that produces (being crude benzol) in Industrial processes, specifically, relating in particular to a kind of is raw material with the crude benzol, through the prefractionation unit, two-stage extracting rectifying unit prepares the method for purified petroleum benzin and thiophene enriched material.
Background technology
Benzene is a kind of important basic Organic Chemicals, China accounts for the 45%--50% of domestic benzene yield every year as the intermediate benzene consumption of organic chemical industry and fine chemical material, supply falls short of demand always for the domestic petroleum benzene raw materials, and price is higher relatively, this makes coking benzene become the important source of local fine chemical material, and its demand improves year by year.
Thiophene is a kind of ten minutes expensive chemical raw material, is mainly used in pharmaceutical industry.Though China's coking industry has abundant thiophene resource, because the course of processing generally adopts acid wash technology or hydrogenation technique, thiophene can't reclaim, thereby causes the market of this raw material in short supply, the external import of main at present dependence, and also price is very expensive.
Traditional sulfuric acid scrubbing method is handled coking-light benzene not only can not guarantee quality product, and in treating process, cause the heavy corrosion of equipment, produce a large amount of acid tars and the regenerating acid that can't utilize again at present, to the environment structure severe contamination, benzene hydrocarbon also has to a certain degree loss, and valuable thiophene resource can not get reclaiming.
Traditional shortening method scale of investment is big, the technical qualification harshness, and Catalyst Production cost height, thiophene is thoroughly destroyed in the hydrogenation process.In addition, this technology only is suitable for handling the large-tonnage coking benzene, is not suitable for promoting at medium-sized and small enterprises.Therefore, still do not find a kind of method preferably that crude benzol is prepared into purified petroleum benzin and concentrated thiophene up to now.
Summary of the invention
The objective of the invention is to avoid the weak point of above-mentioned acid wash and shortening method Technology, and propose that a kind of cost of investment is low, process approach is simple, equipment corrosion and environmental pollution degree are little purified petroleum benzin and concentrate the preparation method of thiophene.
Purpose of the present invention can reach by following measure, adopt the two-stage extraction rectifying method, with coking-light benzene or coking-light benzene through the distillation cutting obtain contain benzene-toluene fraction or coking-light benzene is a raw material through the thiophene benzene-toluene fraction that contains that the distillation cutting obtains, obtain containing thiophene concentration through the one-level extracting rectifying and meet the coking benzene product that is not less than GB planned quality of the product secondary standard and the enriched material of thiophene, and then further concentrate through the thiophene enriched material that the secondary extracting rectifying obtains the one-level extracting rectifying, obtain the thiophene product of higher concentration.
Crude benzol comes from the byproduct of iron and steel enterprise and coking enterprise.One-level extracting rectifying raw material come from crude benzol through the prefractionation unit, cutter unit separates the benzene-toluene that the contains thiophene-dimethylbenzene mixed fraction obtain, or the benzene-toluene fraction that contains thiophene that obtains through fractionation by distillation of the benzene cut that contains thiophene that obtains through fractionation by distillation of this mixed fraction or this mixed fraction.The raw material of secondary extracting rectifying comes from one-level solvent recovery tower overhead benzene cut.
The employed extraction solvent of two-stage extracting rectifying comprises N-Methyl pyrrolidone, N, and dinethylformamide, N-formyl morpholine, glycol, tetramethylene sulfone etc. are to the solvent of the selective absorption of thiophene.
The present invention has following advantage compared to existing technology: the two-stage extraction rectification technique, and adopt advanced petrochemical complex isolation technique that existing Produce Reagent technology is transformed, to produce purified petroleum benzin, reclaim thiophene simultaneously, technical process is simple; Save white picking operation in the traditional method, equipment corrosion is little, and waste treatment amount and environmental pollution no longer are subject matter, and environment is not constituted destruction, belongs to environmentally friendly technology; The desulfurization condition gentleness does not consume hydrogen in addition, does not need to adopt expensive hydrogenation catalyst and harsh relatively hydroconversion condition, and valuable thiophene resource can obtain reclaiming, and the benzene loss is few, and resulting product quality specifications is than traditional acid wash technology height.
Description of drawings
Fig. 1 is as extracting rectifying raw material system purified petroleum benzin and the spissated process flow diagram of thiophene with narrow benzene cut.
Embodiment
From figure as can be known; one-level extracting rectifying: with N-Methyl pyrrolidone, N; dinethylformamide, N-formyl morpholine, glycol, tetramethylene sulfone etc.; is that raw material carry out one-level extracting rectifying through narrow benzene cut or the coking-light benzene that the distillation cutting obtains through distillation cutting benzene, toluene fraction to the coking-light benzene that contains finite concentration thiophene sulfide or coking-light benzene; obtain thiophene content from cat head and be not higher than GB planned quality of the product secondary standard coking benzene product; tower base stream obtains preliminary spissated thiophene product through distillation, and this logistics is as the raw material of secondary extracting rectifying.
The secondary extracting rectifying: the thiophene enriched material that obtains with the one-level extracting rectifying is a raw material, after the secondary extracting rectifying further concentrates, obtain the thiophene product of high density through follow-up rectifying separation, secondary extracting rectifying cat head benzene cut turns back to the one-level extractive distillation column, as one-level extracting rectifying part of raw materials.
The invention will be further described below in conjunction with embodiment:
Embodiment one:
With the coking-light benzene that contains the 3350mg/L thiophene, promptly coming from the benzene-toluene-dimethylbenzene mixed fraction of crude benzol after the prefractionation cell processing is raw material, wherein contain benzene 80.7%, toluene 15.4%, dimethylbenzene 3.5%, N-Methyl pyrrolidone is an extraction agent, the rectifying tower number of actual plates is 45, solvent ratio (being extraction agent and the ratio of the volumetric flow rate of raw material coking-light benzene) is 3, reflux ratio is under 3: 1 the condition, the control tower top temperature is 78--80 ℃, tower still temperature is 159--165 ℃, and then the concentration of thiophene is reduced to about 189mg/L in the extracting rectifying overhead fraction coking benzene.Tower bottoms is extracted out and is entered solvent recovery tower, the recovery tower cat head then obtains the enriched material of thiophene, obtain containing the benzene of thiophene concentration 1.98% (wt.) through rectifying separation, this logistics under above-mentioned processing condition, is used N as the raw material of secondary extracting rectifying instead, dinethylformamide is that extraction solvent carries out the secondary extracting rectifying, the control tower top temperature is 78--80 ℃, and tower still temperature is 140--145 ℃, and then the thiophene concentration in the overhead benzene cut of tower still Extract behind the solvent recuperation column distillation can reach 19.5%.
Embodiment two:
With the benzene-toluene system that contains the 4250mg/L thiophene, promptly come from crude benzol through the prefractionation unit, the cut that obtains of benzene cutting and separating is raw material, wherein contain benzene 87.2%, toluene 12.4%, N, dinethylformamide is an extraction agent, the rectifying tower number of actual plates is 40, solvent ratio (being extraction agent and the ratio of the volumetric flow rate of raw material) is 3, reflux ratio is under 3: 1 the condition, the control tower top temperature is 78--80 ℃, tower still temperature is 149--155 ℃, and then the concentration of thiophene is reduced to about 165mg/L in the extracting rectifying overhead fraction coking benzene.Tower bottoms is extracted out and is entered solvent recovery tower, the recovery tower cat head then obtains the enriched material of thiophene, obtain containing the benzene of thiophene concentration 2.12% (wt.) through rectifying separation, this logistics is as the raw material of secondary extracting rectifying, under above-mentioned processing condition, still with N, dinethylformamide is that extraction solvent carries out the secondary extracting rectifying, the control tower top temperature is 78--80 ℃, and tower still temperature is 140--145 ℃, and then the thiophene concentration in the overhead benzene cut of tower still Extract behind the solvent recuperation column distillation can reach 24%.
Claims (5)
1, a kind of method for preparing purified petroleum benzin and concentrated thiophene by crude benzol, it is characterized in that: adopt the two-stage extraction rectifying method, with coking-light benzene or coking-light benzene through the distillation cutting obtain contain benzene-toluene fraction or coking-light benzene is a raw material through the thiophene benzene-toluene fraction that contains that the distillation cutting obtains, obtain containing thiophene concentration through the one-level extracting rectifying and meet the coking benzene product that is not less than GB planned quality of the product secondary standard and the enriched material of thiophene, and then further concentrate through the thiophene enriched material that the secondary extracting rectifying obtains the one-level extracting rectifying, obtain the thiophene product of higher concentration.
2, according to claim 1ly prepare the method for purified petroleum benzin and concentrated thiophene by crude benzol, it is characterized in that: crude benzol comes from the byproduct of iron and steel enterprise and coking enterprise.
3, the method for preparing purified petroleum benzin and concentrated thiophene by crude benzol according to claim 1, it is characterized in that: one-level extracting rectifying raw material come from crude benzol through the prefractionation unit, cutter unit separates the benzene-toluene that the contains thiophene-dimethylbenzene mixed fraction obtain, or the benzene-toluene fraction that contains thiophene that obtains through fractionation by distillation of the benzene cut that contains thiophene that obtains through fractionation by distillation of this mixed fraction or this mixed fraction.
4, according to claim 1ly prepare the method for purified petroleum benzin and concentrated thiophene by crude benzol, it is characterized in that: the raw material of secondary extracting rectifying comes from one-level solvent recovery tower overhead benzene cut.
5, according to claim 3, the 4 described methods that prepare purified petroleum benzin and concentrated thiophene by crude benzol; it is characterized in that: the employed extraction solvent of two-stage extracting rectifying comprises N-Methyl pyrrolidone, N, and dinethylformamide, N-formyl morpholine, glycol, tetramethylene sulfone etc. are to the solvent of the selective absorption of thiophene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031405452A CN100450982C (en) | 2003-05-28 | 2003-05-28 | Method for preparing purified petroleum benzine and concentrating thiofuran by cruden benzol |
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| CNB031405452A CN100450982C (en) | 2003-05-28 | 2003-05-28 | Method for preparing purified petroleum benzine and concentrating thiofuran by cruden benzol |
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| CN1552682A true CN1552682A (en) | 2004-12-08 |
| CN100450982C CN100450982C (en) | 2009-01-14 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319918C (en) * | 2005-05-09 | 2007-06-06 | 天津大学 | Method for refining environmental protection type carbonized benzene |
| CN100336789C (en) * | 2005-12-31 | 2007-09-12 | 石家庄焦化集团有限责任公司 | Process and apparatus for producing reagent benzene by coking benzene |
| CN100400527C (en) * | 2005-09-09 | 2008-07-09 | 太原市侨友化工有限公司 | Method for coke benzene oxydation to produce maleic anhydride |
| CN102382099A (en) * | 2011-11-07 | 2012-03-21 | 潍坊市元利化工有限公司 | Method for preparing thiophene through variable pressure azeotropic distillation |
| CN101440083B (en) * | 2007-11-20 | 2012-04-25 | 河南大学 | Method for extracting thiophen from coking crude benzol |
| CN102432422A (en) * | 2011-09-07 | 2012-05-02 | 山西清盛源化学工业有限公司 | Process flow for refining crude benzol by using halogenation method |
| CN101270026B (en) * | 2008-05-06 | 2012-07-04 | 天津凯赛特科技有限公司 | Abstraction distillation system special for carbonization benezene or sulfureous containing benezene, and fine purification method |
| CN103044385A (en) * | 2013-01-04 | 2013-04-17 | 北京旭阳化工技术研究院有限公司 | Method for extracting thiophene in coking benzene with ionic liquid |
| CN103664480A (en) * | 2013-11-11 | 2014-03-26 | 天津科林泰克科技有限公司 | Method for refining petrobenzene and thiophene by using ionic liquid complex solvent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3879268A (en) * | 1973-10-23 | 1975-04-22 | Leuna Werke Walter Ulbricht 20 | Method for separating thiophene from mixtures thereof with benzene |
-
2003
- 2003-05-28 CN CNB031405452A patent/CN100450982C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319918C (en) * | 2005-05-09 | 2007-06-06 | 天津大学 | Method for refining environmental protection type carbonized benzene |
| CN100400527C (en) * | 2005-09-09 | 2008-07-09 | 太原市侨友化工有限公司 | Method for coke benzene oxydation to produce maleic anhydride |
| CN100336789C (en) * | 2005-12-31 | 2007-09-12 | 石家庄焦化集团有限责任公司 | Process and apparatus for producing reagent benzene by coking benzene |
| CN101440083B (en) * | 2007-11-20 | 2012-04-25 | 河南大学 | Method for extracting thiophen from coking crude benzol |
| CN101270026B (en) * | 2008-05-06 | 2012-07-04 | 天津凯赛特科技有限公司 | Abstraction distillation system special for carbonization benezene or sulfureous containing benezene, and fine purification method |
| CN102432422A (en) * | 2011-09-07 | 2012-05-02 | 山西清盛源化学工业有限公司 | Process flow for refining crude benzol by using halogenation method |
| CN102432422B (en) * | 2011-09-07 | 2016-06-08 | 太原理工大学 | A kind of technological process of halogen process crude benzene refining |
| CN102382099A (en) * | 2011-11-07 | 2012-03-21 | 潍坊市元利化工有限公司 | Method for preparing thiophene through variable pressure azeotropic distillation |
| CN102382099B (en) * | 2011-11-07 | 2013-04-03 | 山东元利科技股份有限公司 | Method for preparing thiophene through variable pressure azeotropic distillation |
| CN103044385A (en) * | 2013-01-04 | 2013-04-17 | 北京旭阳化工技术研究院有限公司 | Method for extracting thiophene in coking benzene with ionic liquid |
| CN103044385B (en) * | 2013-01-04 | 2015-02-18 | 北京旭阳化工技术研究院有限公司 | Method for extracting thiophene in coking benzene with ionic liquid |
| CN103664480A (en) * | 2013-11-11 | 2014-03-26 | 天津科林泰克科技有限公司 | Method for refining petrobenzene and thiophene by using ionic liquid complex solvent |
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| Publication number | Publication date |
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| CN100450982C (en) | 2009-01-14 |
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Granted publication date: 20090114 Termination date: 20110528 |