CN101429091B - Decolorization method for recycling vinyl benzene with abstraction distillation - Google Patents
Decolorization method for recycling vinyl benzene with abstraction distillation Download PDFInfo
- Publication number
- CN101429091B CN101429091B CN2007100478850A CN200710047885A CN101429091B CN 101429091 B CN101429091 B CN 101429091B CN 2007100478850 A CN2007100478850 A CN 2007100478850A CN 200710047885 A CN200710047885 A CN 200710047885A CN 101429091 B CN101429091 B CN 101429091B
- Authority
- CN
- China
- Prior art keywords
- solvent
- tower
- styrene
- cat head
- chrominance
- 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
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a decoloring method for reclaiming styrene by means of extraction and rectification, which mainly solves the problems of a large quantity of solid waste and complex technology caused by adoption of gumbrine for decolorization or high equipment requirement and complex flow caused by adoption of a nitric acid for decolorization. The decoloring method comprises the followingsteps: a decoloring agent is added into a solvent and mixed and dissolved to obtain a material one; the material one and styrene-bearing raw oil enter into the upper part and the middle part of a rectification tower respectively; light constituents the boiling point of which is lower than that of the styrene are rectified on the top of the tower, and the chrominance of the light constituents is less than or equal to 100 as calculated by the platinum-cobalt chrominance unit; a mixture material two of the styrene and the solvent is obtained at the bottom of the tower, wherein the decoloring agent is selected from at least one of an organic acid or organic anhydride, and the solvent is selected from at least one among polar solvents the boiling point of which is more than 160 DEG C; the material two enters into the middle of a solvent reclaiming tower, coarse styrene the chrominance of which is less than or equal to 10 as calculated by the platinum-cobalt chrominance unit is rectified onthe top of the tower, and a reclaimed solvent is obtained at the bottom of the tower; and the coarse styrene enters into the middle of a refined styrene tower, pure styrene the chrominance of which is less than or equal to 10 as calculated by the platinum-cobalt chrominance unit is rectified on the top of the tower, and heavy constituents the boiling point of which is higher than that of the styrene are obtained at the bottom of the tower. The technical proposal well solves the problems.
Description
Technical field
The present invention relates to a kind of decoloring method of recycling vinyl benzene with abstraction distillation.
Background technology
Adopting naphthas is in the ethylene cracker of raw material, and the content of its dimethylbenzene is 0.06～0.07 ton of/ton ethene, and pyrolysis gasoline C
8Dimethylbenzene in the cut: vinylbenzene: the ratio of ethylbenzene is generally 4: 3: 1.Calculate in view of the above, the ethylene unit that a cover is 600,000 tons/year, recyclable vinylbenzene is about 2.9 ten thousand tons/year, if ethylbenzene dehydrogenation is wherein reclaimed, vinylbenzene output also can improve, and has certain recovery value.From pyrolysis gasoline, reclaim vinylbenzene and can eliminate the hydrogen gas consumption of vinylbenzene hydrogenation in traditional pyrolysis gasoline device, thereby alleviate the load of hydrogenation unit; The ethyl-benzene level that reclaims in the Mixed XYLENE significantly reduces, and can be used as the raw material that xylene isomerization is produced p-Xylol; Recyclable a considerable amount of vinylbenzene.
Pyrolysis gasoline C
8The colourity of cut (platinum cobalt chromaticity unit) can't solve vinylbenzene colourity problem greater than 500 through extracting rectifying, solvent recuperation and commercial benzene ethene three rectification cells, and the colourity that obtains pure styrene is still more than 500.Traditional technology adopts the carclazyte decolouring, patent CN1220300 and CN1040218 have introduced the employing carclazyte respectively synthetic hydrocarbon oil and Viscotrol C have been decoloured, this decoloration process produces many carclazyte solid waste, and carclazyte decolouring is thermopositive reaction in addition, makes the easy polymerization of vinylbenzene.
Patent US3763015 has introduced and has adopted nitric acid that the vinylbenzene that reclaims from pyrolysis gasoline is decoloured, a decolouring of this arts demand unit, thus make the technical process complexity, in addition, because nitric acid has severe corrosive, to the equipment requirements height.
Summary of the invention
Technical problem to be solved by this invention is to adopt a large amount of solid waste and the complex process that the carclazyte decolouring brings or adopt the nitric acid decolouring to have equipment requirements height and flow process complicated problems in prior art, a kind of decoloring method of new recycling vinyl benzene with abstraction distillation is provided, and this method has simple, the free of contamination characteristics of flow process.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of decoloring method of recycling vinyl benzene with abstraction distillation, may further comprise the steps: a) discoloring agent is added that mixed dissolution gets stream I in the solvent, stream I and contain the top that the styrene material oil content does not enter extractive distillation column, the middle part, cat head distillates the boiling point light constituent lower than vinylbenzene, its colourity with platinum cobalt chromaticity unit count≤100, the tower still obtains the mixture stream passes II of vinylbenzene and solvent, wherein discoloring agent is selected from least a in organic acid or the organic acid anhydride, and solvent is selected from least a greater than in 160 ℃ the polar solvent of boiling point; B) stream I I enters the middle part of solvent recovery tower, and cat head distillates colourity and counts≤10 crude styrene with platinum cobalt chromaticity unit, and the tower still obtains reclaiming solvent; C) crude styrene enters the middle part of refining benzene ethylene column, and cat head distillates colourity and counts≤10 pure styrene with platinum cobalt chromaticity unit, and the tower still obtains the boiling point heavy constituent higher than vinylbenzene.
In the technique scheme, the number of theoretical plate preferable range of extractive distillation column is 30～60, solvent feed optimum seeking site scheme is the 4th～8 theoretical stage, raw material feed entrance point preferred version is the tower middle part, the solvent ratio preferable range is 5～12, the working pressure preferable range is 8～12KPa, and the reflux ratio preferable range is 0.5～5, and cat head controlled temperature preferable range is 70～85 ℃; The number of theoretical plate preferable range of solvent recovery tower is 10～50, and the working pressure preferable range is 8～12KPa, and the reflux ratio preferable range is 1～5, and cat head controlled temperature preferable range is 75～90 ℃; The number of theoretical plate preferable range of refining benzene ethylene column is 10～50, and the working pressure preferable range is 8～12KPa, and the reflux ratio preferable range is 1～5, and cat head controlled temperature preferable range is 75～90 ℃; Discoloring agent is preferably MALEIC ANHYDRIDE and diacetyl oxide; Solvent is at least a in N-N-formyl morpholine N-, N-Methyl pyrrolidone and tetramethylene sulfone preferably; Discoloring agent consumption preferable range is 0.3～3% of a stock oil weight.
Because micro-content organisms such as nitrogenous, diolefin are arranged in the stock oil, cause the colourity of oil higher, it must be reduced into the saturated structures organism and just can make the colourity of oil reach the quality product requirement.Organic acid and organic acid anhydride have the good solubility energy on the one hand, has good redox property on the other hand again, organism such as organic acid or organic acid anhydride and nitrogenous, diolefin react in extractive distillation column and solvent recovery tower, thus so that vinylbenzene colourity reaches specification of quality.The present invention makes pure styrene colourity reach specification of quality by add the scheme of organic acid or organic acid anhydride in extraction distillation solvent, has obtained better technical effect.
Description of drawings
Fig. 1 is the decoloration process schema of recycling vinyl benzene with abstraction distillation.
1 is mixing tank among Fig. 1, and 2 is extractive distillation column, and 3 is solvent recovery tower, 4 is the refining benzene ethylene column, and 5 is solvent, and 6 is discoloring agent, 7 for containing the discoloring agent solvent, 8 is stock oil, and 9 is light constituent, and 10 is the mixture of vinylbenzene and solvent, 11 is crude styrene, 12 for reclaiming solvent, and 13 is pure styrene, and 14 are heavy constituent.
By flow process shown in Figure 1, discoloring agent 6 becomes to contain discoloring agent solvent 7 with solvent 5 through mixing tank 1 mixed dissolution, contain discoloring agent solvent 7 and stock oil 8 enters extractive distillation column 2 respectively, cat head distillates light constituent 9, and the tower still obtains the mixture 10 of vinylbenzene and solvent, the mixture 10 of vinylbenzene and solvent enters solvent recovery tower 3, cat head distillates crude styrene 11, and the tower still obtains reclaiming solvent 12, and crude styrene 11 enters refining benzene ethylene column 4, cat head distillates pure styrene 13, and the tower still obtains heavy constituent 14.
The present invention is further illustrated below by specific embodiment, and still, scope of the present invention has more than and is limited to the scope that embodiment covers.
Embodiment
[embodiment 1]
Behind discoloring agent maleic acid and the N-N-formyl morpholine N-mixed dissolution, enter number of theoretical plate and be 30 extractive distillation column, feed entrance point is the 4th theoretical stage, the discoloring agent consumption is 3% of a stock oil inlet amount, the stock oil feed entrance point is the 15th theoretical stage, reflux ratio is 5, the working pressure of extractive distillation column is 10KPa, the control tower top temperature is 73.5～75 ℃, cat head obtains than the low-boiling light constituent of vinylbenzene, light constituent colourity is (in platinum cobalt chromaticity unit, as follows) be 50, the tower still is vinylbenzene and solvent mixture, it is 10 solvent recovery tower that this mixture enters number of theoretical plate, feed entrance point is the 5th theoretical stage, reflux ratio is 5, the working pressure of solvent recovery tower is 10KPa, and the control tower top temperature is 76～78.5 ℃, and it is 5 crude styrene that cat head obtains colourity, the tower still is for reclaiming solvent, it is 10 refining benzene ethylene column that the crude styrene solvent enters number of theoretical plate, and feed entrance point is the 5th theoretical stage, and reflux ratio is 5, working pressure is 10KPa, the control tower top temperature is 75～75.5 ℃, and it is 5 pure styrene that overhead distillate obtains colourity, and the tower still obtains heavy constituent.
[embodiment 2]
Behind discoloring agent MALEIC ANHYDRIDE and the N-Methyl pyrrolidone mixed dissolution, enter number of theoretical plate and be 60 extractive distillation column, feed entrance point is the 6th theoretical stage, the discoloring agent consumption is 1% of a stock oil inlet amount, the stock oil feed entrance point is the 30th theoretical stage, reflux ratio is 1, the working pressure of extractive distillation column is 12KPa, the control tower top temperature is 76～78 ℃, cat head obtains than the low-boiling light constituent of vinylbenzene, light constituent colourity is (in platinum cobalt chromaticity unit, as follows) be 80, the tower still is vinylbenzene and solvent mixture, it is 30 solvent recovery tower that this mixture enters number of theoretical plate, feed entrance point is the 15th theoretical stage, reflux ratio is 3, the working pressure of solvent recovery tower is 10KPa, and the control tower top temperature is 80～81.5 ℃, and it is 10 crude styrene that cat head obtains colourity, the tower still is for reclaiming solvent, it is 30 refining benzene ethylene column that the crude styrene solvent enters number of theoretical plate, and feed entrance point is the 15th theoretical stage, and reflux ratio is 3, working pressure is 12KPa, the control tower top temperature is 79～79.5 ℃, and it is 10 pure styrene that overhead distillate obtains colourity, and the tower still obtains heavy constituent.
[embodiment 3]
Behind discoloring agent diacetyl oxide and the tetramethylene sulfone mixed dissolution, enter number of theoretical plate and be 80 extractive distillation column, feed entrance point is the 8th theoretical stage, the discoloring agent consumption is 0.3% of a stock oil inlet amount, the stock oil feed entrance point is the 40th theoretical stage, reflux ratio is 0.5, the working pressure of extractive distillation column is 8KPa, the control tower top temperature is 66～67.5 ℃, cat head obtains than the low-boiling light constituent of vinylbenzene, light constituent colourity is (in platinum cobalt chromaticity unit, as follows) be 100, the tower still is vinylbenzene and solvent mixture, it is 50 solvent recovery tower that this mixture enters number of theoretical plate, feed entrance point is the 25th theoretical stage, reflux ratio is 1, the working pressure of solvent recovery tower is 8KPa, and the control tower top temperature is 69.5～72 ℃, and it is 10 crude styrene that cat head obtains colourity, the tower still is for reclaiming solvent, it is 50 refining benzene ethylene column that the crude styrene solvent enters number of theoretical plate, and feed entrance point is the 25th theoretical stage, and reflux ratio is 1, working pressure is 8KPa, the control tower top temperature is 69～69.5 ℃, and it is 10 pure styrene that overhead distillate obtains colourity, and the tower still obtains heavy constituent.
Claims (3)
1. the decoloring method of a recycling vinyl benzene with abstraction distillation may further comprise the steps:
A, discoloring agent added mixed dissolution gets stream I in the solvent, stream I and contain top, the middle part that the styrene material oil content does not enter extractive distillation column, cat head distillates the boiling point light constituent lower than vinylbenzene, its colourity with platinum cobalt chromaticity unit count≤100, the tower still obtains the mixture stream passes II of vinylbenzene and solvent, wherein discoloring agent is selected from least a in MALEIC ANHYDRIDE and the diacetyl oxide, solvent is selected from least a greater than in 160 ℃ the polar solvent of boiling point, and the discoloring agent consumption is 0.3～3% of a stock oil weight;
B, stream I I enter the middle part of solvent recovery tower, and cat head distillates colourity and counts≤10 crude styrene with platinum cobalt chromaticity unit, and the tower still obtains reclaiming solvent;
C, crude styrene enter the middle part of refining benzene ethylene column, and cat head distillates colourity and counts≤10 pure styrene with platinum cobalt chromaticity unit, and the tower still obtains the boiling point heavy constituent higher than vinylbenzene.
2. according to the decoloring method of the described recycling vinyl benzene with abstraction distillation of claim 1, the number of theoretical plate that it is characterized in that extractive distillation column is 30～80, the solvent feed position is the 4th～8 theoretical stage, the raw material feed entrance point is the tower middle part, solvent ratio is 5～12, working pressure is 8～12KPa, and reflux ratio is 0.5～5, and the cat head controlled temperature is 70～85 ℃; The number of theoretical plate of solvent recovery tower is 10～50, and working pressure is 8～12KPa, and reflux ratio is 1～5, and the cat head controlled temperature is 75～90 ℃; The number of theoretical plate of refining benzene ethylene column is 10～50, and working pressure is 8～12KPa, and reflux ratio is 1～5, and the cat head controlled temperature is 75～90 ℃.
3. according to the decoloring method of the described recycling vinyl benzene with abstraction distillation of claim 1, it is characterized in that solvent is selected from least a in N-N-formyl morpholine N-, N-Methyl pyrrolidone and the tetramethylene sulfone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100478850A CN101429091B (en) | 2007-11-07 | 2007-11-07 | Decolorization method for recycling vinyl benzene with abstraction distillation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100478850A CN101429091B (en) | 2007-11-07 | 2007-11-07 | Decolorization method for recycling vinyl benzene with abstraction distillation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101429091A CN101429091A (en) | 2009-05-13 |
| CN101429091B true CN101429091B (en) | 2011-07-20 |
Family
ID=40644765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100478850A Active CN101429091B (en) | 2007-11-07 | 2007-11-07 | Decolorization method for recycling vinyl benzene with abstraction distillation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101429091B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211560B (en) * | 2013-06-05 | 2016-08-10 | 中国石油天然气股份有限公司 | A kind of drippolene C8 fraction reclaims the discoloration method in styrene technique |
| CN104276926B (en) * | 2013-07-01 | 2017-03-01 | 中国石油化工股份有限公司 | By drippolene C8The discoloration method of the crude styrene that fraction extracting rectifying obtains |
| CN104744206B (en) * | 2013-12-30 | 2016-08-17 | 中国石油化工股份有限公司 | From drippolene C8in fraction, cinnamic method is reclaimed in extractive distillation |
| CN109422613B (en) * | 2017-08-29 | 2021-06-11 | 中国石油化工股份有限公司 | Method and device for decoloring crude styrene separated from pyrolysis gasoline |
| CN109422615B (en) * | 2017-08-29 | 2022-03-11 | 中国石油化工股份有限公司 | Method and device for decoloring crude styrene separated from pyrolysis gasoline |
| CN113912470A (en) * | 2020-07-09 | 2022-01-11 | 中国石化工程建设有限公司 | Method and device for recovering nitric acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3763015A (en) * | 1970-07-18 | 1973-10-02 | Toray Industries | Process for the separation of styrene from thermally cracked petroleum by polymer inhibition and extractive distillation |
| CN1225081A (en) * | 1996-05-21 | 1999-08-04 | Hfm国际公司 | Recovery of styrene from pyrolysis gasoline by extractive distillation |
-
2007
- 2007-11-07 CN CN2007100478850A patent/CN101429091B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3763015A (en) * | 1970-07-18 | 1973-10-02 | Toray Industries | Process for the separation of styrene from thermally cracked petroleum by polymer inhibition and extractive distillation |
| CN1225081A (en) * | 1996-05-21 | 1999-08-04 | Hfm国际公司 | Recovery of styrene from pyrolysis gasoline by extractive distillation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101429091A (en) | 2009-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101429091B (en) | Decolorization method for recycling vinyl benzene with abstraction distillation | |
| CN101050159B (en) | Method for separating butane and butylenes, and dedicated installation | |
| CN105367368B (en) | The method that high-purity isobutylene is prepared from C_4 hydrocarbon | |
| CN103086823B (en) | Method and device for separating n-hexane, isohexane and benzene | |
| CN103073383B (en) | Method and device for separating isohexane, n-hexane and benzene | |
| CN203923057U (en) | Improved Butanol Recycling device | |
| CN101492360A (en) | Process for the separation of aqueous phase by-product of fischer-tropsch synthesis reaction | |
| CN103664446A (en) | Technology for separating n-hexane-methylcyclopentane through extractive distillation | |
| CN102190555B (en) | Method for recovering styrene | |
| CN101429090B (en) | Decolorization method for recycling vinyl benzene with pyrolysis gasoline | |
| CN101250079A (en) | Heat-exchange network device for refining crude benzene and method of operation | |
| CN1085646C (en) | Method for separating arene from hydrocarbons mixture by use of extraction and rectification | |
| CN101081993B (en) | Method for recovering aromatic hydrocarbons from hydrocarbons mixture with high content of aromatic hydrocarbons | |
| CN109704907B (en) | Method for preparing hexane from raffinate oil | |
| CN104829408A (en) | Method for separation of ethyl acetate and cyclohexane | |
| CN101492332A (en) | Process for the separation of aqueous phase by-product of fischer-tropsch synthesis reaction | |
| CN101555194B (en) | Method for separating aqueous phase byproduct from Fischer-Tropsch synthesis reaction | |
| CN202246472U (en) | Device for extracting normal hexane and isohexane from crude hexane | |
| CN100460373C (en) | Method for extracting rectifying and separating benzene | |
| CN109704908B (en) | Method for preparing hexane from aromatic raffinate oil | |
| CN101077849B (en) | Extraction, distillation and separation method for m-methylethylbenzene and p-methylethylbenzene | |
| CN103012102B (en) | Method of recovering acetic acid and water in production of aromatic carboxylic acid | |
| CN216236869U (en) | Multi-stage countercurrent extraction device for catalyzing diesel polycyclic aromatic hydrocarbon by using ionic liquid | |
| CN212504657U (en) | System for hydrogenation and extractive distillation of crude benzene | |
| CN101962311B (en) | Method and device for increasing service life of extractant in hydrofining process of crude benzene |
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 |