CN101429090B - Decolorization method for recycling vinyl benzene with pyrolysis gasoline - Google Patents
Decolorization method for recycling vinyl benzene with pyrolysis gasoline Download PDFInfo
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- CN101429090B CN101429090B CN2007100478846A CN200710047884A CN101429090B CN 101429090 B CN101429090 B CN 101429090B CN 2007100478846 A CN2007100478846 A CN 2007100478846A CN 200710047884 A CN200710047884 A CN 200710047884A CN 101429090 B CN101429090 B CN 101429090B
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Abstract
The invention relates to a decoloring method for reclaiming styrene from pyrolysis gasoline, 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 is as follows: coarse styrene enters into the middle of a refined styrene tower, and pure styrene vapor is obtained on the top of the tower; after the pure styrene vapor is condensed by a condenser, one part is extracted to prepare pure styrene the chrominance of which is less than or equal to 10 as calculated by the platinum-cobalt chrominance unit, and the other part of the pure styrene vapor enters into a return tank, mixed and dissolved with a decoloring agent, and enters into the top of the tower for reflux, and heavy constituents are obtained at the bottom of the tower, wherein the decoloring agent is selected from at least one of an organic acid or organic anhydride. The technical proposal well solves the problems, and the decoloring method can be used in industrial production for reclaiming the styrene from the pyrolysis gasoline.
Description
Technical field
The present invention relates to a kind of decoloring method of recycling vinyl benzene with pyrolysis gasoline.
Background technology
Adopting naphthas is in the ethylene cracker of raw material, and the content of its YLENE is 0.06～0.07 ton of/ton ethene, and pyrolysis gasoline C
8YLENE 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 from pyrolysis gasoline, reclaims is decoloured, a decolouring of this arts demand unit, thus make technical process complicated, in addition,, high to equipment requirements because nitric acid has severe corrosive.
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 pyrolysis gasoline 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 scheme that the present invention adopts is following: a kind of crude styrene gets into the middle part of refining benzene ethylene column; Cat head gets pure styrene steam after condenser condenses, and a part of extraction is a pure styrene, and pure styrene colourity is in platinum cobalt chromaticity unit≤10; Another part pure styrene gets into trim the top of column after getting into return tank and discoloring agent mixed dissolution, and the tower still obtains heavy constituent, and wherein discoloring agent is selected from least a in organic acid or the organic acid anhydride.
In technique scheme, 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 control tower top temperature preferable range is 75～90 ℃; The discoloring agent preferred version is to be selected from least a in oxalic acid, MALEIC ANHYDRIDE and the diacetyl oxide; Discoloring agent consumption preferable range is 0.5～5% of a crude styrene weight.
Because micro-content organisms such as nitrogenous, diolefin are arranged in the crude styrene, cause cinnamic colourity higher, must it 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 good solubility on the one hand can; Has good redox property on the other hand again; Organism such as organic acid or organic acid anhydride and nitrogenous, diolefin react in the refining benzene ethylene column; Generate the heavy constituent of saturated structures, thereby get so that pure styrene colourity reaches specification of quality.The present invention makes pure styrene colourity reach specification of quality through in the trim the top of column vinylbenzene of refining benzene ethylene column, adding the scheme of decolouring, has obtained better technical effect.
Description of drawings
Fig. 1 is the decoloration process synoptic diagram of recycling vinyl benzene with pyrolysis gasoline.
1 is the refining benzene ethylene column among Fig. 1, and 2 is condensing surface, and 3 is return tank, and 4 is reboiler, and 5 is crude styrene, and 6 is pure styrene, and 7 are heavy constituent, and 8 is discoloring agent.
By flow process shown in Figure 1; Crude styrene 5 gets into refining benzene ethylene column 1; Cat head pure styrene steam is after condensing surface 2 condensations; Part extraction is a pure styrene 5, and another part vinylbenzene gets into refining benzene ethylene column 1 as refluxing after getting into return tank 3 and discoloring agent 8 mixed dissolutions, and the tower still obtains heavy constituent 7 extraction.
Through specific embodiment the present invention is further described below, still, scope of the present invention has more than and is limited to the scope that embodiment covers.
Embodiment
[embodiment 1]
It is 10 refining benzene ethylene column that crude styrene gets into number of theoretical plate with 10 gram/minute, and feed entrance point is the 5th theoretical stage, and reflux ratio is 5; Working pressure is 12KPa, and the control tower top temperature is 79～79.5 ℃, and cat head pure styrene steam is after condenser condenses; The flow of extraction pure styrene is 8 gram/minute; Pure styrene colourity counts 10 with platinum cobalt chromaticity unit, and remaining vinylbenzene flows into return tank with 40 gram/minute, and the discoloring agent maleic acid gets into return tank with 0.05 gram/minute; Get into refining benzene ethylene column cat head behind both mixed dissolutions, the tower still obtains heavy constituent with 2 gram/minute extraction.
[embodiment 2]
It is 50 refining benzene ethylene column that crude styrene gets into number of theoretical plate with 10 gram/minute, and feed entrance point is the 25th theoretical stage, and working pressure is 10KPa; Reflux ratio is 1, and the control tower top temperature is 75～75.5 ℃, and cat head pure styrene steam is after condenser condenses; The flow of extraction pure styrene is 8 gram/minute; Pure styrene colourity counts 5 with platinum cobalt chromaticity unit, and remaining vinylbenzene flows into return tank with 8 gram/minute, and the discoloring agent oxalic acid gets into return tank with 0.5 gram/minute; Get into refining benzene ethylene column cat head behind both mixed dissolutions, the heavy constituent of tower still are with 2 gram/minute extraction.
[embodiment 3]
It is 30 refining benzene ethylene column that crude styrene gets into number of theoretical plate with 10 gram/minute, the 15th theoretical stage of feed entrance point, and working pressure is 8KPa; Reflux ratio is 2, and the control tower top temperature is 69～69.5 ℃, and cat head pure styrene steam is after condenser condenses; The flow of extraction pure styrene is 8 gram/minute; Pure styrene colourity counts 5 with platinum cobalt chromaticity unit, and remaining vinylbenzene flows into return tank with 16 gram/minute, and the discoloring agent MALEIC ANHYDRIDE gets into return tank with 0.05 gram/minute; Get into refining benzene ethylene column cat head behind both mixed dissolutions, the heavy constituent of tower still are with 2 gram/minute extraction.
[embodiment 4]
It is 30 refining benzene ethylene column that crude styrene gets into number of theoretical plate with 10 gram/minute, and feed entrance point is the 10th theoretical stage, and working pressure is 8KPa; Reflux ratio is 2.5, and the control tower top temperature is 69～69.5 ℃, and cat head pure styrene steam is after condenser condenses; The flow of extraction pure styrene is 8 gram/minute; Pure styrene colourity counts 10 with platinum cobalt chromaticity unit, and remaining vinylbenzene flows into return tank with 20 gram/minute, and the discoloring agent diacetyl oxide gets into return tank with 0.1 gram/minute; Get into refining benzene ethylene column cat head behind both mixed dissolutions, the heavy constituent of tower still are with 2 gram/minute extraction.
Claims (3)
1. the decoloring method of a recycling vinyl benzene with pyrolysis gasoline; It is characterized by and be that crude styrene gets into the middle part of refining benzene ethylene column; Cat head gets pure styrene steam after condenser condenses, and a part of extraction is a pure styrene, and pure styrene colourity is in platinum cobalt chromaticity unit≤10; Another part pure styrene gets into trim the top of column after getting into return tank and discoloring agent mixed dissolution, and the tower still obtains heavy constituent, and wherein discoloring agent is selected from least a in oxalic acid, MALEIC ANHYDRIDE and the diacetyl oxide.
2. according to the decoloring method of the said recycling vinyl benzene with pyrolysis gasoline of claim 1, the number of theoretical plate that it is characterized in that the refining benzene ethylene column is 10～50, and working pressure is 8～12KPa, and reflux ratio is 1～5, and the control tower top temperature is 75～90 ℃.
3. according to the decoloring method of the said recycling vinyl benzene with pyrolysis gasoline of claim 1, it is characterized in that the discoloring agent consumption is 0.5～5% of a crude styrene weight.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007100478846A CN101429090B (en) | 2007-11-07 | 2007-11-07 | Decolorization method for recycling vinyl benzene with pyrolysis gasoline |
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| CN2007100478846A CN101429090B (en) | 2007-11-07 | 2007-11-07 | Decolorization method for recycling vinyl benzene with pyrolysis gasoline |
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| CN101429090A CN101429090A (en) | 2009-05-13 |
| CN101429090B true CN101429090B (en) | 2012-05-09 |
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Families Citing this family (4)
| 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 | Decoloring method in process for recovering styrene from pyrolysis gasoline C8 fraction |
| 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 |
| 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 |
| CN108610231A (en) * | 2018-03-09 | 2018-10-02 | 惠州大亚湾伊科思新材料科技发展有限公司 | A kind of method and apparatus controlling decolorising agent system temperature in styrene extraction device |
Citations (3)
| 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 |
| CN1456543A (en) * | 2002-05-10 | 2003-11-19 | 长春市环境保护技术开发公司 | Polystyrene treating method |
| CN1623695A (en) * | 2003-12-05 | 2005-06-08 | 刘艳平 | Process for treating waste material of poly phenylethylene |
-
2007
- 2007-11-07 CN CN2007100478846A patent/CN101429090B/en active Active
Patent Citations (3)
| 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 |
| CN1456543A (en) * | 2002-05-10 | 2003-11-19 | 长春市环境保护技术开发公司 | Polystyrene treating method |
| CN1623695A (en) * | 2003-12-05 | 2005-06-08 | 刘艳平 | Process for treating waste material of poly phenylethylene |
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