CN101514137A - Method for removing trace sulfur in styrene by catalytic rectification - Google Patents
Method for removing trace sulfur in styrene by catalytic rectification Download PDFInfo
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- CN101514137A CN101514137A CNA2008100431327A CN200810043132A CN101514137A CN 101514137 A CN101514137 A CN 101514137A CN A2008100431327 A CNA2008100431327 A CN A2008100431327A CN 200810043132 A CN200810043132 A CN 200810043132A CN 101514137 A CN101514137 A CN 101514137A
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- vinylbenzene
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Abstract
The invention relates to a method for removing trace sulfur in styrene by catalytic rectification, which mainly solves the problem of difficult removal of the trace sulfur in the styrene recovered from pyrolysis gasoline. The method comprises the following steps that: sulfur-containing styrene (the sulfur content is less than or equal to 500ppm) and isobutene enter from a stripping section and the tower bottom of a catalytic distillation tower respectively, a sulfur-containing component in the styrene and the isobutene react to form a heavy component in a reaction section, the separation of the styrene and the generated heavy component is realized in the catalytic distillation tower at the same time, the tower top is provided with a fractional condenser, isobutene is extracted by a gas phase, desulfurized styrene is extracted by a liquid phase, the sulfur content is less than or equal to 10ppm, and the styrene containing the heavy component sulfur is obtained in the tower. The technical proposal better solves the problem, and can be used for industrial application of the trace sulfur removal in the styrene recovered from the pyrolysis gasoline.
Description
Technical field
The present invention relates to the method that a kind of catalytic distillation removes Determination of Trace Sulfur in the vinylbenzene.
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
8Cut is through behind extracting rectifying, solvent recuperation and commercial benzene ethene three rectification cells, obtains purity and be 99.9% vinylbenzene, but the sulphur content in the vinylbenzene more than 150ppm, can't be as the raw material of some polymer production.There are not sulfur-bearing removes in the relevant recycling vinyl benzene with pyrolysis gasoline document and patent report at present.
Introduce the technology that a kind of catalytic distillation removes sulfur-bearing in the petroleum hydrocarbon among the patent CN1412279A, by removing of sulfur component in the coupling realization petroleum hydrocarbon of catalytic hydrogenation reaction and rectifying, overhead distillate is no sulphur petroleum hydrocarbon, and the tower still obtains the heavy constituent sulphur after the hydrogenation reaction.Introduced the method that a kind of oil by catalytic oxidation and extracting and separating removes among the patent CN1683476A, this method is oxygenant with the hydrogen peroxide, the mineral acid of tungstenic and the mixture of quaternary ammonium salt are catalyzer, with organic sulfide catalyzed oxidations such as the thionaphthene in the sour product, dibenzothiophene, oil product after the catalyzed reaction is that extraction agent extracts with the acetonitrile/water azeotrope, and then reaction product is transferred to the polar solvent phase, realize desulfurizing oil.Patent WO2005/073348 has introduced a kind of sulfur method of hydrocarbon ils, has the gac of transistion metal compound to contact by hydrocarbon ils and strong solid acid catalyst or load, carries out desulfurization.
Summary of the invention
The present invention relates to the method that a kind of catalytic distillation removes Determination of Trace Sulfur in the vinylbenzene, mainly solve the problem that from the vinylbenzene that pyrolysis gasoline reclaims Determination of Trace Sulfur removes difficulty, provide a kind of catalytic distillation to remove the method for Determination of Trace Sulfur in the recycling vinyl benzene with pyrolysis gasoline.This method has the high characteristics of desulfuration efficiency.
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 catalytic distillation removes the method for Determination of Trace Sulfur in the vinylbenzene, it is characterized in that sulphur content is not more than the sulfur-bearing vinylbenzene of 500ppm, iso-butylene enters at the bottom of the stripping section of catalytic rectifying tower and tower respectively, sulfur component in the vinylbenzene and iso-butylene react the generation heavy constituent at conversion zone, vinylbenzene is realized separating in catalytic rectifying tower with the heavy constituent of generation simultaneously, cat head is provided with partial condenser, the unreacted iso-butylene of gas phase extraction, liquid phase extraction desulfurization vinylbenzene, sulphur content≤10ppm, the tower still obtains containing the vinylbenzene of heavy constituent sulphur.
In technique scheme, the theoretical number of plates of rectifying section preferred version of catalytic rectifying tower is 10～30, and stripping section number of theoretical plate preferred version is 10～30, and the height of conversion zone is equivalent to the height of 5～20 theoretical stages; The sulfur component raw materials components mole ratio is 1～30 in iso-butylene and the styrene material, and reflux ratio is 0.3～6, and recovery ratio is 90～98%, and working pressure is 4～20KPa; Sulfur component raw materials components mole ratio preferable range is 5～10 in iso-butylene and the styrene material, and the reflux ratio preferable range is 0.7～1.5, and the recovery ratio preferable range is 92～95%, and the working pressure preferable range is 8～12KPa; The conversion zone catalyst filling is at least a in acidic ion exchange resin or the solid acid catalyst.
Sulfur component is a thiophenes in the vinylbenzene that pyrolysis gasoline reclaims, and this sulfur component and cinnamic boiling point are more approaching, can't realize separating by rectifying, because thiophenes and iso-butylene can alkylation generate heavy constituent sulphur under the acid catalyst effect, heavy constituent can be used rectifying separation with vinylbenzene again, thereby sulfur component removes in the realization vinylbenzene.The present invention is by the technical scheme of catalytic distillation, reached to remove removing of sulfur component in the vinylbenzene that pyrolysis gasoline reclaims, and makes vinylbenzene to have obtained better technical effect as producing the cinnamic raw material of polymerization-grade.
Description of drawings
Fig. 1 is the process diagram that catalytic distillation removes Determination of Trace Sulfur in the vinylbenzene.
1 is catalytic rectifying tower among Fig. 1, and 2 is rectifying section, and 3 is conversion zone, and 4 is stripping section, and 5 is partial condenser, and 6 is reboiler, and 7 is sulfur-bearing vinylbenzene, and 8 is iso-butylene, and 9 is unreacted iso-butylene, and 10 are desulfurization vinylbenzene, and 11 for containing the vinylbenzene of heavy constituent sulphur.
By flow process shown in Figure 1, sulfur-bearing styrene 7, isobutene 8 are respectively from stripping section 4 and the tower reactor of catalytic rectifying tower 1 Enter, the sulphur component in the sulfur-bearing styrene 7 and isobutene 8 carry out alkylated reaction at conversion zone 3, and generate restructuring and divide sulphur, Restructuring divides sulphur to realize separating the unreacted isobutyl of dephlegmator of top of the tower 5 gas phase extraction with stripping section 4 at rectifying section 2 with styrene Alkene 9, liquid phase extraction desulfurization styrene 11, tower reactor part liquid phase is through reboiler 6 vaporizations, and a part is contained as extraction Restructuring divides the styrene of sulphur.
The present invention is further illustrated below by specific embodiment, and still, scope of the present invention has more than and is limited to enforcement The scope that example covers.
Embodiment
[embodiment 1]
The number of theoretical plate of catalytic rectifying tower rectifying section is 10, the number of theoretical plate of stripping section is 10, the height of conversion zone is equivalent to the height of 5 theoretical stages, catalyzer is the D001 macroporous ion exchange resin, ion exchange resin ion kenel is the hydrogen radical ion, sulfur-bearing vinylbenzene, iso-butylene (is counted from top to bottom from the 5th theoretical stage of catalytic rectifying tower stripping section respectively, as follows) and the tower still enter, sulfur-bearing vinylbenzene flow is 30 gram/minute, sulphur content is 150ppm, the flow of iso-butylene is 5 ml/min, reflux ratio is 6, cat head liquid phase produced quantity is 27 gram/minute, working pressure is 4KPa, and behind the stable operation, the cinnamic sulphur content of cat head desulfurization is 10ppm, the unreacted iso-butylene of gas phase extraction, the vinylbenzene that contains heavy constituent sulphur that the extraction of tower still obtains.
[embodiment 2]
The number of theoretical plate of catalytic rectifying tower rectifying section is 30, the number of theoretical plate of stripping section is 30, the height of conversion zone is equivalent to the height of 20 theoretical stages, catalyzer is the ZSM-5 molecular sieve catalyst, silica alumina ratio is 45, sulfur-bearing vinylbenzene, iso-butylene (is counted from top to bottom from the 10th theoretical stage of catalytic rectifying tower stripping section respectively, as follows) and the tower still enter, sulfur-bearing vinylbenzene flow is 30 gram/minute, sulphur content is 200ppm, the flow of iso-butylene is 135 ml/min, reflux ratio is 0.3, cat head liquid phase produced quantity is 28.5 gram/minute, working pressure is 20KPa, and behind the stable operation, the cinnamic sulphur content of cat head desulfurization is 4ppm, the unreacted iso-butylene of gas phase extraction, the vinylbenzene that contains heavy constituent sulphur that the extraction of tower still obtains.
[embodiment 3]
The number of theoretical plate of catalytic rectifying tower rectifying section is 15, the number of theoretical plate of stripping section is 20, the height of conversion zone is equivalent to the height of 10 theoretical stages, catalyzer is the ZSM-5 molecular sieve catalyst, silica alumina ratio is 45, sulfur-bearing vinylbenzene, iso-butylene (is counted from top to bottom from the 10th theoretical stage of catalytic rectifying tower stripping section respectively, as follows) and the tower still enter, sulfur-bearing vinylbenzene flow is 30 gram/minute, sulphur content is 180ppm, the flow of iso-butylene is 45 ml/min, reflux ratio is 1.2, cat head liquid phase produced quantity is 28.5 gram/minute, working pressure is 10KPa, and behind the stable operation, the cinnamic sulphur content of cat head desulfurization is 8ppm, the unreacted iso-butylene of gas phase extraction, the vinylbenzene that contains heavy constituent sulphur that the extraction of tower still obtains.
[embodiment 4]
The number of theoretical plate of catalytic rectifying tower rectifying section is 20, the number of theoretical plate of stripping section is 15, the height of conversion zone is equivalent to the height of 10 theoretical stages, catalyzer is a Y type aluminium oxide catalyst, silica alumina ratio is 30, sulfur-bearing vinylbenzene, iso-butylene (is counted from top to bottom from the 8th theoretical stage of catalytic rectifying tower stripping section respectively, as follows) and the tower still enter, sulfur-bearing vinylbenzene flow is 30 gram/minute, sulphur content is 180ppm, the flow of iso-butylene is 65 ml/min, reflux ratio is 1.2, cat head liquid phase produced quantity is 28.4 gram/minute, working pressure is 10KPa, and behind the stable operation, the cinnamic sulphur content of cat head desulfurization is 2ppm, the unreacted iso-butylene of gas phase extraction, the vinylbenzene that contains heavy constituent sulphur that the extraction of tower still obtains.
[embodiment 5]
The number of theoretical plate of catalytic rectifying tower rectifying section is 30, the number of theoretical plate of stripping section is 30, the height of conversion zone is equivalent to the height of 20 theoretical stages, catalyzer is the ZSM-5 molecular sieve catalyst, silica alumina ratio is 45, sulfur-bearing vinylbenzene, iso-butylene (is counted from top to bottom from the 10th theoretical stage of catalytic rectifying tower stripping section respectively, as follows) and the tower still enter, sulfur-bearing vinylbenzene flow is 30 gram/minute, sulphur content is 500ppm, the flow of iso-butylene is 270 ml/min, reflux ratio is 0.3, cat head liquid phase produced quantity is 28.5 gram/minute, working pressure is 15KPa, and behind the stable operation, the cinnamic sulphur content of cat head desulfurization is 9ppm, the unreacted iso-butylene of gas phase extraction, the vinylbenzene that contains heavy constituent sulphur that the extraction of tower still obtains
Claims (5)
1, a kind of catalytic distillation removes the method for Determination of Trace Sulfur in the vinylbenzene, it is characterized in that sulphur content is not more than the sulfur-bearing vinylbenzene of 500ppm, iso-butylene and enters respectively at the bottom of the stripping section of catalytic rectifying tower and tower, sulfur component in the vinylbenzene and iso-butylene react the generation heavy constituent at conversion zone, vinylbenzene is realized separating in catalytic rectifying tower with the heavy constituent of generation simultaneously, cat head is provided with partial condenser, the unreacted iso-butylene of gas phase extraction, liquid phase extraction desulfurization vinylbenzene, sulphur content≤10ppm, the tower still obtains containing the vinylbenzene of heavy constituent sulphur.
2, remove the method for Determination of Trace Sulfur in the vinylbenzene according to right 1 described catalytic distillation, the theoretical number of plates of rectifying section that it is characterized in that catalytic rectifying tower is 10～30, and the stripping section number of theoretical plate is 10～30, and the height of conversion zone is equivalent to the height of 5～20 theoretical stages.
3, remove the method for Determination of Trace Sulfur in the vinylbenzene according to right 1 described catalytic distillation, it is characterized in that the sulfur component raw materials components mole ratio is 1～30 in iso-butylene and the styrene material, reflux ratio is 0.3～6, and recovery ratio is 90～98%, and working pressure is 4～20KPa.
4, remove the method for Determination of Trace Sulfur in the vinylbenzene according to right 3 described catalytic distillations, it is characterized in that the sulfur component raw materials components mole ratio is 5～10 in iso-butylene and the styrene material, reflux ratio is 0.7～1.5, and recovery ratio is 92～95%, and working pressure is 8～12KPa.
5, remove the method for Determination of Trace Sulfur in the vinylbenzene according to right 1 described catalytic distillation, it is characterized in that the conversion zone catalyst filling is at least a in acidic ion exchange resin or the solid acid catalyst.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712848A (en) * | 2016-03-23 | 2016-06-29 | 陆明全 | Methyl tertiary butyl ether desulfurizing agent and application method thereof |
| CN116023225A (en) * | 2023-02-20 | 2023-04-28 | 天津科技大学 | Method for removing thiophenic sulfur in styrene by catalytic alkylation |
| CN116396139A (en) * | 2023-06-08 | 2023-07-07 | 新疆天利石化股份有限公司 | Method for catalytic removal of thiophene aromatic heterocyclic sulfur compounds in styrene in fixed bed reactor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1204229C (en) * | 2001-10-20 | 2005-06-01 | 中国石化集团齐鲁石油化工公司 | Petroleum hydrocarbon hydrogenation desulfurization catalytic distillation process and its catalytic distillation equipment |
| CN101062879B (en) * | 2006-04-28 | 2013-03-20 | 北京石油化工学院 | Coking benzene deep desulfuration purification method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712848A (en) * | 2016-03-23 | 2016-06-29 | 陆明全 | Methyl tertiary butyl ether desulfurizing agent and application method thereof |
| CN116023225A (en) * | 2023-02-20 | 2023-04-28 | 天津科技大学 | Method for removing thiophenic sulfur in styrene by catalytic alkylation |
| CN116396139A (en) * | 2023-06-08 | 2023-07-07 | 新疆天利石化股份有限公司 | Method for catalytic removal of thiophene aromatic heterocyclic sulfur compounds in styrene in fixed bed reactor |
| CN116396139B (en) * | 2023-06-08 | 2023-08-18 | 新疆天利石化股份有限公司 | Method for catalytic removal of thiophene aromatic heterocyclic sulfur compounds in styrene in fixed bed reactor |
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