CN103121919A - Ethylbenzene dehydrogenation method in presence of mild oxidant - Google Patents
Ethylbenzene dehydrogenation method in presence of mild oxidant Download PDFInfo
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- CN103121919A CN103121919A CN2011103695973A CN201110369597A CN103121919A CN 103121919 A CN103121919 A CN 103121919A CN 2011103695973 A CN2011103695973 A CN 2011103695973A CN 201110369597 A CN201110369597 A CN 201110369597A CN 103121919 A CN103121919 A CN 103121919A
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- ethylbenzene
- ethylbenzene dehydrogenation
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Abstract
The invention relates to an ethylbenzene dehydrogenation method in the presence of a mild oxidant, which is mainly used for solving the problems that the dehydrogenation reaction temperature is high, the steam consumption is large and the energy consumption is high under the water vapor atmosphere in the prior art. The technical scheme of the ethylbenzene dehydrogenation method under the carbon dioxide atmosphere is as follows: the catalyst comprises the following components in parts by weight: 0.1-30.0 parts of active components in terms of V2O5 and 55.0-98.0 parts of a catalyst carrier, wherein the catalyst carrier is selected from MCF (Monolithic Crystal Filter) molecular sieve. The ethylbenzene dehydrogenation method can be used for solving the difficult problems well and can be used for the industrial production.
Description
Technical field
The present invention relates to a kind of ethylbenzene dehydrogenation method under mild oxidizer existence.
Background technology
Vinylbenzene is a kind of important basic organic, is widely used in to produce plastics, resin and synthetic rubber.
At present, consume a large amount of water vapors in the production of styrene process as the dehydrogenation medium, water vapor/ethylbenzene mol ratio is between 8-10, in today that world's energy prices skyrocket, high energy consumption becomes the bottleneck of restriction vinylbenzene industry healthy development, and exploitation production of styrene power-saving technology becomes trend of the times.
The latest reports such as Sato using CO without water vapor
2Carry out the effect of ethylbenzene dehydrogenation reaction, use Na
2The Al that O promotes
2O
3Be catalyzer, conversion of ethylbenzene reaches 70%, and selectivity of styrene is more than 81%, but the stability of catalyzer is not high.The people such as Korea S Chemical Engineering Technology research institute Do-Young Hong have reported that on Chemistry Letter magazine V-Sb is oxide carried at MgO-Al
2O
3The result of catalysis dehydrogenation of ethylbenzene to styrene on carrier, when Mg/Al=0.1, the stability of catalyzer is the highest, but fails to provide the activity and selectivity data of catalyzer.
At present, the vinylbenzene more than 90% adopts the ethylbenzene catalytic dehydrogenation method to produce in the world.Adopt water vapor as the dehydrogenation medium in production process, as United States Patent (USP) WO2008148707, WO2009068486 and Chinese patent CN01802428.9, the effect of report water vapor is: (1) makes reaction raw materials be heated to required temperature; (2) additional heat is in order to avoid because endothermic heat of reaction is lowered the temperature; (3) reduce the ethylbenzene dividing potential drop, increase equilibrium conversion; (4) with catalyzer on the coke generation water-gas reaction separated out, to keep catalyst activity.Yet in current technology, the use of a large amount of water vapors, occupied one larger in the production of styrene cost, and one ton of required energy consumption of vinylbenzene of every production is about 6.3 * 10
9KJ is even consider that recovery of latent heat also needs 5.4 * 10
9More than kJ.Recently, the people such as the Park Sang Yon of Korea S chemical research institute have reported in USP 6 034 032 in the temperature range of 500-700 ℃, at (Fe (II)) at Japanese Patent JP11165069 A2 and US Patent No. P 6 037511
x(Fe (III))
yO
z/ S and 5%Fe
3O
4On/ZSM-5 catalyzer, use CO
2Carry out ethylbenzene mild oxidation Oxidative Dehydrogenation vinylbenzene as thinner, can obtain 48% vinylbenzene, but he and fail to develop high performance catalyzer.
Summary of the invention
Technical problem to be solved by this invention is that under the water vapour atmosphere that exists in conventional art, the dehydrogenation reaction temperature is high, and steam consumption quantity is large, and the problem that energy consumption is high provides a kind of mild oxidizer to have lower ethylbenzene dehydrogenation method.The method has that the dehydrogenation reaction temperature is low, and steam consumption quantity is few, the advantage that energy consumption is low.
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 method of ethylbenzene dehydrogenation under carbon dioxide atmosphere, and catalyzer used comprises following composition in parts by weight:
A) active constituent is with V
2O
5Count 0.1-30.0 part;
B) support of the catalyst is 55.0-98.0 part;
Wherein support of the catalyst is selected from the MCF molecular sieve.
In technique scheme, in catalyzer in parts by weight active constituent V
2O
5The consumption preferable range be 1-20 part.In catalyzer take the consumption preferable range of parts by weight support of the catalyst as 70-98 part.
In technique scheme, in reaction, take ethylbenzene as reaction raw materials, reaction is 500-600 ℃ in temperature of reaction, ethylbenzene air speed 0.5～3.0 hour
-1, preferable range is 0.5-1.5, reaction pressure 0～20Kpa, CO
2: the mol ratio of ethylbenzene is 5-30: carry out under 1 condition.
In the present invention, due to catalyzer with V
2O
5Be active constituent, to be selected from the MCF molecular sieve as support of the catalyst, the inventor is surprised to find and has exempted water vapor consumption in reaction process, under 550 ℃ of conditions of temperature of reaction, conversion of ethylbenzene can reach 70.0%, and cinnamic selectivity can reach 99.5%, and temperature of reaction is low, steam consumption quantity is few, the low technique effect preferably of having obtained of energy consumption.
In catalyzer, the preparation method of MCF molecular sieve carrier is as follows: a certain amount of P123 is dissolved in appropriate 1.6M hydrochloric acid soln, be stirred under 30 ℃ evenly, continue to stir again 3h under 40 ℃, then add a certain amount of TMB (1,3,5-trimethylbenzene), stir 3h, then add a certain amount of TEOS (tetraethoxy), the quality proportioning of raw material is P123: TMB: 1.6MHCl: TEOS=2: 1.5: 75: 4.25.Above-mentioned system stirs 24h under 40 ℃, be transferred to subsequently autoclave, at 100 ℃ of hydrothermal crystallizing 24h.The solid product suction filtration is washed with massive laundering, dries under 100 ℃ and spends the night, and roasting 5h removes tensio-active agent in 600 ℃ of air atmospheres at last, gets carrier mesopore silicon oxide foam MCF, and its specific surface is 612m
2g
-1
With a certain amount of NH
3VO
3Be dissolved in the oxalic acid aqueous solution of 0.25M, add carrier MCF, and dry under infrared lamp, then roasting 4h in 550 ℃ of air atmospheres.The catalyzer that obtains is labeled as n V
2O
5/ MCF, n represents V
2O
5Charge capacity, the wt% of unit.
Catalyzer is at CO
2Ethylbenzene dehydrogenation reaction under atmosphere carries out in normal pressure quartz tube type fixed bed continuous flow microreactor, catalyst particle size 40-60 order, product composition gas chromatographic analysis.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
With 80mg V
2O
5Charge capacity is the V of 3.56wt%
2O
5/ MCF catalyzer is packed in the stainless steel reactor of a diameter 5mm, temperature programming to 550 ℃, and 20 ℃/min of temperature rise rate, 550 ℃ of temperature of reaction, the reaction procatalyst is first at 550 ℃ of nitrogen atmospheres activation 2h.Make N
2With CO
2Mixed gas bring ethylbenzene into reactor, N by the ethylbenzene saturated vapo(u)r producer of 15 ℃
2, CO
2With the mol ratio of ethylbenzene be 120: 20: 1, the gas overall flow rate is 60ml min
-1Composition and the reaction conditions of catalyzer see Table 1, and catalyzer performance under all conditions sees Table 2.
[embodiment 2,3,4]
The amount of catalyzer is constant, just with the V in catalyzer
2O
5Charge capacity is adjusted into respectively 7.12,10.68 and 14.24wt%, and all the other are with embodiment 1.Composition and the reaction conditions of catalyzer see Table 1, and catalyzer performance under all conditions sees Table 2.
[comparative example 1]
Use common SiO
2(specific surface is 303m
2g
-1) as carrier, adopt equally equi-volume impregnating to prepare V
2O
5Charge capacity is the V of 10.68wt%
2O
5/ SiO
2, and carry out dehydrogenation reaction under embodiment 1 equal conditions.Composition and the reaction conditions of catalyzer see Table 1, and catalyzer performance under all conditions sees Table 2.
[comparative example 2]
As carrier, adopt equally equi-volume impregnating to prepare V with MCM-41
2O
5Charge capacity is the V of 10.68wt%
2O
5/ MCM-41, and carry out dehydrogenation reaction under embodiment 1 equal conditions.Composition and the reaction conditions of catalyzer see Table 1, and catalyzer performance under all conditions sees Table 2.
[comparative example 3]
Use common Al
2O
3(specific surface is 500m
2g
-1) as carrier, adopt equally equi-volume impregnating to prepare V
2O
5Charge capacity is the V of 10.68wt%
2O
5/ MCM-41, and carry out dehydrogenation reaction under embodiment 1 equal conditions.
Composition and the reaction conditions of catalyzer see Table 1, and catalyzer performance under all conditions sees Table 2.
The composition of table 1 catalyzer and reaction conditions
The dehydrogenation of table 2 catalyzer under carbon dioxide atmosphere
| Transformation efficiency % | Selectivity % | |
| Embodiment 1 | 52.0 | 99.2 |
| Embodiment 2 | 65.0 | 99.0 |
| Embodiment 3 | 70.0 | 99.5 |
| Embodiment 4 | 63.0 | 98.7 |
| Comparative example 1 | 44.5 | 97.3 |
| Comparative example 2 | 54.0 | 99.5 |
| Comparative example 3 | 48.2 | 97.6 |
Claims (3)
1. the method for ethylbenzene dehydrogenation under a carbon dioxide atmosphere, catalyzer used comprises following composition in parts by weight:
A) active constituent is with V
2O
5Count 0.1-30.0 part;
B) support of the catalyst is 55.0-98.0 part;
Wherein support of the catalyst is selected from the MCF molecular sieve.
2. the method for ethylbenzene dehydrogenation under carbon dioxide atmosphere according to claim 1, is characterized in that catalyzer is in parts by weight active constituent V
2O
5Consumption be 1-20 part.
3. the method for ethylbenzene dehydrogenation under carbon dioxide atmosphere according to claim 1 is characterized in that catalyzer is take the consumption of parts by weight support of the catalyst as 70-98 part.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103695973A CN103121919A (en) | 2011-11-18 | 2011-11-18 | Ethylbenzene dehydrogenation method in presence of mild oxidant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103695973A CN103121919A (en) | 2011-11-18 | 2011-11-18 | Ethylbenzene dehydrogenation method in presence of mild oxidant |
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| Publication Number | Publication Date |
|---|---|
| CN103121919A true CN103121919A (en) | 2013-05-29 |
Family
ID=48453107
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|---|---|---|---|
| CN2011103695973A Pending CN103121919A (en) | 2011-11-18 | 2011-11-18 | Ethylbenzene dehydrogenation method in presence of mild oxidant |
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|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582775A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814346A (en) * | 2005-02-05 | 2006-08-09 | 中国石油化工股份有限公司 | Ethyl benzene oxidizing-dehydrogenation catalyst |
-
2011
- 2011-11-18 CN CN2011103695973A patent/CN103121919A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814346A (en) * | 2005-02-05 | 2006-08-09 | 中国石油化工股份有限公司 | Ethyl benzene oxidizing-dehydrogenation catalyst |
Non-Patent Citations (3)
| Title |
|---|
| 张春武等: "CO2选择氧化乙苯制苯乙烯催化剂研究进展", 《化工生产与技术》, vol. 16, no. 4, 31 December 2009 (2009-12-31), pages 44 - 47 * |
| 李春光: "二氧化碳气氛下乙苯脱氢制苯乙烯研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, 15 March 2011 (2011-03-15), pages 28 - 29 * |
| 李春光等: "CO2气氛下MCF负载氧化钒催化剂上乙苯脱氢反应", 《催化学报》, vol. 31, no. 8, 30 August 2010 (2010-08-30), pages 993 - 994 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582775A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene |
| CN106582775B (en) * | 2015-10-16 | 2020-08-07 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene |
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Application publication date: 20130529 |