CN103121920A - Ethylbenzene dehydrogenation method in presence of carbon dioxide - Google Patents
Ethylbenzene dehydrogenation method in presence of carbon dioxide Download PDFInfo
- Publication number
- CN103121920A CN103121920A CN2011103696389A CN201110369638A CN103121920A CN 103121920 A CN103121920 A CN 103121920A CN 2011103696389 A CN2011103696389 A CN 2011103696389A CN 201110369638 A CN201110369638 A CN 201110369638A CN 103121920 A CN103121920 A CN 103121920A
- Authority
- CN
- China
- Prior art keywords
- carbon dioxide
- ethylbenzene
- catalyzer
- ethylbenzene dehydrogenation
- dehydrogenation
- 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.)
- Pending
Links
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to an ethylbenzene dehydrogenation method in the presence of carbon dioxide, which mainly solves the problems in the prior art that the dehydrogenation reaction temperature is high in the presence of steam, the steam consumption is large and the energy consumption is high. By adopting the ethylbenzene dehydrogenation method in the presence of carbon dioxide, a catalyst comprises the following components in parts by weight: a) 0.1-40.0 parts of active components in terms of V2O5; and b) 60.0-99.9 parts of catalyst carriers. Therefore, the problems are better solved, and the method can be used for industrial production of ethylbenzene dehydrogenation.
Description
Technical field
The present invention relates to a kind of ethylbenzene dehydrogenation method under carbon dioxide atmosphere.
Background technology
Vinylbenzene is important Organic Chemicals, is widely used in to produce plastics, resin and synthetic rubber.It is the fourth-largest ethylene derivative product that is only second to PE, PVC, EO, and the output of styrene series resin is only second to PE, PVC and comes in third in synthetic resins.At present, world's vinylbenzene yearly capacity reaches 3,100 ten thousand tons, and the domestic production ability is also 4,700,000 ton/years of left and right.
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 JP11165069A2 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 ethylbenzene dehydrogenation method under new carbon dioxide atmosphere.The method has can save water vapor consumption, the advantage that conversion of ethylbenzene and selectivity of styrene are high.
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, catalyzer used contain following composition in parts by weight:
A) active constituent is with V
2O
5Count 0.1-40.0 part;
B) support of the catalyst is 60.0-99.9 part;
Wherein support of the catalyst is the MCM-41 molecular sieve.
In technique scheme, in the parts by weight active constituent with V
2O
5The consumption preferable range be 1-25 part.Take the consumption preferable range of parts by weight support of the catalyst as 80-99 part.
In technique scheme, in reaction, take ethylbenzene as reaction raw materials, reaction is 500-600 ℃ in temperature of reaction, and the ethylbenzene air speed is 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, catalyzer is due to V
2O
5Be active constituent, to be selected from the MCM-41 molecular sieve as support of the catalyst.The inventor is surprised to find and has exempted water vapor consumption in reaction process, conversion of ethylbenzene can reach 55.0% under 550 ℃ of conditions of temperature of reaction, cinnamic selectivity can reach more than 99%, have and to save water vapor consumption, the high advantage of conversion of ethylbenzene and selectivity of styrene has obtained technique effect preferably.
In catalyzer, the preparation method of MCM-41 molecular sieve carrier is as follows: under 27 ℃ of conditions, a certain amount of CTAB (cetyl trimethylammonium bromide) is soluble in water, stir 0.5h, and add EA (ethamine), under agitation slowly splash into TEOS (tetraethoxy), mole proportioning of raw material is 1SiO
2: 0.2CTAB: 0.6EA: 140H
2O。Above-mentioned system stirs 3h under 27 ℃, be transferred to subsequently autoclave, at 100 ℃ of hydrothermal crystallizing 48h.The solid product suction filtration is washed with massive laundering, dries under 100 ℃ and spends the night, and roasting 6h removes tensio-active agent in 550 ℃ of air atmospheres at last, gets carrier MCM-41 molecular sieve, and its specific surface is 949m
2g
-1
With a certain amount of NH
3VO
3Be dissolved in the oxalic acid aqueous solution of 0.25M, add carrier MCM-41, and dry under infrared lamp, then roasting 4h in 550 ℃ of air atmospheres.The catalyzer that obtains is labeled as n V
2O
5/ MCM-41, 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 4.34wt%
2O
5/ MCM-41 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
-1The composition of catalyzer sees Table 1, and the dehydrogenation of catalyzer under carbon dioxide atmosphere 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 8.34,11.97 and 21.36wt%, and all the other are with embodiment 1.The composition of catalyzer sees Table 1, and the dehydrogenation of catalyzer under carbon dioxide atmosphere 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 11.97% V
2O
5//SiO
2, and carry out dehydrogenation reaction under embodiment 1 equal conditions.The composition of catalyzer sees Table 1, and the dehydrogenation of catalyzer under carbon dioxide atmosphere sees Table 2.
[comparative example 2]
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 that 11.97% charge capacity is 6.73 V
2O
5/ Al
2O
3, and carry out dehydrogenation reaction under embodiment 1 equal conditions.
The composition of catalyzer sees Table 1, and the dehydrogenation of catalyzer under carbon dioxide atmosphere sees Table 2.
The composition of table 1 catalyzer
The dehydrogenation of table 2 catalyzer under carbon dioxide atmosphere
| Transformation efficiency % | Selectivity % | |
| Embodiment 1 | 40.0 | 98.0 |
| Embodiment 2 | 50.0 | 98.8 |
| Embodiment 3 | 55.0 | 99.5 |
| Embodiment 4 | 47.0 | 98.2 |
| Comparative example 1 | 45.0 | 97.3 |
| Comparative example 2 | 44.0 | 97.2 |
Claims (3)
1. the method for ethylbenzene dehydrogenation under a carbon dioxide atmosphere, catalyzer used contains following composition in parts by weight:
A) active constituent is with V
2O
5Count 0.1-40.0 part;
B) support of the catalyst is 60.0-99.9 part;
Wherein support of the catalyst is the MCM-41 molecular sieve.
2. the method for ethylbenzene dehydrogenation under carbon dioxide atmosphere according to claim 1, is characterized in that in the parts by weight active constituent with V
2O
5The consumption of meter is 1-25 part.
3. the method for ethylbenzene dehydrogenation under carbon dioxide atmosphere according to claim 1 is characterized in that consumption take the parts by weight support of the catalyst is as 80-99 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103696389A CN103121920A (en) | 2011-11-18 | 2011-11-18 | Ethylbenzene dehydrogenation method in presence of carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103696389A CN103121920A (en) | 2011-11-18 | 2011-11-18 | Ethylbenzene dehydrogenation method in presence of carbon dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103121920A true CN103121920A (en) | 2013-05-29 |
Family
ID=48453108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103696389A Pending CN103121920A (en) | 2011-11-18 | 2011-11-18 | Ethylbenzene dehydrogenation method in presence of carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103121920A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217658A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Method for preparing ethylbenzene and styrene from biomass platform compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040110630A1 (en) * | 2002-12-10 | 2004-06-10 | Iver Schmidt | Process for catalytic dehydrogenation and catalyst therefor |
| CN102000598A (en) * | 2010-10-29 | 2011-04-06 | 广西壮族自治区化工研究院 | Preparation method and application of CO2 oxidation low carbon alkane dehydrogenation olefin catalyst |
-
2011
- 2011-11-18 CN CN2011103696389A patent/CN103121920A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040110630A1 (en) * | 2002-12-10 | 2004-06-10 | Iver Schmidt | Process for catalytic dehydrogenation and catalyst therefor |
| CN102000598A (en) * | 2010-10-29 | 2011-04-06 | 广西壮族自治区化工研究院 | Preparation method and application of CO2 oxidation low carbon alkane dehydrogenation olefin catalyst |
Non-Patent Citations (2)
| Title |
|---|
| YOSHIHIKO OHISHI等: "Dehydrogenation of ethylbenzene with CO2 over Cr-MCM-41 catalyst", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| 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》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217658A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Method for preparing ethylbenzene and styrene from biomass platform compound |
| CN111217658B (en) * | 2018-11-27 | 2021-05-25 | 中国科学院大连化学物理研究所 | Method for preparing ethylbenzene and styrene from biomass platform compound |
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| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130529 |