CN102241559A - Method for performing oxydehydrogenation of ethylbenzene by using carbon nanofibers loaded on surface of carbon foams as catalyst - Google Patents
Method for performing oxydehydrogenation of ethylbenzene by using carbon nanofibers loaded on surface of carbon foams as catalyst Download PDFInfo
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- CN102241559A CN102241559A CN201110102922XA CN201110102922A CN102241559A CN 102241559 A CN102241559 A CN 102241559A CN 201110102922X A CN201110102922X A CN 201110102922XA CN 201110102922 A CN201110102922 A CN 201110102922A CN 102241559 A CN102241559 A CN 102241559A
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Abstract
A method for performing the oxydehydrogenation of ethylbenzene by using carbon nanofibers loaded on the surface of carbon foams as a catalyst, and belongs to the technical field of the inorganic nonmetallic carbon material science. The method is to use the carbon nanofibers loaded on the surface of carbon foams as a catalyst in the oxydehydrogenation reaction of ethylbenzene, wherein the conversion rate of ethylbenzene is up to 26%, the selectivity is up to 74% and the method shows excellent stability. The method is characterized in that the technology is simple, the production cost is low, the method is environmentally-friendly, the pressure of the catalyst bed is reduced, and the catalyst is easy to separate and recycle, etc.
Description
Technical field
The present invention relates to a kind of method of Carbon foam area load carbon nano fiber catalysis oxidative dehydrogenation of ethylbenzene, belong to inorganic non-metallic materials science technology branch---carbon material science and technology field.
Background technology
Vinylbenzene is one of most important chemical monomer, at present industrially mainly under the superheated vapour condition, promote that with potassium ferriferous oxide is that catalyzer ethylbenzene direct dehydrogenation makes, but there are a lot of drawbacks in this process, as thermodynamical restriction, high energy consumption, the irreversible inactivation of catalyzer and coking.In order to overcome these problems, the various countries scientist is devoted to improve oxidative dehydrogenation of ethylbenzene technology, successfully develops oxydehydrogenation, technology such as auxiliary dehydrogenation of carbonic acid gas and membrane technique.Wherein, oxidative dehydrogenation of ethylbenzene is broken away from thermodynamical restriction with it and lower exothermic temperature becomes most promising novel vinylbenzene technology of preparing.In this course, carbon deposit is considered to substantial catalyzer, so carbonaceous catalyst becomes the focus of people's research.Gac is with its cheap price, the attention that excellent surface chemical property and structural performance have been subjected to scientists.But be easy to oxidizedly owing to the gac reactive behavior is too high, make temperature of reaction need keep low state, thereby can't improve vinylbenzene productive rate and selectivity.On the other hand, the nano-carbon material with certain carbonization structure but shows good catalytic performance, as having obtained gratifying result with carbon nano fiber as ethyl benzene oxidizing-dehydrogenation catalyst.
Though carbon nano fiber shows tempting application prospect in laboratory scale oxidative dehydrogenation of ethylbenzene reaction, powder form makes it be difficult to industrialization.When for example being applied to heterogeneous catalysis field, because the powder morphology of nano-carbon material, thereby cause high bed tap density to bring high bed layer pressure to fall, and this inevitably brings consequences such as high energy consumption and reaction preference reduction.Simultaneously, the bed that causes of dusty material is difficult to control, stops up reactor and catalyzer and be difficult to recycling and cause problem such as dust pollution to ignore.Carbon nano fiber is combined and can effectively address the above problem with the macroscopic material with a fixed structure.
People such as Delgado (Journal of Catalysis, 2006,244 (1): be the synthetic CNTs/ charcoal felt composite material of matrix 126-129), and it is applied to obtain ideal results in the preparing phenylethylene by oxidation-dehydrogenation of ethyl benzene reaction as fixed bed reactor catalyst with the charcoal felt.Su Dangsheng is supporting the activated carbon surface growing nano carbon fiber of iron catalyst, obtain having the carbon/carbon compound material of hierarchy, preliminary adsorption experiment shows that this matrix material has excellent absorption property (AngewandteChemie-International Edition, 2005,44 (34): 5488-5492).People such as Patrick (Journal of MaterialsChemistry, 2008,18 (21): 2426-2436) support nickel catalyzator, obtain the CNFs coverture, and investigated of the influence of Ni loading to diameter and the pattern of CNFs by catalytic pyrolysis ethene on the Carbon foam surface.The result shows that after the CVD process, the Carbon foam specific surface area is by 0.12m
2G
-1Be increased to 146m
2G
-1People such as Calvo (Fuel, 2009,88 (1): 46-53) obtain CNFs/ Carbon foam matrix material by carrying out chemical vapour deposition on catalyst-loaded coal-based Carbon foam surface, and system thinking in the CVD process hydrogen and ethene ratio for the output of CNFs and the influence of pattern.Though in the preparation to Carbon foam area load carbon nano fiber matrix material certain research has been arranged, the research of using for this novel carbon/carbon compound material does not particularly also launch in the applied research of heterogeneous catalysis field.
Summary of the invention
The method that the purpose of this invention is to provide a kind of Carbon foam area load carbon nano fiber catalysis oxidative dehydrogenation of ethylbenzene.This method technology is simple, with low cost, Carbon foam area load carbon nano fiber matrix material catalytic performance excellence, catalyst bed stressor layer reduce, catalyzer is easy to reclaim.
The technical solution used in the present invention is:
0.01-50g is had integrally-built Carbon foam area load carbon nano fiber matrix material put into reactor as beds, the gas reactant air speed is 5000-1000000mL/gh, ethylbenzene and oxidizing gas mol ratio are 0.1-10: 1, and ethylbenzene concentration is 0.1-5%; Temperature of reaction is 380-550 ℃, forms with being furnished with methane conversion furnace gas analysis of hplc instrument assay products, and conversion of ethylbenzene is 10-70%, and selectivity of styrene is 30-95%.
The Carbon foam aperture is the 80-1200 micron, and carbon nano fiber length is the 0.5-700 micron.
Oxidizing gas is selected from oxygen and carbonic acid gas.
The present invention compared with prior art has following advantage:
(1) Carbon foam is the complete Carbon foam surface that is covered in of large pore material carbon nano fiber, effectively utilizes area height and fixed bed bed layer pressure to reduce.
(2) the present invention can regulate pore structure, density and the intensity of foams integral composite easily.
(3) preparation process is simple, not high to equipment requirements, and parameter is controlled easily, processing ease, is easy to amplify.
Embodiment
The present invention is further described below by embodiment.
Embodiment one
0.09g is had integrally-built Carbon foam area load carbon nano fiber matrix material put into reactor as beds, the Carbon foam aperture is 500 microns, carbon nano fiber length is about 50 microns, the gas reactant air speed is 34300mL/gh, ethylbenzene and oxygen mol ratio are 0.5: 1, and ethylbenzene concentration is 2%; Temperature of reaction is 450 ℃, forms with being furnished with methane conversion furnace gas analysis of hplc instrument assay products, and conversion of ethylbenzene is 26%, and selectivity of styrene is 74%.
Embodiment two
0.15g is had integrally-built Carbon foam area load carbon nano fiber matrix material put into reactor as beds, the Carbon foam aperture is 500 microns, carbon nano fiber length is about 30 microns, the gas reactant air speed is 34300mL/gh, ethylbenzene and oxygen mol ratio are 0.5: 1, and ethylbenzene concentration is 2%; Temperature of reaction is 400 ℃, forms with being furnished with methane conversion furnace gas analysis of hplc instrument assay products, and conversion of ethylbenzene is 15%, and selectivity of styrene is 85%.
Embodiment three
0.2g is had integrally-built Carbon foam area load carbon nano fiber matrix material put into reactor as beds, the Carbon foam aperture is 300 microns, carbon nano fiber length is about 80 microns, the gas reactant air speed is 14000mL/gh, ethylbenzene and oxygen mol ratio are 0.5: 1, and ethylbenzene concentration is 2%; Temperature of reaction is 480 ℃, forms with being furnished with methane conversion furnace gas analysis of hplc instrument assay products, and conversion of ethylbenzene is 45%, and selectivity of styrene is 52%.
Claims (3)
1. the method for a Carbon foam area load carbon nano fiber catalysis oxidative dehydrogenation of ethylbenzene, it is characterized in that: this method is 0.01-50g to be had integrally-built Carbon foam area load carbon nano fiber matrix material put into reactor as beds, the gas reactant air speed is 5000-1000000mL/g.h, ethylbenzene and oxidizing gas mol ratio are 0.1-10: 1, and ethylbenzene concentration is 0.1-5%; Temperature of reaction is 380-550 ℃, forms with the gas chromatographicanalyzer assay products of being furnished with the methane conversion stove, and conversion of ethylbenzene is 10-70%, and selectivity of styrene is 30-95%.
2. the method for a kind of Carbon foam area load carbon nano fiber catalysis oxidative dehydrogenation of ethylbenzene according to claim 1, it is characterized in that: the aperture of described Carbon foam is the 80-1200 micron, the length of described carbon nano fiber is the 0.5-700 micron.
3. the method for a kind of Carbon foam area load carbon nano fiber catalysis oxidative dehydrogenation of ethylbenzene according to claim 1, it is characterized in that: described oxidizing gas is selected from oxygen and carbonic acid gas.
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| CN201110102922XA CN102241559A (en) | 2011-04-24 | 2011-04-24 | Method for performing oxydehydrogenation of ethylbenzene by using carbon nanofibers loaded on surface of carbon foams as catalyst |
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| CN201110102922XA CN102241559A (en) | 2011-04-24 | 2011-04-24 | Method for performing oxydehydrogenation of ethylbenzene by using carbon nanofibers loaded on surface of carbon foams as catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923160A (en) * | 2015-07-03 | 2015-09-23 | 河北工业大学 | Preparation method for composite material for adsorbing heavy metal ions in sewage and wastewater |
| CN107285979A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The method of oxidative dehydrogenation of ethylbenzene preparation of styrene |
| CN109368615A (en) * | 2018-12-11 | 2019-02-22 | 广东双虹新材料科技有限公司 | A kind of composite Nano carbon material and preparation method thereof |
| CN110066416A (en) * | 2019-04-29 | 2019-07-30 | 山东师范大学 | A kind of preparation method of phenolic resin foam and Carbon foam |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1586714A (en) * | 2004-07-13 | 2005-03-02 | 华东理工大学 | Nano carbon fiber catalyst for preparing styrene by ethyl benzene oxidation and dehydrogenation and its forming method |
| CN101693533A (en) * | 2009-10-23 | 2010-04-14 | 大连理工大学 | Method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials |
-
2011
- 2011-04-24 CN CN201110102922XA patent/CN102241559A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1586714A (en) * | 2004-07-13 | 2005-03-02 | 华东理工大学 | Nano carbon fiber catalyst for preparing styrene by ethyl benzene oxidation and dehydrogenation and its forming method |
| CN101693533A (en) * | 2009-10-23 | 2010-04-14 | 大连理工大学 | Method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials |
Non-Patent Citations (1)
| Title |
|---|
| J.J.DELGADO ET AL.，: "Immobilized carbon nanofibers as industrial catalyst for ODH reactions", 《JOURNAL OF CATALYSIS》, vol. 244, 27 September 2006 (2006-09-27), pages 126 - 129, XP024913369, DOI: doi:10.1016/j.jcat.2006.08.007 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923160A (en) * | 2015-07-03 | 2015-09-23 | 河北工业大学 | Preparation method for composite material for adsorbing heavy metal ions in sewage and wastewater |
| CN104923160B (en) * | 2015-07-03 | 2017-06-27 | 河北工业大学 | Preparation method for adsorbing the composite of heavy metal ion in stain disease |
| CN107285979A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The method of oxidative dehydrogenation of ethylbenzene preparation of styrene |
| CN107285979B (en) * | 2016-04-12 | 2020-07-07 | 中国石油化工股份有限公司 | Method for preparing styrene by oxidative dehydrogenation of ethylbenzene |
| CN109368615A (en) * | 2018-12-11 | 2019-02-22 | 广东双虹新材料科技有限公司 | A kind of composite Nano carbon material and preparation method thereof |
| CN110066416A (en) * | 2019-04-29 | 2019-07-30 | 山东师范大学 | A kind of preparation method of phenolic resin foam and Carbon foam |
| CN110066416B (en) * | 2019-04-29 | 2021-07-20 | 山东师范大学 | Preparation method of phenolic resin foam and carbon foam |
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Application publication date: 20111116 |