CN102451697A - Ethylbenzene carbon dioxide hydrogenation catalyst and preparation method thereof - Google Patents
Ethylbenzene carbon dioxide hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN102451697A CN102451697A CN2010105222467A CN201010522246A CN102451697A CN 102451697 A CN102451697 A CN 102451697A CN 2010105222467 A CN2010105222467 A CN 2010105222467A CN 201010522246 A CN201010522246 A CN 201010522246A CN 102451697 A CN102451697 A CN 102451697A
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- honeycomb ceramic
- ethylbenzene
- carbon dioxide
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- 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
Abstract
The invention relates to an ethylbenzene carbon dioxide hydrogenation catalyst and a preparation method thereof. A catalyst carrier is alumina-coated dichroite honeycomb ceramic; the cross section of the dichroite honeycomb ceramic is circular, square or elliptical; the diameter of the dichroite honeycomb ceramic is 1.5-20 centimeters; the height of the dichroite honeycomb ceramic is 2-20 centimeters; active ingredients are selected from at least two of Fe, Li, K, Na, Mg, Ca, Ce, La and Zr; the loading amount of Fe is 1-30 percent of the total weight of the catalyst counted by Fe2O3; and each aid accounts for 0.05-5 percent of the total weight of the catalyst respectively. The preparation method of the catalyst comprises the following step of: loading a coating of the dichroite honeycomb ceramic and the active ingredients of the catalyst. The ethylbenzene carbon dioxide hydrogenation catalyst disclosed by the invention has relatively high activity, high selectivity and long service life. Due to industrial application of the ethylbenzene carbon dioxide hydrogenation catalyst, the pressure reduction of a bed layer can be reduced, the influence of diffusion resistance in the catalyst is eliminated, and the economic efficiency of a process is increased.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that utilizes carbon dioxide to carry out ethyl benzene dehydrogenation preparation of styrene.
Background technology
Different with ethylbenzene direct dehydrogenation catalyst, ethylbenzene carbon dioxide de hydrogen catalyst adopts the form of loaded catalyst usually.Carrier common in the research has Al
2O
3, ZnO, WO
3, SiO
2, ZrO
2, zeolite and active carbon carbonaceous materials such as (AC) etc., wherein the research of aluminium oxide and active carbon is more.For ethylbenzene carbon dioxide dehydrogenation process, two kinds of catalyst carriers respectively have pluses and minuses.Aluminium oxide is as commercial Application catalyst carrier the most widely, and is cheap and easy to get, and it is easy to have a moulding, characteristics such as formed body mechanical strength height.But aluminium oxide acidity is stronger, makes catalyst surface generation coking and deactivation phenomenon easily.Relative aluminium oxide, activated carbon surface acidity a little less than, help reducing coking rate.But often there is more micropore in active carbon, brings inside diffusional resistance easily; It derives from natural products, and composition and quality are not easy to stablize; Shortcomings such as the bad mechanical property of activated carbon granule.Modern catalytic chemistry research shows that catalyst carrier is not only the active effect of forming of dispersed catalyst of inertia.Carrier and the active interaction of forming, overflow effect of carrier or the like all plays significant effects to catalytic performance.Therefore, select the precondition that the appropriate catalyst carrier is the catalyst commercial Application.
Consider from the response characteristic equal angles of ethylbenzene carbon dioxide dehydrogenation, adopt ordered structure catalyst to prepare and have more high performance ethylbenzene CO
2Dehydrogenation.At first, no matter be ethylbenzene dehydrogenation and ethylbenzene CO
2Certain embodiments all helps the raising of process conversion ratio under lower pressure.For this reason, industry is at present gone up large-scale Ethyl Benzene Dehydrogenation Plant and has all been adopted radial reactor, reduces the pressure drop of reactor with this.Simultaneously because traditional catalyst for phenylethylene dehydrogenation type of feed and particle characteristics have limited the further reduction of beds pressure drop.And regular catalyst has bigger flow area, under identical hydrodynamics condition, has lower bed pressure drop.There are some researches show, adopt cellular regular catalyst can with the beds pressure drop be reduced to pellet type catalyst 1/20 (Wei Liu, Ind.Eng.Chem.Res.2002,41,3131-3138).Secondly, in ordered structure catalyst, base material is used to provide the shape of catalyst, need carry out coating such as aluminium oxide on the base material usually to increase its specific area.The thickness of coating generally has only about tens microns, and the catalyst activity composition is carried on the coating.Therefore the catalyst inside diffusional resistance is less, and this can improve the selectivity of complex reaction in some cases.Therefore, when adopting ordered structure catalyst, can make dehydrogenation reactor have low pressure drop more, higher reaction conversion ratio and selectivity.But the report that does not still have ethylbenzene carbon dioxide dehydrogenation ordered structure catalyst at present.
Summary of the invention
The object of the present invention is to provide a kind of have high activity, high selectivity and long-life ordered structure ethylbenzene carbon dioxide dehydrogenation process Catalysts and its preparation method.
Its carrier of ordered structure ethylbenzene carbon dioxide de hydrogen catalyst according to the invention is a cordierite honeycomb ceramic, and this ceramic honey comb cross section is circular, square or oval, and diameter highly is 2～20cm between 1.5～20cm.The active oxidation aluminized coating is carried out in duct to ceramic honey comb, and coating layer thickness is 10～50 μ m, is 10～50m through its specific area of ceramic honey comb after the coating
2/ g, the aperture of coating concentrates between 10～200nm.
Its activity of ethylbenzene carbon dioxide de hydrogen catalyst according to the invention consists of Fe, and auxiliary agent is at least 2 kinds among Li, K, Mg, Ca, Ce, La, the Zr, and wherein the load capacity of Fe is (with Fe
2O
3The meter) account for total catalyst weight 1～30% between, the content of every kind of auxiliary agent account for respectively total catalyst weight 0.05～5% between.Various components such as above active composition and auxiliary agent are carried on the above-mentioned cordierite honeycomb ceramic.
Ordered structure ethylbenzene carbon dioxide dehydrogenation Preparation of catalysts method of the present invention may further comprise the steps:
Its preparation method is divided into the cordierite honeycomb ceramic coating and active component flooded for two steps:
(1) the boehmite powder is added processes suspension in the entry; The pH value of adding nitric acid to feed liquid is 3-4; This suspension adds after 12～36 hours through the ball mill ball milling again and accounts for the slurry that total weight of material 0.05%～1.0% aluminium colloidal sol and polyethylene glycol obtain being used for the cordierite honeycomb ceramic coating; Cordierite honeycomb ceramic impregnated in the slurry 5-20 minute; Purging is removed unnecessary slurry, and carrier after 1～6 hour, is warming up to the carrier that 400～600 ℃ of calcining 3～10h obtain ethylbenzene carbon dioxide de hydrogen catalyst through 120 ℃ of dryings after the coating in air atmosphere;
Coating layer thickness is 10～50 μ m, is 10～50m through the cordierite honeycomb ceramic specific area after the coating
2/ g, the aperture of coating concentrates between 10～200nm;
(2) at least 2 kinds slaine among active component molysite and Li, K, Na, Mg, Ca, Ce, La, the Zr is dissolved in the water; Adding the nitre acid for adjusting pH value is 4～6; Adopt spray method to be carried on the cordierite honeycomb ceramic that scribbles aluminum oxide coating layer, wherein the load capacity of Fe is with Fe
2O
3Meter accounts for 1～30% of total catalyst weight, and the content of every kind of auxiliary agent accounts for 0.05～5% of total catalyst weight respectively;
The load rear catalyst 120 ℃ dry 12 hours down, 400～600 ℃ of roastings 1～6 hour in air again.
Said various slaine is nitrate, acetate, oxalates, carbonate, and is wherein best with nitrate;
The prepared ethylbenzene carbon dioxide dehydrogenation ordered structure catalyst that obtains of method of the present invention has following characteristics:
1. the ordered structure catalyst of gained of the present invention conveniently is used for ethylbenzene carbon dioxide dehydrogenation industrial process, has outstanding advantages such as the beds pressure drop is low, helps the energy-saving and cost-reducing of ethylbenzene carbon dioxide dehydrogenation industrial process.
2. form through the activity of selecting catalyst, add proper assistant, preferred load process rationally makes catalyst have the catalytic performance of high activity, selectivity and stability;
3. through controlling the character of aluminum oxide coating layer on the cordierite honeycomb; Like the specific area of coating, pore-size distribution, coating layer thickness etc.; Each component of catalyst is carried on the carrier with best proportioning; Guaranteeing that catalyst has the inside diffusional resistance influence of having got rid of catalyst on the basis of high catalytic performance, helps improving activity of such catalysts and selectivity;
The specific embodiment
Embodiment 1
The preparation of ordered structure catalyst carrier
The preparation of aluminium colloidal sol: take by weighing 10g boehmite powder, add 100ml water, add nitre acid for adjusting pH value to 3～4, reflux 24h obtains aluminium colloidal sol.
Coating paste preparation: take by weighing 500 gram boehmite powders, join in the distilled water of 750ml, add the nitric acid of 25ml then; The polyethylene glycol PEG20000 of 10g; Mixture is carried out ball milling, add 100g aluminium colloidal sol at last and mix, promptly get the slurry that is used for coating.
Production of coatings: diameter is kept taking out after 10 minutes for the cordierite honeycomb of 10cm immerses in the coating paste of above-mentioned gained with high, adopt compressed air that cordierite honeycomb was purged 5 minutes.Subsequently with cordierite honeycomb in 120 ℃ dry 3 hours down, 600 ℃ of calcinings 5 hours under air atmosphere afterwards promptly get the ordered structure catalyst carrier.
Embodiment 2
The preparation of supported ferric catalyst
Take by weighing the Fe (NO of 5.05g
3)
39H
2O also is dissolved in it in 10ml water, and above maceration extract is packed in the sprayer, equably it is sprayed on the carrier of ordered structure.Then it was inserted in 120 ℃ of baking ovens dry 12 hours, 600 ℃ of roastings 3 hours under air atmosphere again prepare 20 gram 5.0wt%Fe
2O
3Catalyst, this catalyst called after catalyst A.
Embodiment 3
The Fe-K-Ce Preparation of catalysts
Take by weighing the Fe (NO of 5.05g
3)
39H
2O, the KNO of 0.43g
3, the Ce (NO of 1.30g
3)
36H
2O is dissolved in it in 10ml water, and above maceration extract is packed in the sprayer, equably it is sprayed on the carrier of ordered structure.Then it was inserted in 100 ℃ of baking ovens dry 12 hours, 400 ℃ of roastings 6 hours under air atmosphere again prepare 20 gram 5.0wt%Fe
2O
3-1.0wt%K
2O-2.5wt%Ce
2O
3Catalyst, this catalyst called after catalyst B.
Embodiment 4
The Fe-K-Mg-La Preparation of catalysts
Take by weighing the Fe (NO of 5.05g
3)
39H
2O, the KNO of 0.043g
3, the Mg (NO of 1.28g
3)
26H
2O, the La (NO of 1.00g
3)
36H
2O is dissolved in it in 10ml water, and above maceration extract is packed in the sprayer, equably it is sprayed on the carrier of ordered structure.Then it was inserted in 120 ℃ of baking ovens dry 12 hours, 600 ℃ of roastings 3 hours under air atmosphere again prepare 20 gram 5.0wt%Fe
2O
3-0.1wt%K
2O-1wt%MgO-2.5wt%La
2O
3Catalyst, this catalyst called after catalyst C.
Embodiment 5
The Fe-K-Ca-Zr Preparation of catalysts
Take by weighing the Fe (NO of 5.05g
3)
39H
2O, the KNO of 0.022g
3, the Ca (NO of 0.84g
3)
24H
2O, the Zr (NO of 0.31g
3)
43H
2O is dissolved in it in 10ml water, and above maceration extract is packed in the sprayer, equably it is sprayed on the carrier of ordered structure.Then it was inserted in 120 ℃ of baking ovens dry 12 hours, 500 ℃ of roastings 3 hours under air atmosphere again prepare 20 gram 5.0wt%Fe
2O
3-0.05wt%K
2O-1wt%CaO-1wt%ZrO
2Catalyst, this catalyst called after catalyst D.
Embodiment 6
The Fe-K-Ca-Ce Preparation of catalysts
Take by weighing the Fe (NO of 5.05g
3)
39H
2O, the KNO of 0.043g
3, the Ca (NO of 0.42g
3)
24H
2O, the Ce (NO of 1.06g
3)
36H
2O is dissolved in it in 10ml water, and above maceration extract is packed in the sprayer, equably it is sprayed on the carrier of ordered structure.Then it was inserted in 120 ℃ of baking ovens dry 12 hours, 600 ℃ of roastings 1 hour under inert atmosphere again prepare 20 gram 5.0wt%Fe
2O
3-0.1wt%K
2O-0.5wt%CaO-2wt%Ce
2O
3Catalyst, this catalyst called after catalyst E.
Embodiment 7
The Fe-Li-Ca-Ce Preparation of catalysts
Take by weighing the Fe (NO of 5.05g
3)
39H
2O, the LiNO of 0.092g
3, the Ca (NO of 1.68g
3)
24H
2O, the Ce (NO of 2.60g
3)
36H
2O is dissolved in it in 10ml water, and above maceration extract is packed in the sprayer, equably it is sprayed on the carrier of ordered structure.Then it was inserted in 120 ℃ of baking ovens dry 12 hours, 600 ℃ of roastings 6 hours under inert atmosphere again prepare 20 gram 5.0wt%Fe
2O
3-0.1wt%Li
2O-2wt%CaO-5wt%Ce
2O
3Catalyst, this catalyst called after catalyst F.
Embodiment 8
The comparison of different carriers supported catalyst
The difference of the carrier loaded Fe catalyst performance of this example explanation heterogeneity.
Take by weighing the Fe (NO of 5.05g
3)
39H
2O also is dissolved in it in 10ml water, and above maceration extract is packed in the sprayer, equably it is sprayed to the γ-Al of cloverleaf pattern
2O
3Particle on (diameter 1.5mm, long by 3～8mm).Then it was inserted in 120 ℃ of baking ovens dry 12 hours, 600 ℃ of roastings 3 hours under air atmosphere again prepare 20 gram 5.0wt%Fe
2O
3Catalyst, this catalyst called after catalyst G.
Take by weighing the Fe (NO of 5.05g
3)
39H
2O also is dissolved in it in 10ml water, and above maceration extract is packed in the sprayer, it is sprayed to does not carry out on the cordierite that coating handles equably.Then it was inserted in 120 ℃ of baking ovens dry 12 hours, 600 ℃ of roastings 3 hours under air atmosphere again prepare 20 gram 5.0wt%Fe
2O
3Catalyst, this catalyst called after catalyst H.
Embodiment 9
The performance test of ethylbenzene carbon dioxide de hydrogen catalyst
The method for using and the performance of this example explanation catalyst of the present invention.
The catalyst performance examination is carried out on the isothermal fixed bed reactors of laboratory.Because laboratory reaction device diameter is less, need ordered structure catalyst is broken into pieces, choosing diameter is that 10～20 purpose catalyst granules are checked and rated.The process conditions of active examination are: reaction temperature is 600 ℃, and reaction pressure is 0.1MPa (absolute pressure), and catalyst amount is 10ml, and the ethylbenzene liquid hourly space velocity (LHSV) is 1h
-1, ethylbenzene: carbon dioxide=1: 10 (mol: mol).Tail gas is collected product liquid and is analyzed behind condenser and gas-liquid separator, and analysis condition is: gas chromatograph; The PEG20m/6201-5wt% packed column; Fid detector.Each catalyst appraisal result is as shown in table 1.
Visible by last table data, carrier has obvious influence for catalyst performance, and catalyst G has bigger particle, and it is serious to extend influence in therefore, makes catalyst performance lower.The coating cordierite is the catalyst H of carrier and adopt not, because the specific area of cordierite is very little, so the catalyst cupport effect is relatively poor, and catalytic performance is very low.After reasonably selecting catalyst was formed, the initial activity of catalyst was significantly improved, and selectivity slightly increases, and stability improves greatly.
Claims (2)
1. ethylbenzene carbon dioxide de hydrogen catalyst is characterized in that: catalyst carrier is the cordierite honeycomb ceramic through aluminum oxide coating layer; The cordierite honeycomb ceramic cross section is circular, square or oval, and diameter highly is 2～20cm between 1.5～20cm; Active component is at least 2 kinds among Fe and Li, K, Na, Mg, Ca, Ce, La, the Zr, and the load capacity of Fe is with Fe
2O
3Meter accounts for 1～30% of total catalyst weight, and the content of every kind of auxiliary agent accounts for 0.05～5% of total catalyst weight respectively.
2. ethylbenzene carbon dioxide dehydrogenation Preparation of catalysts method according to claim 1, it is characterized in that: its preparation method is divided into the cordierite honeycomb ceramic coating and active component flooded for two steps:
(1) the boehmite powder is added processes suspension in the entry; The pH value of adding nitric acid to feed liquid is 3-4; This suspension adds after 12～36 hours through the ball mill ball milling again and accounts for the slurry that total weight of material 0.05%～1.0% aluminium colloidal sol and polyethylene glycol obtain being used for the cordierite honeycomb ceramic coating; Cordierite honeycomb ceramic impregnated in the slurry 5-20 minute; Purging is removed unnecessary slurry, and carrier after 1～6 hour, is warming up to the carrier that 400～600 ℃ of calcining 3～10h obtain ethylbenzene carbon dioxide de hydrogen catalyst through 120 ℃ of dryings after the coating in air atmosphere;
Coating layer thickness is 10～50 μ m, is 10～50m through the cordierite honeycomb ceramic specific area after the coating
2/ g, the aperture of coating concentrates between 10～200nm;
(2) at least 2 kinds slaine among active component molysite and Li, K, Na, Mg, Ca, Ce, La, the Zr is dissolved in the water; Adding the nitre acid for adjusting pH value is 4～6; Adopt spray method to be carried on the cordierite honeycomb ceramic that scribbles aluminum oxide coating layer, wherein the load capacity of Fe is with Fe
2O
3Meter accounts for 1～30% of total catalyst weight, and the content of every kind of auxiliary agent accounts for 0.05～5% of total catalyst weight respectively;
The load rear catalyst 120 ℃ dry 12 hours down, 400～600 ℃ of roastings 1～6 hour in air again.
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Cited By (5)
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| CN103772135A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation method |
| CN106268833A (en) * | 2015-05-20 | 2017-01-04 | 中国科学院兰州化学物理研究所苏州研究院 | Iron-based diisobutylene xylol catalyst, its preparation method and application |
| CN110624554A (en) * | 2018-06-22 | 2019-12-31 | 中国石油天然气股份有限公司 | Catalyst for preparing 1, 3-butadiene and preparation method and application thereof |
| CN113578331A (en) * | 2021-08-05 | 2021-11-02 | 大连海事大学 | Cobalt-cerium-zirconium composite oxide catalyst and preparation method thereof |
| CN114515570A (en) * | 2022-01-30 | 2022-05-20 | 华南理工大学 | Catalyst for ethyl acetate oxidation molding and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772135A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation method |
| CN103772135B (en) * | 2012-10-25 | 2015-10-21 | 中国石油化工股份有限公司 | The method of ethylbenzene dehydrogenation |
| CN106268833A (en) * | 2015-05-20 | 2017-01-04 | 中国科学院兰州化学物理研究所苏州研究院 | Iron-based diisobutylene xylol catalyst, its preparation method and application |
| CN106268833B (en) * | 2015-05-20 | 2019-01-22 | 中国科学院兰州化学物理研究所苏州研究院 | Iron-based diisobutylene paraxylene catalyst, preparation method and application |
| CN110624554A (en) * | 2018-06-22 | 2019-12-31 | 中国石油天然气股份有限公司 | Catalyst for preparing 1, 3-butadiene and preparation method and application thereof |
| CN110624554B (en) * | 2018-06-22 | 2022-07-05 | 中国石油天然气股份有限公司 | Catalyst for preparing 1, 3-butadiene and preparation method and application thereof |
| CN113578331A (en) * | 2021-08-05 | 2021-11-02 | 大连海事大学 | Cobalt-cerium-zirconium composite oxide catalyst and preparation method thereof |
| CN113578331B (en) * | 2021-08-05 | 2023-10-24 | 大连海事大学 | Cobalt cerium zirconium composite oxide catalyst and preparation method thereof |
| CN114515570A (en) * | 2022-01-30 | 2022-05-20 | 华南理工大学 | Catalyst for ethyl acetate oxidation molding and preparation method thereof |
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