CN1263541C - Oxide catalyst used in ethyl benzene dehydrogen for preparing phenyl ethylene - Google Patents
Oxide catalyst used in ethyl benzene dehydrogen for preparing phenyl ethylene Download PDFInfo
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- CN1263541C CN1263541C CNB031507204A CN03150720A CN1263541C CN 1263541 C CN1263541 C CN 1263541C CN B031507204 A CNB031507204 A CN B031507204A CN 03150720 A CN03150720 A CN 03150720A CN 1263541 C CN1263541 C CN 1263541C
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- catalyst
- oxide catalyst
- ethyl benzene
- styrene
- oxide
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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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to an oxide catalyst for preparing styrene from ethylbenzene by dehydrogenation, which mainly solves problems which exist in a former technology that the activity and the selectivity of catalysts are poor, and by-products in a production process are not efficiently reduced. The oxide catalyst better solves the problems by adopting the technical scheme that a cerous precursor which is chosen from at least one of Ce (OH) 4, Ce2 (C2O4)3 and Ce2 (CO3)3 is adopted in an iron-kalium-cerium-molybdenum system, the particle size of the precursor is from 0.5 to 20 microns, and the oxide catalyst can be used in industrial production for preparing styrene from ethylbenzene by dehydrogenation.
Description
Technical field
The present invention relates to a kind of oxide catalyst of ethyl benzene dehydrogenation preparation of styrene.
Background technology
The manufacturing of industrial alkenyl arene realizes by alkyl aromatics dehydrogenation.Catalyst system therefor basic composition is major catalyst, co-catalyst and pore-foaming agent, reinforcing agent etc.The catalyst of patent report can be divided into two big classes.One class is the Fe-K series catalysts that contains Cr, as laid-open U.S. Patents 4467046,4684619, European patent 0195252A2, though such activity of such catalysts and stability are better, but owing to more or less there is the oxide of Cr in forming, thereby can cause certain environmental pollution in Preparation of Catalyst, operation and the dead catalyst processing procedure, eliminated gradually.Another kind of is the Fe-K-Ce-Mo series of succeeding in developing the beginning of the eighties, as laid-open U.S. Patents 5190906,4804799, world patent 09839278A1, this type of catalyst substitutes Cr with Ce, Mo, make catalyst keep on the basis of original stability, active also have by a relatively large margin raising than the former, adopted by countries in the world production of styrene producer, its main existing problems are that selectivity of styrene is not high, by-product benzene content is more, brings difficulty for principal product output and later separation step.Therefore, seek a kind of catalyst of production alkenyl arene of high selectivity, improve the yield of principal product alkenyl arene, be the very interested problems of people always.
Summary of the invention
Subject matter to be solved by this invention is to have activity of such catalysts, poor selectivity in the conventional art, can not effectively reduce the problem of accessory substance in the production process, and a kind of oxide catalyst of new ethyl benzene dehydrogenation preparation of styrene is provided.This catalyst has higher activity and selectivity, can effectively reduce the characteristics that accessory substance generates in the course of reaction.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of oxide catalyst of ethyl benzene dehydrogenation preparation of styrene contains following active constituent by weight percentage:
A) 48～80% Fe
2O
3
B) 3～30% K
2O;
C) 0.5～7% MoO
3
D) 3～15% CeO
2
Be binding agent with kaolin, diatomite or cement in the catalyst, the consumption of binding agent is 0.1～10% of a catalyst weight;
CeO wherein
2Presoma be selected from Ce (OH)
4, Ce
2(C
2O
4)
3Or Ce
2(CO
3)
3In at least a, the particle size of presoma is 0.5～20 micron.
The particle size preferable range of presoma is 1～8 micron in the technique scheme, and the catalyst preferred version is also to contain alkaline earth oxide in the active constituent by weight percentage, and its consumption is 0.05～8%; The alkaline earth oxide preferred version is a magnesia.
Method for preparing catalyst of the present invention is as follows: after will evenly mixing by Fe, K, Ce, Mo, other active constituent that need add, adhesive, the perforating agent of proportioning weighing, add an amount of deionized water, make the paste of toughness, suitable extrusion, becoming diameter through extrusion, pelletizing is 3 millimeters, long 8～10 millimeters particle, in 60～120 ℃ of dryings 4 hours, 400～1000 ℃ of following roastings 4 hours, just can obtain finished catalyst then.
Fe is with Fe among the present invention
2O
3Form add; Potassium adds with potassium salt form; Molybdenum adds with its salt or oxide; Other active constituent that need add adds with the form of oxide or its salt; Perforating agent is selected from graphite, polystyrene microsphere or carboxymethyl cellulose, and its consumption is 0.5～4% of the preceding raw material gross weight of catalyst roasting.
Among the present invention, the catalyst that makes as stated above carries out activity rating in the isotherm formula fixed bed, and for the ethyl benzene dehydrogenation preparation of styrene activity rating, the summary process is as follows:
Deionized water and ethylbenzene are imported preheating mixer through measuring pump respectively, and preheating enters reactor after being mixed into gaseous state, and reactor adopts the heating wire heating, makes it to reach predetermined temperature.Reactor inside diameter is 1 " stainless steel tube, interiorly load 100 milliliters, particle diameter is 3 millimeters a catalyst.Analyzing it with gas chromatograph by the reactant of reactor outflow behind water condensation forms.
Conversion of ethylbenzene and selectivity of styrene calculate as follows:
The evaluating catalyst condition is as follows: reaction pressure is that normal pressure, 1.0 liters of ethylbenzene of liquid air speed/rise catalyst hour, 620 ℃ of reaction temperatures, water are than (water/ethylbenzene) 2.0 (weight ratio).Evaluation result sees Table 1.
The stability result of catalyst sees Table 2.
Dehydrogenation of the present invention under certain process conditions, can be applicable to fully that ethylbenzene, diethylbenzene, Alpha-Methyl ethylbenzene dehydrogenation generate styrene, divinylbenzene and AMS.
Pass through among the present invention to adopt in iron-potassium-cerium-molybdenum system, change the precursor material source of cerium, and the size of control granular precursor size, the inventor is surprised to find that when catalyst that this technical scheme makes is used for ethyl benzene dehydrogenation preparation of styrene, catalyst has higher activity, and product styrene has higher selectivity and yield, and same catalyst is formed conversion ratio can improve nearly 2%, selectivity can improve more than 3%, has obtained better technical effect.The composition of catalyst of the present invention is not subjected to the restriction of open scope, adds other active constituent, and activity of such catalysts, selectivity will be further improved.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 307.2 the gram common iron oxide, 59.6 the gram potash, 53.7 the gram granular sizes be 4 microns cerous carbonate, 23.2 the gram molybdenum oxides, 15.1 the gram magnesia and 60.4 the gram cement, 25.7 the gram carboxymethyl celluloses in kneading machine, stirred 1 hour, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 8～10 millimeters of length, put into baking oven, 80 ℃ were dried by the fire 2 hours, 120 ℃ were dried by the fire 2 hours, placed muffle furnace then, made catalyst in 4 hours in 900 ℃ of roastings.
The examination condition of catalyst as mentioned above, its appraisal result sees Table 1, its catalyst weight percentage composition sees Table 2.
[embodiment 2～9]
The preparation method of embodiment 2～9, the composition of catalyst are with embodiment 1, and just the oxidation predecessor is different with granular size, and wherein embodiment 2 and 3 is that its granular size of predecessor is respectively 8 and 16 microns with sour cerium, and embodiment 4,5 and 6 is with 48.5 gram Ce (OH)
4For its granular size of predecessor is respectively 4,8,16 microns, embodiment 7,8 and 9 is with 127.3 gram Ce
2(C
2O
4)
3For its granular size of predecessor is respectively 4,8,16 microns, the examination condition of catalyst as mentioned above, its appraisal result sees Table 1, its catalyst weight percentage composition sees Table 2, wherein the catalyst stability data of embodiment 7 see Table 3.
[comparative example 1～9]
The method for preparing catalyst of comparative example 1～9, inventory, composition are distinguished identical with embodiment 1～9, wherein comparative example 1,2 and 3 is that its size of predecessor is respectively 25,35,40 microns with the cerous carbonate, and comparative example 4～6 is with Ce (OH)
4For its granular size of predecessor is respectively 25,35,40 microns, comparative example 7～9 is with Ce
2(C
2O
4)
3For its granular size of predecessor is respectively 25,35,40 microns, the examination condition of catalyst as mentioned above, its appraisal result sees Table 1, its catalyst weight percentage composition sees Table 2.
The contrast of table 1 catalyst dehydrogenation
| Catalyst | Conversion ratio % | Selectivity % | Single % that receives |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 comparative examples 1 comparative example 2 comparative examples 3 comparative examples 4 comparative examples 5 comparative examples 6 comparative examples 7 comparative examples 8 comparative examples 9 | 70.2 71.0 70.5 70.2 70.5 70.5 73.5 72.6 72.5 68.3 67.5 68.3 67.2 66.5 66.7 67.8 68.2 67.8 | 95.6 95.1 94.3 95.1 94.8 94.2 95.2 95.1 94.0 92.2 91.3 90.3 91.5 92.1 90.3 90.2 90.4 91.5 | 67.1 67.5 66.4 66.7 66.8 66.4 69.9 69.0 68.1 62.9 61.6 61.6 61.4 61.2 60.2 61.1 61.6 62.0 |
The weight percent of table 2 catalyst activity component is formed
| Form | Embodiment 1～9 (%) | Comparative example 1～9 (%) |
| Fe 2O 3 K 2O MgO MoO 3 CeO 2 | 75.0 5.8 3.7 5.6 9.9 | 75.0 5.8 3.7 5.6 9.9 |
The stability of table 3 embodiment 7 catalyst
| Reaction time | |||||||||||
| 50 hours | 100 hours | 200 hours | 300 hours | 400 hours | 500 hours | ||||||
| Con (％) | Sel (％) | Con (％) | Sel (％) | Con (％) | Sel (％) | Con (％) | Sel (％) | Con (％) | Sel (％) | Con (％) | Sel (％) |
| 72.6 | 95.1 | 73.4 | 950 | 73.5 | 95.0 | 73.4 | 95.5 | 73.3 | 95.3 | 73.4 | 95.1 |
Con is a conversion of ethylbenzene, and Sel is a selectivity of styrene.
From implementation, catalyst of the present invention, its basic composition is with Fe
2O
3, K
2O, CeO
2, MoO
3, MgO is main component, suitably selects CeO
3Predecessor and the big or small made dehydrogenation of particle both had high activity, selectivity, good stability is arranged again.
Claims (4)
1, a kind of oxide catalyst of ethyl benzene dehydrogenation preparation of styrene comprises following active constituent by weight percentage:
A) 48～80% Fe
2O
3
B) 3～30% K
2O;
C) 0.5～7% MoO
3
D) 3～15% CeO
2
Be binding agent with kaolin, diatomite or cement in the catalyst, the consumption of binding agent is 0.1～10% of a catalyst weight;
CeO wherein
2Presoma be selected from Ce (OH)
4, Ce
2(C
2O
4)
3Or Ce
2(CO
3)
3In at least a, the particle size of presoma is 0.5～20 micron.
2, according to the oxide catalyst of the described ethyl benzene dehydrogenation preparation of styrene of claim 1, the particle size that it is characterized in that presoma is 1～8 micron.
3, according to the oxide catalyst of the described ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that also containing alkaline earth oxide in the catalyst activity component by weight percentage, its consumption is 0.05～8%.
4,, it is characterized in that alkaline earth oxide is a magnesia according to the oxide catalyst of the described ethyl benzene dehydrogenation preparation of styrene of claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031507204A CN1263541C (en) | 2003-09-03 | 2003-09-03 | Oxide catalyst used in ethyl benzene dehydrogen for preparing phenyl ethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031507204A CN1263541C (en) | 2003-09-03 | 2003-09-03 | Oxide catalyst used in ethyl benzene dehydrogen for preparing phenyl ethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1589963A CN1589963A (en) | 2005-03-09 |
| CN1263541C true CN1263541C (en) | 2006-07-12 |
Family
ID=34597654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031507204A Expired - Lifetime CN1263541C (en) | 2003-09-03 | 2003-09-03 | Oxide catalyst used in ethyl benzene dehydrogen for preparing phenyl ethylene |
Country Status (1)
| Country | Link |
|---|---|
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408167C (en) * | 2005-09-07 | 2008-08-06 | 中国石油化工股份有限公司 | Catalyst for ethylbenzene dehydrogenation-hydroxide reaction |
| CN101091915B (en) * | 2006-06-21 | 2010-05-12 | 中国石油化工股份有限公司 | Catalyst of ethyl benzene dehydrogenation |
| CN104368355B (en) * | 2014-12-02 | 2016-06-15 | 厦门大学 | A kind of catalyst for phenylethylene dehydrogenation and preparation method thereof |
| CN104959146A (en) * | 2015-05-27 | 2015-10-07 | 廖仕杰 | Ethylbenzene dehydrogenation catalyst with low steam-to-oil ratio |
-
2003
- 2003-09-03 CN CNB031507204A patent/CN1263541C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1589963A (en) | 2005-03-09 |
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