CN103539626B - The method of dehydrogenation of ethylbenzene to styrene - Google Patents
The method of dehydrogenation of ethylbenzene to styrene Download PDFInfo
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- CN103539626B CN103539626B CN201210240058.4A CN201210240058A CN103539626B CN 103539626 B CN103539626 B CN 103539626B CN 201210240058 A CN201210240058 A CN 201210240058A CN 103539626 B CN103539626 B CN 103539626B
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- ethylbenzene
- styrene
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- dehydrogenation
- catalyzer
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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)
Abstract
The present invention relates to a kind of method of ethyl benzene dehydrogenation preparation of styrene.Mainly solve in previous methods and there is the problem that selectivity of styrene is low, catalyst strength is low, catalyzer life cycle is short.The present invention is by using a kind of employing coprecipitation method Kaolinite Preparation of Catalyst presoma cerium iron complex oxides, make again and solve this problem preferably with the technical scheme of the catalyst for phenylethylene dehydrogenation of iron-potassium-cerium-molybdenum-magnesium system, can be used in the industrial production of ethyl benzene dehydrogenation preparation of styrene.
Description
Technical field
The present invention relates to a kind of method of ethyl benzene dehydrogenation preparation of styrene.
Background technology
The current industrial cinnamic overwhelming majority is produced and is realized by ethylbenzene dehydrogenation.Catalyzer composition used comprises Primary Catalysts, promotor and pore-creating agent etc.The catalyzer be widely used at present take Fe-K-Ce-Mo as the mixed oxide catalyst of essentially consist.Preparation method normally by the oxide compound of each component or salt through being dry mixed, adding water kneading, extrusion, oven dry, roasting form, US Patent No. 4804799 as has been publicly, US5190906 etc.Chinese patent 95113340.3 discloses one or more elements adding I B-VIII B race and III A-V A race in Fe-K-Mo system, and catalyzer has higher activity and selectivity.The feature of this type of catalyzer be active, selectivity is higher, stability is better, environmental friendliness.Cinnamic single cover industrial scale is substantially all more than 100,000 tons/year in the world at present, and the production cycle of full scale plant also constantly extends, thus also improves gradually the requirement of catalyzer.In the past in catalyst for phenylethylene dehydrogenation in order to strengthen its ultimate compression strength and the life-span often adds cement adjuvant in the catalyst, the selectivity on reaction such as the material that makes silicon oxide wherein, aluminum oxide, sulfate radical that adds of cement produces certain impact, usually the increase of by product toluene is caused, negative impact is brought to the separation of principal product and productivity effect, and the use minimizing of cement amount also can cause the intensity of catalyzer to reduce, the defects such as the pore structure of catalyzer is abundant, thus the activity of catalyzer and life-span are affected.For this reason, solve the problem in current industrial production, invent a kind of high yield, to produce cinnamic method be the problem that people extremely pay close attention to high stability always.
Summary of the invention
Technical problem to be solved by this invention is the problem that in production of styrene, selectivity is low, catalyst strength is low, life cycle is short, provides a kind of method of ethyl benzene dehydrogenation preparation of styrene.The method has the advantage that selectivity is high, catalyst strength is high, life cycle is long.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of dehydrogenation of ethylbenzene to styrene, take ethylbenzene as raw material, and temperature of reaction is 550 ~ 640 DEG C, the weight ratio of water vapour and ethylbenzene raw material is between 0.9 ~ 3.0, and air speed is 0.5 ~ 1.5 hour
-1under, raw material contacts with the beds in reactor, reaction of styrene, and catalyst wherein used comprises following component:
A) Fe of 60-88%
2o
3;
B) K of 6-22%
2o;
C) CeO of 2-13%
2;
D) MoO of 0.5-6%
3;
E) MgO of 0.5-6%;
Wherein first catalyzer prepares CeO by coprecipitation method in preparation process
2-Fe
2o
3composite oxides.
In technique scheme, the preferable range of temperature of reaction is 600 ~ 620 DEG C; The weight preferable range of water vapour and ethylbenzene raw material is 1.5 ~ 2.0; CeO in catalyzer
2-Fe
2o
3oxide compound prepared by coprecipitation method,
Preparation Fe
2o
3molysite preferred version be at least one in iron nitrate, ferrous sulfate or iron(ic) chloride.
The preparation method of catalyzer in technique scheme, comprises the following steps:
A) the Ce salts solution 1 of the required ratio of configuration
B) the Fe salts solution 2 of the required ratio of configuration
C) above-mentioned solution 1,2 is mixed to get solution 3
D) alkaline solution of the required ratio of configuration, mixes it with solution 3, obtains Ce-Fe precipitation
E) by obtain Ce-Fe sedimentation and filtration, washing, oven dry, obtain CeO 700 ~ 900 DEG C of roastings
2-Fe
2o
3composite oxides;
F) by the oxide compound of K, Mo, Mg of aequum in above-mentioned catalyzer or the CeO of salt component and preparation
2-Fe
2o
3composite oxides in required ratio dry mixed, then add water, through kneading, extrusion, pelletizing, drying, at 700 ~ 900 DEG C roasting finished catalyst.
In technique scheme, will include the first dry mixed of each composition of active ingredient, then add deionized water, through kneading, extrusion, pelletizing, drying, preferred version is roasting at 750 ~ 850 DEG C.
In the present invention, first we owing to adopting the presoma cerium iron complex oxides of precipitator method Kaolinite Preparation of Catalyst, this is conducive in catalyst preparing, form firm ferrocerium skeleton, final formation is with the technical scheme of the Catalysts and its preparation method of iron-potassium-cerium-molybdenum-magnesium system, enhance the intensity of catalyzer, extend work-ing life, and be surprised to find that and improve selectivity of catalyst.Normal pressure, liquid air speed 1.0 hours
-1, temperature of reaction 620 DEG C, water ratio (water/ethylbenzene) 2.0 (weight ratio) reaction conditions under, the transformation efficiency adopting this programme to carry out ethylbenzene dehydrogenation reaction can reach more than 74%, the yield of toluene can be down to 3%, cinnamic selectivity reaches more than 95%, the stability of catalyzer is better, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Respectively with Ce (NO
3)
26H
2o, Fe (NO
3)
39H
2o is raw material, is the proportions solution of 1: 1 by n (Ce): n (Fe).Slowly 0.1 molL is dripped under vigorous stirring in mixing solutions
-1naOH solution, regulates its pH value to 10, after leaving standstill for some time, filters.Precipitate and put into the dry 24h of loft drier after washing, alcohol wash.Ready sample is obtained at 800 DEG C of roasting 6h after oven dry; By 240 grams of red iron oxides, 200 grams of CeO
2-Fe
2o
3the mixing of composite oxides, 50 grams of salt of wormwood, 5 grams of ammonium molybdates, 7 grams of magnesium oxide and 80 grams of deionized waters, mediate to be extruded into 3 millimeters after 1 hour, length is the particle of 5 ~ 8 millimeters, after oven dry, at 800 DEG C, roasting obtains finished catalyst in 4 hours.
Catalyzer was normal pressure, liquid air speed 1.0 hours
-1, temperature of reaction 620 DEG C, water ratio (water/ethylbenzene) 2.0 (weight ratio) reaction conditions under carry out activity rating, evaluation result lists in table 1.
[embodiment 2]
According to the method Kaolinite Preparation of Catalyst of embodiment 1, difference is CeO
2-Fe
2o
3the preparation of composite oxides adopts Ce (NO
3)
26H
2o and FeSO
47H
2o is raw material.Carry out activity rating according to the condition of embodiment 1, evaluation result is in table 1.
[embodiment 3]
According to the method Kaolinite Preparation of Catalyst of embodiment 1, difference is the Ce (NO added
3)
26H
2o, Fe (NO
3)
39H
2o is material quantity is 220 grams.Carry out activity rating according to the condition of embodiment 1, evaluation result is in table 1.
[embodiment 4]
According to the method Kaolinite Preparation of Catalyst of embodiment 1, difference is the Ce (NO added
3)
26H
2o, Fe (NO
3)
39H
2o is material quantity is 240 grams.Carry out activity rating according to the condition of embodiment 1, evaluation result is in table 1.
[embodiment 5]
According to the method Kaolinite Preparation of Catalyst of embodiment 1, difference is change activity rating of catalyst condition is normal pressure, liquid air speed 1.0 hours
-1, temperature of reaction 610 DEG C, water ratio (water/ethylbenzene) 2.0.
[embodiment 6]
According to the method Kaolinite Preparation of Catalyst of embodiment 1, difference is change activity rating of catalyst condition is normal pressure, liquid air speed 1.0 hours
-1, temperature of reaction 620 DEG C, water ratio (water/ethylbenzene) 1.6.
[comparative example 1]
According to the method Kaolinite Preparation of Catalyst of embodiment 1, difference is directly mixed with catalyzer with 360 grams of red iron oxides, 50 grams of salt of wormwood, 110 grams of Sedemesiss, 5 grams of ammonium molybdates, 7 grams of magnesium oxide.Carry out activity rating according to the condition of embodiment 1, evaluation result is in table 1.
The performance comparison of table 1 dehydrogenation catalyst
| Catalyzer | Transformation efficiency % | Selectivity % | Toluene yield % | Average intensity Nmm -1 |
| Embodiment 1 | 75.8 | 95.87 | 2.10 | 21.8 |
| Embodiment 2 | 74.1 | 96.16 | 2.88 | 20.3 |
| Embodiment 3 | 75.3 | 95.35 | 3.87 | 21.5 |
| Embodiment 4 | 74.3 | 96.75 | 2.62 | 22.0 |
| Embodiment 5 | 75.0 | 96.32 | 2.53 | 21.8 |
| Embodiment 6 | 74.9 | 96.15 | 2.96 | 21.8 |
| Comparative example 1 | 71.2 | 92.84 | 3.98 | 19.8 |
The stability of table 2 embodiment 1 catalyzer
Above embodiment explanation, adopt the presoma cerium iron complex oxides of precipitator method Kaolinite Preparation of Catalyst, effectively constitute firm ferrocerium skeleton, final formation is with the catalyzer of iron-potassium-cerium-molybdenum-magnesium system, enhance the physical strength of catalyzer, and improve selectivity of catalyst and stability, the method can be used in industrial production.
Claims (4)
1. a method for dehydrogenation of ethylbenzene to styrene, take ethylbenzene as raw material, temperature of reaction is 550 ~ 640 DEG C, and the weight ratio of water vapour and ethylbenzene raw material is between 0.9 ~ 3.0, and air speed is 0.5 ~ 1.5 hour
-1under, raw material contacts with the beds in reactor, reaction of styrene, and catalyst wherein used comprises following component:
A) Fe of 60-88%
2o
3;
B) K of 6-22%
2o;
C) CeO of 2-13%
2;
D) MoO of 0.5-6%
3;
E) MgO of 0.5-6%;
Wherein first catalyzer prepares CeO by coprecipitation method in preparation process
2-Fe
2o
3composite oxides.
2. the method for dehydrogenation of ethylbenzene to styrene according to claim 1, is characterized in that temperature of reaction is 600 ~ 620 DEG C.
3. the method for dehydrogenation of ethylbenzene to styrene according to claim 1, is characterized in that the weight ratio of water vapour and ethylbenzene raw material is 1.5 ~ 2.0.
4. the method for dehydrogenation of ethylbenzene to styrene according to claim 1, is characterized in that preparing Fe
2o
3molysite be at least one in iron nitrate, ferrous sulfate or iron(ic) chloride.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210240058.4A CN103539626B (en) | 2012-07-12 | 2012-07-12 | The method of dehydrogenation of ethylbenzene to styrene |
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|---|---|---|---|
| CN201210240058.4A CN103539626B (en) | 2012-07-12 | 2012-07-12 | The method of dehydrogenation of ethylbenzene to styrene |
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| CN103539626B true CN103539626B (en) | 2015-08-12 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4804799A (en) * | 1987-08-28 | 1989-02-14 | The Dow Chemical Company | Dehydrogenation catalyst |
| CN102040467A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for producing styrene by ethylbenzene dehydrogenation |
-
2012
- 2012-07-12 CN CN201210240058.4A patent/CN103539626B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4804799A (en) * | 1987-08-28 | 1989-02-14 | The Dow Chemical Company | Dehydrogenation catalyst |
| CN102040467A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for producing styrene by ethylbenzene dehydrogenation |
Non-Patent Citations (1)
| Title |
|---|
| Ce1-xFexO2复合氧化物的结构及其催化碳烟低温燃烧性能;晏冬霞等;《物理化学学报》;201002;第26卷(第02期);331-337 * |
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| CN103539626A (en) | 2014-01-29 |
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