CN100413830C - Method for preparing phenethylene through dehydrogenation of ethyl benzene - Google Patents
Method for preparing phenethylene through dehydrogenation of ethyl benzene Download PDFInfo
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- CN100413830C CN100413830C CNB200510028777XA CN200510028777A CN100413830C CN 100413830 C CN100413830 C CN 100413830C CN B200510028777X A CNB200510028777X A CN B200510028777XA CN 200510028777 A CN200510028777 A CN 200510028777A CN 100413830 C CN100413830 C CN 100413830C
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- ethylbenzene
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Abstract
This invention relates to a method for preparing styrene by ethyl benzene dehydrogenation. Styrene is prepared at 450-550 deg.C, normal pressure, space velocity of 0.1-1.0h-1, and CO2/ethyl benzene mol ratio of (10-30): 1 in the presence of Cr2O3/Al2O3 catalyst. The method solves the problems of high energy consumption by steam diluter, or low catalyst performance at low temperatures caused by CO2 diluter. The method can be used for manufacture of styrene by ethyl benzene dehydrogenation.
Description
Technical field
The present invention relates to a kind of method that is used for ethyl benzene dehydrogenation preparation of styrene.
Background technology
Vinylbenzene is important Organic Chemicals, is widely used in to produce plastics, resin and synthetic rubber.Be to be only second to PE, PVC, the 4th big ethylene derivative product of EO, in recent years, demand continues to increase (speed increases with 3～4%).Estimate that 2004 annual requirements will be above 2.1 * 10
8Ton.China introduces 8 covers over nearly 7 years and domestic technology builds up 3 cover production of styrene devices, and yearly capacity is about 900,000 tons.After the China's entry into the WTO, the price competition fierceness of globalization chemical product.Therefore, develop new technological process, reduce cost.Have great importance for the economic benefit that improves petroleum chemical enterprise.
The method of industrialized production of styrene has ethylbenzene dehydrogenation method and styrene and propylene oxide co-production method.Wherein, the co-production method complex process, one-time investment is big, the energy consumption height.Therefore 90% vinylbenzene is produced by the ethylbenzene dehydrogenation method.The principal reaction of ethylbenzene dehydrogenation is: C
6H
5-C
2H
5→ C
6H
5CH=CH
2+ H
2+ 124 kj/mol.Analyze from thermodynamics, improve temperature, to reduce system pressure favourable to balance.But the raising of temperature of reaction is very restricted, and produces benzene, toluene, CO, CO because too high temperature of reaction not only causes the ethylbenzene cracking
2In byproduct, and energy consumption is very big.Thereby industrial great majority adopt a large amount of water vapour as the dehydrogenation medium.Its effect is: (1) makes reaction raw materials be heated to required temperature, and (2) additional heat is in order to avoid lower the temperature because of endothermic heat of reaction, and (3) reduce the dividing potential drop of ethylbenzene, increase equilibrium conversion, and the coke reaction that generates on (4) and the catalyzer is to keep the stability of catalyzer.But the utilization of a large amount of water vapors has occupied the bigger production cost of vinylbenzene.Vinylbenzene energy consumption about 6.3 * 10 per ton
9KJ (kilojoule) at least also needs 5.4 * 10 even consider the latent heat recovery
9KJ (kilojoule).
By the improvement of catalyzer, reduce the consumption of water vapor, 1997 southern chemical group (S ü d Chemie Group) developed Styromax-3 and 5 type catalyzer, have good low temperature properties.Its outstanding feature is to be suitable for low water than (S/O=1: 1) operation.Recently, U.S.'s Criterion catalyst Co. has been developed the C-055 catalyzer, it is said to make water drop to 1: 1 than (S/O) from 1.7: 1, and selectivity remains unchanged.But, the C-045 catalyzer of releasing from market, performance is not outstanding.In addition, U.S. DOW company has developed heat insulation-type D-0239E catalyzer.Water, when operation water ratio is 1: 1, can reduces energy consumption 40%, and not shorten life of catalyst between 1.1～1.7 than subject range.When the water ratio was 1.7, it was nearly 10% to improve cinnamic yield, external in a word, dropped into great amount of manpower and material resources aspect Study of Catalyst and the exploitation, and the development technology height is maintained secrecy.At present, vinylbenzene dirt produces quite maturation of technology, the novel reactor that nearly all production of styrene device has all adopted low-resistance to fall, and measures such as negative dehydrogenation technology and total energy approach make the material consumption of production of styrene and energy consumption drop to Limiting Level.Therefore, press for the new styrene Production of exploitation.
On the other hand, another approach of production of styrene is an oxidative dehydrogenation process.Provide heat by reacting inner hydroxide reaction heat release, cut down the consumption of energy.But because side reactions such as deep oxidation and oxygen molecule insertion increase, selectivity of styrene is not high fails industrialization.In recent years, utilized CO
2The research of carrying out the oxidative dehydrogenation of ethylbenzene preparation of styrene as the mild oxidation agent has caused World Science man's concern.The paper report that Tower delivers on the Chem.Eng.Prog. magazine, at 600 ℃, CO
2With the ratio of ethylbenzene be 5: 1, the equilibrium conversion of ethylbenzene can reach 95%.Without CO
2Situation under, equilibrium conversion only is 67%, has industrially obtained similar transformation efficiency.CO
2As thinner, itself have high thermal capacity, be very favorable to reducing the catalyst surface focus with the stability and the life-span of keeping catalyzer.In addition, CO
2Replace steam oxidation dehydrogenation preparation of styrene technology and may be CO
2Utilization open up a new approach (methane steam reforming hydrogen manufacturing process particularly, a large amount of CO
2Fail effectively to utilize), significant to reducing greenhouse gas emission.But business-like Fe-K-Ce-Mo catalyzer is to CO
2Ethylbenzene dehydrogenation under existing is unconformable.Some new catalyzer are developed, with A1
2O
3, ZnO, SiO
2, ZrO
2, zeolite and gac make carrier, different transition metal Fe, V, Cr, Co oxide compound are active ingredient, basic metal Li, Na etc. are auxiliary agent., reported among the USP6034032 in 500～700 ℃ temperature range, at Japanese Patent JP11165069 A2 and U.S. Pat P6037511 as people such as the Park Sang Yon of Korea S chemical research institute at (Fe (II))
x(Fe (III))
yO
z/ S and 5%Fe
3O
4On/ZSM-5 the catalyzer, use CO
2Carry out ethylbenzene mild oxidation dehydrogenation preparation of styrene as thinner, can obtain 48% vinylbenzene.But the key that hinders this skilled industryization is activity of such catalysts and stability.Under the high conversion condition, catalyzer obvious inactivation in 10 hours scopes.
Summary of the invention
Technical problem to be solved by this invention is the big or employing CO of available technology adopting steam diluter energy consumption
2The problem of catalyzer poor performance at low temperatures when making thinner provides a kind of new method that is used for ethyl benzene dehydrogenation preparation of styrene.This method is used for ethylbenzene dehydrogenation reaction, adopts CO
2When making thinner, it is low to have an energy consumption of reaction, catalyzer low-temperature catalytic activity height, the advantage that the product selectivity of styrene is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that is used for ethyl benzene dehydrogenation preparation of styrene is a raw material with ethylbenzene, at CO
2Atmosphere, temperature of reaction are 450～550 ℃, and reaction pressure is a normal pressure, and air speed is 0.1～1.0 hour
-1, CO
2: the ethylbenzene mol ratio is that ethylbenzene generates vinylbenzene by beds under 10～30: 1 condition, and wherein used catalyzer comprises following component by weight percentage:
A) 10～30% Cr
2O
3
B) 60～75% Al
2O
3
C) 0.1～20% be selected from least a transition metal oxide among V, Ce, Mn, Mo, Zn or the Sb.
In the technique scheme, catalyzer is Cr by weight percentage
2O
3The consumption preferable range be 15～25%, the consumption preferable range of transition metal oxide is 5～15%.Used catalyzer preferred version is for also comprising 0.01～1.5% precious metal or its oxide compound by weight percentage, and the precious metal preferred version is to be selected from least a among Pd or the Pt, and the consumption preferable range of precious metal or its oxide compound is 0.2～0.8%.
The Preparation of catalysts method of using in the inventive method is as follows: at first with compound solution, the transition metal element compound solution of the precious metal element of aequum, the salts solution of chromium, impregnated on the aluminum oxide with equi-volume impregnating, kneaded and formed, drying is 1～10 hour under 80～150 ℃ of conditions, and roasting got required catalyzer in 0.5～12 hour under 450～650 ℃ of conditions then.
The raw material that uses in the catalyzer that uses in the inventive method is as follows: the raw material of Pd is selected from palladium acid or its salt; The raw material of Pt is selected from Platinic chloride or its salt; The raw material of Mo is selected from ammonium molybdate; The raw material of Ce is selected from cerous nitrate; The raw material of Cr is selected from chromium nitrate; The raw material of Al is selected from aluminum oxide, and the raw material of vanadium is selected from ammonium meta-vanadate, and remaining all selects its nitrate for use.
The catalyzer that uses in the inventive method is owing to adopt Cr
2O
3And Al
2O
3Form catalyst system, the carrying transition metal oxide compound is used for the ethylbenzene catalytic dehydrogenation reaction or/and precious metal or its oxide compound are formed catalyzer simultaneously, with CO
2Do under the condition of thinner, the inventor finds that unexpectedly this catalyzer is under 500 ℃ of temperature of reaction, condition of normal pressure, and conversion of ethylbenzene can reach 74.6%, and cinnamic selectivity can reach more than 98%, simultaneously owing to adopt CO
2Make thinner and under 500 ℃ of temperature, react, can save a large amount of energy consumptions, obtained better technical effect.
The appreciation condition of the inventive method gained catalyzer is that temperature is controlled at 450～550 ℃, and reaction pressure is a normal pressure, and the mol ratio of carbonic acid gas and ethylbenzene maintains 10～30: 1, and the air speed of ethylbenzene is 0.1～1.0 hour
-1Reaction product is directly by online gas chromatographic analysis.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
0.1 gram weight is formed 20%Cr
2O
3/ 80%Al
2O
3Catalyzer is packed in the stainless steel reactor of 5 millimeters of diameters, temperature programming to 500 ℃, and the pre-treatment 2 hours under N2 atmosphere of 20 ℃/minute of temperature rise rates, catalyzer, ethylbenzene is through the gasification of saturated vapo(u)r producer, then with CO
2Mix the formation unstripped gas and enter catalyst bed reaction.Be reflected at 500 ℃ and carry out, pressure is normal pressure, CO
2With the mol ratio of ethylbenzene be 20: 1, the ethylbenzene flow be 0.42 mmole/hour, its weight is formed and is investigated that performance sees Table 1, table 2.
[embodiment 2～4]
Press each Step By Condition preparation and the examination catalyzer of embodiment 1, just change Cr
2O
3And Al
2O
3Component content, the weight percent of catalyzer is formed, and the dehydrogenation under the carbon dioxide atmosphere and the stability of catalyzer see Table 1 respectively, table 2.
The weight percent of table 1 catalyzer is formed
The dehydrogenation of table 2 catalyzer under carbon dioxide atmosphere
| Embodiment | Transformation efficiency % | Selectivity % |
| Embodiment 1 | 57.5 | 99.0 |
| Embodiment 2 | 48.6 | 99.2 |
| Embodiment 3 | 59.3 | 98.9 |
| Embodiment 4 | 56.4 | 98.7 |
[embodiment 5]
0.1 gram weight percentage composition is consisted of 5%CeO
2/ 20%Cr
2O
3/ 75%Al
2O
3Catalyzer, in the stainless steel reactor of 5 millimeters of the diameters of packing into, temperature programming to 500 ℃, 20 ℃/minute of temperature rise rates, catalyzer is at N
2Pre-treatment is 2 hours under the atmosphere, and ethylbenzene is through the gasification of saturated vapo(u)r producer, then with CO
2Mix the formation unstripped gas and enter catalyst bed reaction.Be reflected at 500 ℃ and carry out, pressure is normal pressure, CO
2With the mol ratio of ethylbenzene be 20: 1, the ethylbenzene flow be 0.42 mmole/hour, its weight is formed, evaluation result and performance see Table 3, table 4 and table 5.
[embodiment 6～11]
Press each Step By Condition preparation and the examination catalyzer of embodiment 5, just change transition metal kind, each component concentration, the weight percent of catalyzer is formed, the stability of the dehydrogenation under the carbon dioxide atmosphere and catalyzer sees Table 3 respectively, table 4, table 5.
The weight percent of table 3 catalyzer is formed
The dehydrogenation of table 4 catalyzer under carbon dioxide atmosphere
| Transformation efficiency % | Selectivity % | |
| Embodiment 5 | 69.9 | 99.1 |
| Embodiment 6 | 65.8 | 98.7 |
| Embodiment 7 | 65.7 | 98.8 |
| Embodiment 8 | 55.5 | 99.3 |
| Embodiment 9 | 49.0 | 99.8 |
| Embodiment 10 | 41.1 | 98.9 |
| Embodiment 11 | 69.6 | 99.0 |
The stability of table 5 embodiment 5 catalyzer
| Reaction times, hour | Transformation efficiency | Selectivity |
| 50 | 69.9 | 99.1 |
| 100 | 69.6 | 99.3 |
| 150 | 69.0 | 99.3 |
| 200 | 68.8 | 99.5 |
[embodiment 12]
0.1 gram weight per-cent is consisted of 0.4%Pd/5%CeO
2/ 20%Cr
2O
3/ 74.6%Al
2O
3Catalyzer, in the stainless steel reactor of 5 millimeters of the diameters of packing into, temperature programming to 500 ℃, 20 ℃/minute of temperature rise rates, catalyzer is at N
2Pre-treatment is 2 hours under the atmosphere, and ethylbenzene is through the gasification of saturated vapo(u)r producer, then with CO
2Mix the formation unstripped gas and enter catalyst bed reaction.Be reflected at 500 ℃ and carry out, pressure is normal pressure, CO
2With the mol ratio of ethylbenzene be 20: 1, the ethylbenzene flow be 0.42 mmole/hour, its catalyzer is formed and dehydrogenation is listed in table 6, table 7 and table 8 respectively.
[embodiment 13～19]
Just change the kind and the weight percent content of precious metal in the catalyzer composition by each step of embodiment 12, the kind of transition metal oxide and weight content, the weight content of chromic oxide and the weight content of aluminum oxide, the weight percent of gained catalyzer is formed, the dehydrogenation under the carbon dioxide atmosphere and stability see Table 6 respectively, table 7, table 8.
The weight percent of table 6 catalyzer is formed
The dehydrogenation of table 7 catalyzer under carbon dioxide atmosphere
| Transformation efficiency % | Selectivity % | |
| Embodiment 12 | 74.6 | 98.6 |
| Embodiment 13 | 69.9 | 99.1 |
| Embodiment 14 | 70.4 | 98.8 |
| Embodiment 15 | 74.2 | 98.0 |
| Embodiment 16 | 73.1 | 98.8 |
| Embodiment 17 | 74.1 | 98.9 |
| Embodiment 18 | 74.4 | 98.6 |
| Embodiment 19 | 74.5 | 98.7 |
The stability of table 8 embodiment 12 catalyzer
| Reaction times, hour | Transformation efficiency | Selectivity |
| 50 | 74.6 | 98.6 |
| 100 | 74.4 | 98.6 |
| 200 | 74.3 | 98.7 |
| 300 | 74.2 | 98.8 |
| 400 | 74.0 | 98.0 |
[embodiment 20]
Press each Step By Condition preparation and evaluate catalysts of embodiment 12, just changing temperature of reaction is 450 ℃, and air speed is 0.1 hour
-1, CO
2: the ethylbenzene mol ratio is 28: 1, and its reaction result is: conversion of ethylbenzene is 71.8%, and selectivity of styrene is 99.4%.
[embodiment 21]
Press each Step By Condition preparation and evaluate catalysts of embodiment 12, just changing temperature of reaction is 550 ℃, and air speed is 1.0 hours
-1, CO
2: the ethylbenzene mol ratio is 12: 1, and its reaction result is: conversion of ethylbenzene is 76.1%, and selectivity of styrene is 97.3%.
Claims (6)
1. a method that is used for ethyl benzene dehydrogenation preparation of styrene is a raw material with ethylbenzene, at CO
2Atmosphere, temperature of reaction are 450～550 ℃, and reaction pressure is a normal pressure, and air speed is 0.1～1.0 hour
-1, CO
2: the ethylbenzene mol ratio is that ethylbenzene generates vinylbenzene by beds under 10～30: 1 condition, and wherein used catalyzer comprises following component by weight percentage:
A) 10～30% Cr
2O
3
B) 60～75% Al
2O
3
C) 0.1～20% be selected from least a transition metal oxide among V, Ce, Mn, Mo, Zn or the Sb.
2. according to the described method that is used for ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that used catalyzer Cr by weight percentage
2O
3Consumption be 15～25%.
3. according to the described method that is used for ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that the consumption of transition metal oxide is 5～15% by weight percentage.
4. according to the described method that is used for ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that used catalyzer also comprises 0.01～1.5% precious metal or its oxide compound by weight percentage.
5. according to the described method that is used for ethyl benzene dehydrogenation preparation of styrene of claim 4, it is characterized in that precious metal is selected from least a among Pd or the Pt.
6. according to the described method that is used for ethyl benzene dehydrogenation preparation of styrene of claim 4, it is characterized in that the consumption of precious metal by weight percentage or its oxide compound is 0.2～0.8%.
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|---|---|---|---|
| CNB200510028777XA CN100413830C (en) | 2005-08-15 | 2005-08-15 | Method for preparing phenethylene through dehydrogenation of ethyl benzene |
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|---|---|---|---|
| CNB200510028777XA CN100413830C (en) | 2005-08-15 | 2005-08-15 | Method for preparing phenethylene through dehydrogenation of ethyl benzene |
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| CN100413830C true CN100413830C (en) | 2008-08-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106423240A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Styrene catalyst and preparation method thereof |
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| CN102198396A (en) * | 2011-03-17 | 2011-09-28 | 大连理工大学 | Chromium-containing light hydrocarbon combustion catalyst and preparation method thereof |
| CN103055879A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Combined catalyst for preparing styrene by ethylbenzene dehydrogenation |
| CN103121921A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for ethylbenzene dehydrogenation in presence of CO2 mild oxidizer |
| CN106423187B (en) * | 2015-08-12 | 2019-02-19 | 中国石油化工股份有限公司 | Phenylethylene catalyst |
| CN106423239B (en) * | 2015-08-12 | 2019-01-25 | 中国石油化工股份有限公司 | High stable phenylethylene catalyst |
| CN106423238B (en) * | 2015-08-12 | 2019-01-25 | 中国石油化工股份有限公司 | Phenylethylene catalyst and preparation method thereof |
| CN113877596B (en) * | 2020-07-02 | 2023-09-29 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst and preparation method and application thereof |
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| 域技术人员而言是显而易见的。因此，该权利要求不具备突出的实质性特点和显著的进步，不符合专利法第二十二条第三款有关创造性的规定。2. 权利要求2对权利要求1所述方法中所用催化剂的Cr2O3含量限定为15～25%。对比文件1的摘要部分公开了："催化剂的催化活性与Cr2O3的负载量? 第一次审查意见通知书正文申请号：200510028777X1. 权利要求1要求保护一种用于乙苯脱氢制备苯乙烯的方法。对比文件1（催化学报第25卷第7期第581-585页，2004年7月）公开了CO2气氛下负载型Cr2O3催化剂上乙苯脱氢制苯乙烯的反应，并具体公开了20%Cr2O3/Al2O3催化剂在500℃下催?苏化工，第vol.32卷第no.6期. 2004 |
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| CN106423240B (en) * | 2015-08-12 | 2019-01-01 | 中国石油化工股份有限公司 | Phenylethylene catalyst and preparation method |
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| CN1915945A (en) | 2007-02-21 |
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