CN106582688B - It is used to prepare the dehydrogenation and preparation method thereof of styrene - Google Patents
It is used to prepare the dehydrogenation and preparation method thereof of styrene Download PDFInfo
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Abstract
The present invention relates to dehydrogenations for being used to prepare styrene and preparation method thereof, and mainly low potassium catalyst choice present in solution conventional art is low, the high problem of by-product toluene.The present invention includes following component: 65~80% Fe by using the dehydrogenation for being used to prepare styrene by weight percentage2O3；6~11% K2O；6~10% CeO2；0.5~5% WO3；0.5~5% MgO；0.5~5% Y2O3；Selected from ZrO2、HfO2Or Ta2O5At least one, content be 0.5~5% technical solution, preferably solve the problems, such as this, 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 dehydrogenations and preparation method thereof for being used to prepare styrene.
Background technique
Ethylbenzene catalytic dehydrogenation method is always the dominant technology route of production styrene both at home and abroad, and production capacity accounts for about benzene second
The 90% of alkene total productive capacity, the key of this method first is that catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene.Catalyst for phenylethylene dehydrogenation
It basic composition is major catalyst, co-catalyst and pore-foaming agent, reinforcing agent etc..The Fe-K-Ce- that early 1980s succeed in developing
Mo catalyst series substitute Cr with Ce, Mo, so that catalyst, on the basis of maintaining original stability, activity has by a relatively large margin
It improves, while avoiding the oxide contaminant environment of Cr, production of styrene producer uses by countries in the world, such as published beauty
State's patent 5190906,4804799, world patent 09839278A1, but that there is also selectivity of styrene is not high, waits breeding grounds dehydrogenation
Reaction selectivity of styrene is generally lower than 95.0%, and the lower toluene of added value is more in reaction product, and content is generally higher than
3.4%, material consumption is higher, brings difficulty to later separation step.Toluene level height is examination catalyst performance in final products
An important indicator, in other identical situations, styrene device preferentially selects that by-product toluene is few, the good catalysis of selectivity
Agent.The Iron oxide catalyst containing noble metal is reported such as published United States Patent (USP) 6177602, it can be with using the catalyst
It is less to obtain higher selectivity, by-product toluene, but the patent has used noble metal, catalyst higher cost, it is difficult to realize work
Industry application.
The commercial plant scale overwhelming majority that ethylbenzene dehydrogenation generates styrene in the world reacts temperature at 100,000 tons/year or more
Degree is high, and generally all at 620 DEG C or more, by-product is more, and material consumption, energy consumption are high, is always the problem for perplexing production of styrene producer.Cause
This, develops the dehydrogenation that a kind of selectivity is high, by-product toluene is few, material consumption is greatly lowered, and is always that researcher's sense is emerging
The project of interest.
Summary of the invention
The first technical problem to be solved by the present invention is that low potassium catalyst choice present in conventional art is low, by-product
The high problem of toluene provides a kind of new dehydrogenation for being used to prepare styrene.The catalyst is used for ethylbenzene dehydrogenation reaction
With very high selectivity of styrene, the production quantity of by-product toluene in production process can be effectively reduced, reduce material consumption.
The second technical problem to be solved by the present invention is to provide a kind of corresponding with one of solution technical problem be used for
Prepare the preparation method of the dehydrogenation of styrene.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: being used to prepare the dehydrogenation of styrene
Catalyst includes following component by weight percentage:
(a) 65~80% Fe2O3；
(b) 6~11% K2O；
(c) 6~10% CeO2；
(d) 0.5~5% WO3；
(e) 0.5~5% MgO；
(f) 0.5~5% Y2O3；
(g) it is selected from ZrO2、HfO2Or Ta2O5At least one, content be 0.5~5%.
In above-mentioned technical proposal, the Fe2O3It is preferred from iron oxide red and iron oxide yellow, more preferable iron oxide red and oxygen
The weight ratio for changing iron oxide yellow is 1.0~3.5:1.
In above-mentioned technical proposal, (g) component preferably includes ZrO simultaneously2And HfO2Or ZrO2And Ta2O5Or HfO2With
Ta2O5, described two oxides are in terms of low potassium catalyst choice raising with binary synergistic effect；(g) component is preferred
It simultaneously include ZrO2、HfO2And Ta2O5, three kinds of oxides have ternary in terms of low potassium catalyst choice raising at this time
Synergistic effect.
In above-mentioned technical proposal, Y2O3Content is preferably 1.5~4%.
In above-mentioned technical proposal, (g) component content is preferably 1.5~5%.
In above-mentioned technical proposal, Ce is added preferably in the form of cerium oxalate or cerous carbonate.
In above-mentioned technical proposal, binder is not added in catalyst preparation process.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: the skill of one of above-mentioned technical problem
The preparation method of catalyst described in art scheme, comprising the following steps: by the Fe, K weighed according to the ratio, Ce, W, Mg, Y, (g) group
Part oxide and perforating agent after mixing, add water to mediate, obtain the catalyst through extrusion, drying and roasting.
The additional amount of water is not particularly limited, and those skilled in the art can rationally grasp humidity to squeeze out needs,
The additional amount of such as, but not limited to water accounts for catalyst raw material gross weight 15~35%.
In above-mentioned technical proposal, drying temperature is not particularly limited, such as 40~150 DEG C, drying time optional 0.55~8
Hour.
In above-mentioned technical proposal, as preferably selecting, drying gradually heats up, such as, but not limited to 40~70 DEG C dryings 2
~4 hours, then 80~150 DEG C drying 0.5~4 hour.
In above-mentioned technical proposal, optional 400~1000 DEG C of maturing temperature, calcining time optional 2~8 hours.
In above-mentioned technical proposal, as preferably roasting condition, maturing temperature is stepped up, such as, but not limited to 400~
650 DEG C roast 2~4 hours, then roast 2~4 hours at 900~1000 DEG C.
Raw material used in catalyst component of the present invention is as follows:
Fe used2O3It is added by iron oxide red and iron oxide yellow form；K used is added with potassium as potassium carbonate；W used is with it
Salt or oxide form be added；Mg used is added with oxide or hydroxide form；Remaining element is with its salt or oxygen
Compound form is added；In preparation process of the invention, it should also be added perforating agent in addition to catalyst body ingredient, perforating agent can be from
Graphite, polystyrene microsphere select in sodium carboxymethylcellulose, and additional amount is the 2~6% of total catalyst weight.
Catalyst obtained carries out activity rating in isotherm formula fixed bed according to the above method, to ethyl benzene dehydrogenation preparation of styrene
For catalyst activity evaluation, process is summarized as follows:
It will be disengaged from sub- water and ethylbenzene and input preheating mixer through metering pump respectively, preheating enters reaction after being mixed into gaseous state
Device, reactor use electric-heating-wire-heating, make up to predetermined temperature.Reactor inside diameter be 1 " stainless steel tube, it is interior filling 100 milli
Liter, 3 millimeters of partial size of catalyst.With chromatographic, it is formed after being coagulated by the reactant of reactor outflow is water cooled.
Conversion of ethylbenzene, selectivity of styrene calculate as follows:
The present invention in iron-potassium-cerium-tungsten-magnesium catalyst system by adding the oxide of appropriate yttrium and selected from ZrO2、
HfO2Or Ta2O5At least one, be surprised to find that made catalyst has that by-product toluene is few, selectivity of styrene is high
Outstanding advantages.Activity rating is carried out in isotherm formula fixed bed using catalyst prepared by the present invention, in normal pressure, ethylbenzene air speed 1.0
Hour- 1, 620 DEG C of reaction temperature, under the conditions of water ratio (weight) 2.0, selectivity of styrene reaches 96.5%, toluene level as low as
2.38%, achieve preferable technical effect.
The present invention will be further described below by way of examples:
Specific embodiment
[embodiment 1]
It will be equivalent to 56.02 parts of Fe2O3Iron oxide red, be equivalent to 15.69 parts of Fe2O3Iron oxide yellow, be equivalent to 9.29
Part K2The potassium carbonate of O is equivalent to 8.76 parts of CeO2Cerium oxalate, be equivalent to 2.76 parts of WO3Ammonium tungstate, be equivalent to 3.3 parts of MgO
Magnesium hydroxide, 2.86 parts of Y2O3, 1.32 parts of HfO2It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalysagen
The deionized water for expecting gross weight 22.3%, is mixed and stirred 0.8 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into
Baking oven, 65 DEG C are dried 2.5 hours, and 130 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 940 DEG C of roastings
Finished catalyst is obtained within 3 hours, catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, ethylbenzene liquid volume air speed 1.0 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 2.0, evaluation result is listed in table 2 and table 3 respectively.
[comparative example 1]
In addition to Y is not added2O3And HfO2Outside, method for preparing catalyst and evaluating catalyst condition be with embodiment 1, specifically:
It will be equivalent to 58.47 parts of Fe2O3Iron oxide red, be equivalent to 16.37 parts of Fe2O3Iron oxide yellow, be equivalent to 9.7
Part K2The potassium carbonate of O is equivalent to 9.14 parts of CeO2Cerium oxalate, be equivalent to 2.88 parts of WO3Ammonium tungstate, be equivalent to 3.44 parts of MgO
Magnesium hydroxide and 5.2 parts of graphite stirred in kneader 2 hours, be added account for catalyst raw material gross weight 22.3% disengaging son
Water mixes and stirs 0.8 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into baking oven, and 65 DEG C are dried 2.5 hours,
130 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 940 DEG C of roastings obtain finished product catalysis for 3 hours
Agent, catalyst composition are listed in table 1.Evaluation result is listed in table 2 and table 3 respectively.
[comparative example 2]
In addition to Y is not added2O3Outside, method for preparing catalyst and evaluating catalyst condition be with embodiment 1, specifically:
It will be equivalent to 57.67 parts of Fe2O3Iron oxide red, be equivalent to 16.15 parts of Fe2O3Iron oxide yellow, be equivalent to 9.56
Part K2The potassium carbonate of O is equivalent to 9.02 parts of CeO2Cerium oxalate, be equivalent to 2.84 parts of WO3Ammonium tungstate, be equivalent to 3.4 parts of MgO
Magnesium hydroxide, 1.36 parts of HfO2It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalyst raw material gross weight
22.3% deionized water mixes and stirs 0.8 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into baking oven, and 65
DEG C dry 2.5 hours, 130 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, roast 3 hours in 550 DEG C, 940 DEG C roasting 3 hours
To finished catalyst, catalyst composition is listed in table 1.Evaluation result is listed in table 2 and table 3 respectively.
[embodiment 2]
In addition to ZrO2Replace HfO2Outside, method for preparing catalyst and evaluating catalyst condition be with embodiment 1, specifically:
It will be equivalent to 56.02 parts of Fe2O3Iron oxide red, be equivalent to 15.69 parts of Fe2O3Iron oxide yellow, be equivalent to 9.29
Part K2The potassium carbonate of O is equivalent to 8.76 parts of CeO2Cerium oxalate, be equivalent to 2.76 parts of WO3Ammonium tungstate, be equivalent to 3.3 parts of MgO
Magnesium hydroxide, 2.86 parts of Y2O3, 1.32 parts of ZrO2It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalysagen
The deionized water for expecting gross weight 22.3%, is mixed and stirred 0.8 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into
Baking oven, 65 DEG C are dried 2.5 hours, and 130 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 940 DEG C of roastings
Finished catalyst is obtained within 3 hours, catalyst composition is listed in table 1.Evaluation result is listed in table 2 and table 3 respectively.
[embodiment 3]
In addition to Ta2O5Replace HfO2Outside, method for preparing catalyst and evaluating catalyst condition be with embodiment 1, specifically:
It will be equivalent to 56.02 parts of Fe2O3Iron oxide red, be equivalent to 15.69 parts of Fe2O3Iron oxide yellow, be equivalent to 9.29
Part K2The potassium carbonate of O is equivalent to 8.76 parts of CeO2Cerium oxalate, be equivalent to 2.76 parts of WO3Ammonium tungstate, be equivalent to 3.3 parts of MgO
Magnesium hydroxide, 2.86 parts of Y2O3, 1.32 parts of Ta2O5It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalysagen
The deionized water for expecting gross weight 22.3%, is mixed and stirred 0.8 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into
Baking oven, 65 DEG C are dried 2.5 hours, and 130 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 940 DEG C of roastings
Finished catalyst is obtained within 3 hours, catalyst composition is listed in table 1.Evaluation result is listed in table 2 and table 3 respectively.
[embodiment 4]
Catalyst and evaluation catalyst are prepared as described in Example 1, except that with 0.66 part of HfO2With 0.66 part
ZrO2Replace 1.32 parts of HfO2。
Catalyst composition is listed in table 1.Evaluation result is listed in table 2 and table 3 respectively.
[embodiment 5]
Catalyst and evaluation catalyst are prepared as described in Example 1, except that with 0.66 part of HfO2With 0.66 part
Ta2O5Replace 1.32 parts of HfO2。
Catalyst composition is listed in table 1.Evaluation result is listed in table 2 and table 3 respectively.
[embodiment 6]
Catalyst and evaluation catalyst are prepared as described in Example 1, except that with 0.66 part of ZrO2With 0.66 part
Ta2O5Replace 1.32 parts of HfO2。
Catalyst composition is listed in table 1.Evaluation result is listed in table 2 and table 3 respectively.
[embodiment 7]
Catalyst and evaluation catalyst are prepared as described in Example 1, except that with 0.44 part of HfO2, 0.44 part
ZrO2With 0.44 part of Ta2O5Replace 1.32 parts of HfO2。
Catalyst composition is listed in table 1.Evaluation result is listed in table 2 and table 3 respectively.
[embodiment 8]
It will be equivalent to 45.21 parts of Fe2O3Iron oxide red, be equivalent to 20.73 parts of Fe2O3Iron oxide yellow, be equivalent to
10.53 part K2The potassium carbonate of O is equivalent to 9.86 parts of CeO2Cerium oxalate, be equivalent to 1.47 parts of WO3Ammonium tungstate, be equivalent to 2.59
Magnesium hydroxide, the 3.97 parts of Y of part MgO2O3, 4.86 parts of ZrO2, 0.78 part of ZnO and 5.2 part of graphite stirred in kneader 2 hours,
The deionized water for accounting for catalyst raw material gross weight 22.3% is added, mixes and stirs 0.8 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 milli
The particle of rice is put into baking oven, and 65 DEG C are dried 2.5 hours, and 130 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, roasts 3 in 550 DEG C
Hour, 940 DEG C of roastings obtain finished catalyst for 3 hours, and catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, ethylbenzene liquid volume air speed 1.0 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 2.0, evaluation result is listed in table 2 and table 3 respectively.
[embodiment 9]
It will be equivalent to 41.2 parts of Fe2O3Iron oxide red, be equivalent to 33.0 parts of Fe2O3Iron oxide yellow, be equivalent to 6.48 parts
K2The potassium carbonate of O is equivalent to 7.84 parts of CeO2Cerium oxalate, be equivalent to 0.83 part of WO3Ammonium tungstate, be equivalent to 3.32 parts of MgO's
Magnesium hydroxide, 4.38 parts of Y2O3, 2.95 parts of HfO2It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalyst raw material
The deionized water of gross weight 22.3% mixes and stirs 0.8 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into baking
Case, 65 DEG C are dried 2.5 hours, and 130 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 940 DEG C of roastings 3
Hour obtains finished catalyst, and catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, ethylbenzene liquid volume air speed 1.0 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 2.0, evaluation result is listed in table 2 and table 3 respectively.
[embodiment 10]
It will be equivalent to 63.44 parts of Fe2O3Iron oxide red, be equivalent to 15.69 parts of Fe2O3Iron oxide yellow, be equivalent to 7.17
Part K2The potassium carbonate of O is equivalent to 8.53 parts of CeO2Cerium oxalate, be equivalent to 1.26 parts of WO3Ammonium tungstate, be equivalent to 0.65 part of MgO
Magnesium hydroxide, 0.82 part of Y2O3, 1.45 parts of ZrO2It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalysagen
The deionized water for expecting gross weight 22.3%, is mixed and stirred 0.8 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into
Baking oven, 65 DEG C are dried 2.5 hours, and 130 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 940 DEG C of roastings
Finished catalyst is obtained within 3 hours, catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, ethylbenzene liquid volume air speed 1.0 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 2.0, evaluation result is listed in table 2 and table 3 respectively.
[embodiment 11]
It will be equivalent to 55.49 parts of Fe2O3Iron oxide red, be equivalent to 17.21 parts of Fe2O3Iron oxide yellow, be equivalent to 8.33
Part K2The potassium carbonate of O is equivalent to 8.64 parts of CeO2Cerium oxalate, be equivalent to 2.65 parts of WO3Ammonium tungstate, be equivalent to 3.52 parts of MgO
Magnesium hydroxide, 0.38 part of Y2O3, 3.78 parts of HfO2It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalysagen
The deionized water for expecting gross weight 22.3%, is mixed and stirred 0.8 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into
Baking oven, 65 DEG C are dried 2.5 hours, and 130 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 940 DEG C of roastings
Finished catalyst is obtained within 3 hours, catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, ethylbenzene liquid volume air speed 1.0 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 2.0, evaluation result is listed in table 2 and table 3 respectively.
[embodiment 12]
It will be equivalent to 51.36 parts of Fe2O3Iron oxide red, be equivalent to 19.69 parts of Fe2O3Iron oxide yellow, be equivalent to 7.55
Part K2The potassium carbonate of O is equivalent to 8.01 parts of CeO2Cerium oxalate, be equivalent to 2.02 parts of WO3Ammonium tungstate, be equivalent to 2.41 parts of MgO
Magnesium hydroxide, 7.21 parts of Y2O3, 1.75 parts of HfO2It is stirred in kneader 2 hours with 5.2 parts of graphite, addition accounts for catalysagen
The deionized water for expecting gross weight 22.3%, is mixed and stirred 0.8 hour, takes out extrusion, is extruded into 3 millimeters of diameter, long 6 millimeters of particle, is put into
Baking oven, 65 DEG C are dried 2.5 hours, and 130 DEG C are dried 3.0 hours, are subsequently placed in muffle furnace, are roasted in 550 DEG C 3 hours, 940 DEG C of roastings
Finished catalyst is obtained within 3 hours, catalyst composition is listed in table 1.
100 milliliters of catalyst are packed into reactor, at normal pressure, ethylbenzene liquid volume air speed 1.0 hours- 1, 620 DEG C, water ratio
Activity rating is carried out under the conditions of (weight) 2.0, evaluation result is listed in table 2 and table 3 respectively.
The weight percent of table 1 (continued) catalyst forms
The weight percent of 1 (Continued) catalyst of table forms
The comparison of 2 catalyst performance of table
The dehydrogenation product of each catalyst of table 3 is distributed
Above embodiments explanation, adds the oxide of appropriate yttrium in iron-potassium-cerium-tungsten-magnesium catalyst system and is selected from
ZrO2、HfO2Or Ta2O5At least one, made catalyst has the protrusion that selectivity of styrene is high, by-product toluene is few excellent
Point is conducive to factory and improves styrene yield, increase economic benefit, meets the developing direction of styrene industrial energy saving consumption reduction, be
A kind of dehydrogenation to meet the market requirement.
Claims (8)
- By weight percentage include following component 1. being used to prepare the dehydrogenation of styrene:(a) 65~80% Fe2O3；(b) 6~11% K2O；(c) 6~10% CeO2；(d) 0.5~5% WO3；(e) 0.5~5% MgO；(f) 1.5~5% Y2O3；(g)ZrO2、HfO2And Ta2O5, content is 0.5~5%.
- 2. being used to prepare the dehydrogenation of styrene according to claim 1, it is characterised in that Y2O3Content be 1.5~ 4%.
- 3. being used to prepare the dehydrogenation of styrene according to claim 1, it is characterised in that the content of component (g) is 1.5~5%.
- 4. the preparation method of catalyst described in claim 1, comprising the following steps: by the Fe, K weighed according to the ratio, Ce, W, Oxide, perforating agent described in Mg, Y, (g) component after mixing, add water to mediate, and obtain described urge through extrusion, drying and roasting Agent.
- 5. the preparation method according to claim 4, it is characterised in that Ce is added in the form of cerium oxalate or cerous carbonate.
- 6. the preparation method according to claim 4, it is characterised in that do not add binder in catalyst preparation process.
- 7. the preparation method according to claim 4, it is characterised in that drying temperature is 40~150 DEG C.
- 8. the preparation method according to claim 4, it is characterised in that maturing temperature is 400~1000 DEG C.
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| CN114425358B (en) * | 2020-10-14 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst for preparing styrene by ethylbenzene dehydrogenation with low toluene byproduct, preparation method and application thereof, and ethylbenzene dehydrogenation method |
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| CN1883796A (en) * | 2005-06-22 | 2006-12-27 | 中国石油化工股份有限公司 | Catalysts for ethyl benzene dehydrogenation preparation of styrene |
| CN103537292A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Dehydrogenation catalyst used for preparing styrene |
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| CN1883796A (en) * | 2005-06-22 | 2006-12-27 | 中国石油化工股份有限公司 | Catalysts for ethyl benzene dehydrogenation preparation of styrene |
| CN103537292A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Dehydrogenation catalyst used for preparing styrene |
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