CN103769141A - Ethylbenzene dehydrogenation catalyst, and preparation method and application thereof - Google Patents
Ethylbenzene dehydrogenation catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an ethylbenzene dehydrogenation catalyst, and a preparation method and application thereof and mainly solves the technical problem that the catalyst is reduced in stability when a low potassium catalyst is not enough in mechanical strength without common calcium silicate cement. According to the invention, in an iron-potassium-cerium-molybdenum-calcium catalyst system, the selected cerium source is uniformly mixed with the iron source, potassium source, molybdenum source, alkaline-earth metal oxide and a pore-foaming agent, and processes of forming, drying and roasting are adopted to prepare the catalyst. With the cerium source, that takes the cerium nitrate and cerous carbonate as raw materials, being added into the catalyst according to a certain proportion, the problem is well solved. Therefore, the method can be applied to the industrial production for phenethylene through ethylbenzene dehydrogenation.
Description
Technical field
The present invention relates to a kind of catalyst for phenylethylene dehydrogenation, preparation method and its usage.
Background technology
The basic composition of current industrial ethyl benzene dehydrogenation preparation of styrene catalyst comprises major catalyst, co-catalyst, perforating agent and binding agent etc.Early stage catalyst is Fe-K-Cr system, as published United States Patent (USP) 4467046 and European patent 0296285A1.Although activity and the stability of such catalyst are better, because catalyst is containing the oxide of Cr, environment is caused to certain pollution, eliminated gradually.Develop into afterwards Fe-K-Ce-Mo series, substituted Cr with Ce, can improve preferably activity and the stability of catalyst, overcome again Cr toxicity large, the drawback of contaminated environment simultaneously.Then develop into the catalyst into Fe-K-Ce-Mo-Mg series, as published EP502510, WO9710898, CN1233604 and CN1470325.Ce adds the activity that can significantly improve catalyst, especially remarkable to the catalysts influence of high potassium content.When but the catalyst of high potassium content is placed in air, the easy adsorption moisture of catalyst, makes the anti-crushing power of catalyst low, is easy to efflorescence.And, in dehydrogenation reaction process, potassium can be little by little to granule interior migration, or be easily washed, thereby cause catalyst stability to decline, affect catalyst service life, therefore, current research concentrates on low potassium catalyst mostly.In research, find that in catalyst preparation process, the source of Ce is very big to the performance impact of catalyst in low potassium catalyst, according to related documents report up to now, scientific research personnel had done a lot of trial.As published United States Patent (USP) 5376613 and 5171914 adopts the cerium source that cerous carbonate is catalyst, it is cerium source that Chinese patent 1298856A adopts cerous nitrate and cerium oxalate, it is cerium source that Chinese patent 1233604 and 1470325 adopts cerous nitrate, and its feature relatively pays close attention to the impact of Ce source on catalyst activity, and in catalyst, all add common calcium silicate cement to guarantee the mechanical strength of catalyst.These documents all do not relate in the situation that does not add cement, change the impact of cerium source on catalyst mechanical strength and catalyst life.For this reason, find that high mechanical properties is prepared in suitable Ce source and long-life low potassium catalyst is the target that researcher makes great efforts.
Summary of the invention
One of technical problem to be solved by this invention is in the situation that does not add common calcium silicate cement of conventional art existence, low potassium catalyst (K
2o weight percentage is less than 14%) mechanical strength is not high enough, thus cause the problem of stability decreases, a kind of new catalyst for phenylethylene dehydrogenation is provided.It is low that this catalyst has potassium content, keeping greater activity and optionally also having advantages of higher mechanical strength and stability simultaneously.Two of technical problem to be solved by this invention is to provide the preparation method of the catalyst-compatible of one of a kind of and technical solution problem.Three of technical problem to be solved by this invention is to provide a kind of purposes of described catalyst.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst for phenylethylene dehydrogenation, comprises following composition by weight percentage: (a) 65～81% Fe
2o
3; (b) 5～13% K
2o; (c) 8～14% CeO
2; (d) 0.5～5% Mo
2o
3; (e) 0.5～5% CaO; Wherein the raw material sources of cerium oxide are in cerous nitrate and cerous carbonate, and in cerium oxide, the weight ratio of cerous nitrate and cerous carbonate is 0.5～30.
In technique scheme, in cerium oxide, the weight ratio preferable range of cerous nitrate and cerous carbonate is 2～18, and more preferably scope is 4～12.By weight percentage, Fe
2o
3consumption preferable range be 70～78%, K
2the consumption preferable range of O is 7～10%, CeO
2consumption preferable range be 9～12%, Mo
2o
3consumption preferable range be 1～3.5%, CaO consumption preferable range is 1.5～4.5%.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of catalyst for phenylethylene dehydrogenation, comprise the following steps: by weight percentage, by the source of iron of aequum cerium source and aequum, potassium source, molybdenum source, alkaline earth oxide and perforating agent mix, add water, make toughness, be applicable to the face dough of extrusion, through extrusion, moulding, after dry, roasting 0.5～24 hour at 500～1000 ℃, make catalyst, wherein the raw material sources of cerium oxide are in cerous nitrate and cerous carbonate, and in cerium oxide, cerous nitrate: the weight ratio of cerous carbonate is 0.5～30: 1.
In technique scheme, catalyst all components comprises following composition by weight percentage: 65～81% Fe
2o
3, 5～13% K
2o, 8～14% CeO
2, 0.5～5% Mo
2o
3, 0.5～5% CaO; Fe
2o
3by iron oxide red and iron oxide yellow form, K used with sylvite or hydroxide form add, Mo used with molybdenum salt or oxide form add, alkaline-earth metal adds with its salt or oxide form; Perforating agent is one or more in graphite, polystyrene microsphere, methylcellulose, hydroxyethylcellulose, carboxymethyl cellulose, and its addition is total catalyst weight 2～7%; Baking temperature is 50～120 ℃, and be 2～24 hours drying time; Sintering temperature preferable range is 600～870 ℃, and roasting time preferable range is 4～15 hours.
The catalyst granules that the present invention makes can be the various shapes such as solid cylindrical, hollow cylinder, trilobal, rhombus, quincunx, honeycombed, the also unfixing restriction of its diameter and particle length, recommending catalyst to adopt diameter is the solid cylindrical particle of 3 millimeters, long 5～10 millimeters.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: described catalyst for phenylethylene dehydrogenation is for the reaction of ethyl benzene dehydrogenation preparation of styrene, reaction condition is: reaction pressure is normal pressure, and reaction temperature is 580～640 ℃, and liquid air speed is 0.5～2.0 hour
-1, steam/ethylbenzene weight ratio is 1.0～3.0.
The catalyst making carries out activity rating in isotherm formula fixed bed, and for catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene activity rating, process is summarized as follows:
By reaction raw materials, respectively through measuring pump input preheating mixer, preheating enters reactor after being mixed into gaseous state, and reactor adopts electric-heating-wire-heating, makes it to reach predetermined temperature.Reactor inside diameter is 1 " stainless steel tube, interiorly load 100 milliliters of catalyst.The reactant being flowed out by reactor is analyzed it with gas chromatograph and is formed after water condensation.
Conversion of ethylbenzene, selectivity of styrene calculate as follows:
Conversion of ethylbenzene %=
Selectivity of styrene %=
In the present invention, the mechanical strength of catalyst is measured by the technical requirement of standard HG/T2782-1996 regulation, uses DL-II type intelligence granule strength instrument.5 millimeters of specimen lengths, test take 40 as one group, and the arithmetic mean of instantaneous value of getting its measurement result is final mechanical strength value, the unit take newton (N) as mechanical strength.
The present invention is by iron-potassium-cerium-molybdenum-calcium system, it is raw material that cerium source adopts the mixture of cerous nitrate and cerous carbonate, and join in catalytic component with suitable mixed proportion, because cerous nitrate is water-soluble, be easy to cerium oxide to be dispersed in the surface of catalyst, thereby improve the activity and selectivity of catalyst, and cerous carbonate belongs to alkaline matter, in catalyst, do not add Portland cement simultaneously, improve the alkalescence of system, stablize the active phase of catalyst, thereby make low potassium catalyst keep greater activity and optionally also there is higher mechanical strength and good stability simultaneously, use catalyst of the present invention, at normal pressure, liquid air speed 1.0 hours
-1, under 620 ℃, steam/ethylbenzene (weight ratio) 2.0 conditions, for the reaction of ethyl benzene dehydrogenation preparation of styrene, its conversion ratio can reach 77.5%, selectively can reach 95.2%, the intensity of catalyst reaches 135N, and stability is greater than 500 hours, obtained good technique effect.
Below by embodiment, the invention will be further elaborated.
The specific embodiment
[embodiment 1]
212.0 grams of iron oxide reds, 80.0 grams of iron oxide yellows, 58.0 grams of potash, 100.0 grams of cerous nitrates, 2.8 grams of cerous carbonates, 10.0 grams of ammonium molybdates, 6.1 grams of calcium hydroxides and 5.0 grams of magnesia and 20.5 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 5～10 millimeters of length, put into baking oven, 80 ℃ are dried 2 hours, 120 ℃ are dried 2 hours, then be placed in muffle furnace, within 4 hours, obtain finished catalyst in 850 ℃ of roastings.
Catalyst is carried out to mechanical strength mensuration, and test result is listed in table 1.
Pack 100 milliliters of catalyst into reactor, normal pressure, liquid air speed 1.0 hours
-1, carry out activity rating under 620 ℃, steam/ethylbenzene (weight ratio) 2.0 conditions, test result is listed in table 1.
[embodiment 2]
210.0 grams of iron oxide reds, 183.0 grams of iron oxide yellows, 52.0 grams of potash, 102.0 grams of cerous nitrates, 9.5 grams of cerous carbonates, 5.1 grams of ammonium molybdates, 8.0 grams of calcium carbonate and 2.0 grams of polystyrene microspheres, 16.5 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 5～10 millimeters of length, put into baking oven, 120 ℃ are dried 2 hours, then be placed in muffle furnace, within 14 hours, obtain finished catalyst in 650 ℃ of roastings.
Carry out activity rating and mechanical strength mensuration by the appreciation condition of [embodiment 1], test result is listed in table 1.
[embodiment 3]
283.0 grams of iron oxide reds, 103.6 grams of iron oxide yellows, 75.1 grams of potash, 89.5 grams of cerous nitrates, 15.2 grams of cerous carbonates, 10.5 grams of ammonium molybdates, 6.0 grams of calcium oxide, 7.0 grams of hydroxyethylcelluloses, 20.3 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 5～10 millimeters of length, put into baking oven, 50 ℃ are dried 12 hours, then be placed in muffle furnace, within 0.5 hour, obtain finished catalyst in 1000 ℃ of roastings.
Carry out activity rating and mechanical strength mensuration by the appreciation condition of [embodiment 1], test result is listed in table 1.
[embodiment 4]
130.8 grams of iron oxide reds, 145.0 grams of iron oxide yellows, 60.0 grams of potash, 50.0 grams of cerous nitrates, 58.0 grams of cerous carbonates, 15.0 grams of ammonium molybdates, 10.8 grams of calcium carbonate, 5.0 grams of magnesia and 3.5 grams of methylcellulose, 16.2 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 5～10 millimeters of length, put into baking oven, 100 ℃ are dried 6 hours, then be placed in muffle furnace, within 24 hours, obtain finished catalyst in 500 ℃ of roastings.
Carry out activity rating and mechanical strength mensuration by the appreciation condition of [embodiment 1], test result is listed in table 1.
[embodiment 5]
241.0 grams of iron oxide reds, 98.0 grams of iron oxide yellows, 60.0 grams of potash, 123.0 grams of cerous nitrates, 5.5 grams of cerous carbonates, 16.8 grams of ammonium molybdates, 18.6 grams of calcium oxide and 4.0 grams of graphite, 15.3 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 5～10 millimeters of length, put into baking oven, 110 ℃ are dried 4 hours, then be placed in muffle furnace, within 12 hours, obtain finished catalyst in 780 ℃ of roastings.
Carry out activity rating and mechanical strength mensuration by the appreciation condition of [embodiment 1], test result is listed in table 1.
[embodiment 6]
190.0 grams of iron oxide reds, 135.0 grams of iron oxide yellows, 78.0 grams of potash, 100.0 grams of cerous nitrates, 8.0 grams of cerous carbonates, 6.3 grams of ammonium molybdates, 11.6 grams of calcium hydroxides, 5.0 grams of magnesia and 3.5 grams of methylcellulose, 16.2 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 5～10 millimeters of length, put into baking oven, 90 ℃ are dried 8 hours, then be placed in muffle furnace, within 4 hours, obtain finished catalyst in 800 ℃ of roastings.
Carry out activity rating and mechanical strength mensuration by the appreciation condition of [embodiment 1], test result is listed in table 1.
[embodiment 7]
165.0 grams of iron oxide reds, 100.8 grams of iron oxide yellows, 70.0 grams of potash, 92.0 grams of cerous nitrates, 8.5 grams of cerous carbonates, 21.6 grams of ammonium molybdates, 6.8 grams of calcium carbonate, 13.2 grams of magnesia and 16.2 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 5～10 millimeters of length, put into baking oven, 90 ℃ are dried 8 hours, then be placed in muffle furnace, within 4 hours, obtain finished catalyst in 810 ℃ of roastings.
Carry out activity rating and mechanical strength mensuration by the appreciation condition of [embodiment 1], test result is listed in table 1.
[embodiment 8]
210.0 grams of iron oxide reds, 103.5 grams of iron oxide yellows, 65.0 grams of potash, 120.0 grams of cerous nitrates, 4.8 grams of cerous carbonates, 15.9 grams of ammonium molybdates, 5.6 grams of calcium carbonate and 4.0 grams of hydroxyethylcelluloses, 22.8 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 5～10 millimeters of length, put into baking oven, 90 ℃ are dried 8 hours, then be placed in muffle furnace, within 4 hours, obtain finished catalyst in 810 ℃ of roastings.
Carry out activity rating and mechanical strength mensuration by the appreciation condition of [embodiment 1], test result is listed in table 1.
[embodiment 9]
214.0 grams of iron oxide reds, 112.8 grams of iron oxide yellows, 68.0 grams of potash, 119.5 grams of cerous nitrates, 8.6 grams of cerous carbonates, 14.5 grams of ammonium molybdates, 5.2 grams of calcium hydroxides, 9.8 grams of magnesia and 18.5 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 5～10 millimeters of length, put into baking oven, 80 ℃ are dried 8 hours, then be placed in muffle furnace, within 4 hours, obtain finished catalyst in 820 ℃ of roastings.
Carry out activity rating and mechanical strength mensuration by the appreciation condition of [embodiment 1], test result is listed in table 1.
[embodiment 10]
198.0 grams of iron oxide reds, 143.2 grams of iron oxide yellows, 70.0 grams of potash, 94.0 grams of cerous nitrates, 7.8 grams of cerous carbonates, 10.2 grams of ammonium molybdates, 5.2 grams of calcium carbonate, 8.6 grams of magnesia and 14.0 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 5～10 millimeters of length, put into baking oven, 90 ℃ are dried 8 hours, then be placed in muffle furnace, within 6 hours, obtain finished catalyst in 810 ℃ of roastings.
Carry out activity rating and mechanical strength mensuration by the appreciation condition of [embodiment 1], test result is listed in table 1.
[embodiment 11]
225.0 grams of iron oxide reds, 80.0 grams of iron oxide yellows, 68.0 grams of potash, 92.0 grams of cerous nitrates, 10.0 grams of cerous carbonates, 10.2 grams of ammonium molybdates, 6.0 grams of calcium hydroxides, 5.0 grams of magnesia and 16.0 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 5～10 millimeters of length, put into baking oven, 90 ℃ are dried 8 hours, then be placed in muffle furnace, within 6 hours, obtain finished catalyst in 810 ℃ of roastings.
Carry out activity rating and mechanical strength mensuration by the appreciation condition of [embodiment 1], test result is listed in table 1.
The percentage by weight of gained catalyst is composed as follows:
| Composition (%) | Fe 2O 3 | K 2O | CeO 2(deriving from cerous nitrate) | CeO 2(deriving from cerous carbonate) | Mo 2O 3 | CaO | MgO | Cerous nitrate/cerous carbonate |
| Embodiment 1 | 73.46 | 10.74 | 10.60 | 0.37 | 2.22 | 1.26 | 1.36 | 28.65 |
| Embodiment 2 | 80.14 | 7.95 | 8.93 | 1.04 | 0.93 | 1.01 | - | 8.59 |
| Embodiment 3 | 77.82 | 11.12 | 7.59 | 1.61 | 1.86 | 1.29 | - | 4.71 |
| Embodiment 4 | 68.99 | 11.32 | 5.40 | 7.84 | 3.39 | 1.68 | 1.39 | 0.69 |
| Embodiment 5 | 72.42 | 9.45 | 11.09 | 0.62 | 3.17 | 3.26 | - | 17.89 |
| Embodiment 6 | 72.07 | 12.91 | 9.48 | 0.95 | 1.25 | 2.13 | 1.21 | 10.00 |
| Embodiment 7 | 65.65 | 12.86 | 11.04 | 1.12 | 4.75 | 1.03 | 3.56 | 9.88 |
| Embodiment 8 | 72.49 | 11.12 | 11.76 | 0.59 | 3.26 | 0.79 | - | 20.00 |
| Embodiment 9 | 71.00 | 10.95 | 11.02 | 0.99 | 2.79 | 0.93 | 2.32 | 11.11 |
| Embodiment 10 | 74.07 | 11.34 | 8.72 | 0.90 | 1.98 | 0.94 | 2.05 | 9.64 |
| Embodiment 11 | 72.92 | 11.95 | 9.26 | 1.26 | 2.15 | 1.17 | 1.29 | 7.36 |
[comparative example 1]
By the method Kaolinite Preparation of Catalyst of [embodiment 1], difference is that all to adopt cerous nitrate be 103.5 grams in cerium source.
Carry out activity rating and mechanical strength mensuration by the appreciation condition of [embodiment 1], test result is listed in table 1.
[comparative example 2]
By the method Kaolinite Preparation of Catalyst of [embodiment 1], difference is that all to adopt cerous carbonate be 82.8 grams in cerium source.
Carry out activity rating and mechanical strength mensuration by the appreciation condition of [embodiment 1], test result is listed in table 1.
The contrast of table 1 catalyst performance
Above embodiment explanation, in the present invention, it is raw material that cerium source adopts the mixture of cerous nitrate and cerous carbonate, and join in catalytic component with suitable proportioning, when the catalyst obtaining reacts for ethyl benzene dehydrogenation preparation of styrene, under low potassium situation, catalyst is keeping greater activity and is optionally also having higher mechanical strength simultaneously, and has good stability.
Claims (10)
1. a catalyst for phenylethylene dehydrogenation, comprises following composition by weight percentage:
(a) 65～81% Fe
2o
3;
(b) 5～13% K
2o;
(c) 8～14% CeO
2;
(d) 0.5～5% Mo
2o
3;
(e) 0.5～5% CaO;
Wherein the raw material sources of cerium oxide are in cerous nitrate and cerous carbonate, and in cerium oxide, the weight ratio of cerous nitrate and cerous carbonate is 0.5～30.
2. catalyst for phenylethylene dehydrogenation according to claim 1, is characterized in that in cerium oxide, and the weight ratio of cerous nitrate and cerous carbonate is 2～18.
3. catalyst for phenylethylene dehydrogenation according to claim 2, is characterized in that in cerium oxide, and the weight ratio of cerous nitrate and cerous carbonate is 4～12.
4. catalyst for phenylethylene dehydrogenation according to claim 1, is characterized in that by weight percentage Fe
2o
3consumption be 70～78%, K
2the consumption of O is 7～10%, CeO
2consumption be 9～12%, Mo
2o
3consumption be 1～3.5%, CaO consumption is 1.5～4.5%.
5. the preparation method of catalyst for phenylethylene dehydrogenation described in claim 1, comprise the following steps: by weight percentage, the source of iron of aequum cerium source and aequum, potassium source, molybdenum source, alkaline earth oxide and perforating agent are mixed, add water, make the face dough of toughness, applicable extrusion, after extrusion, moulding, being dried, roasting 0.5～24 hour at 500～1000 ℃, make catalyst, wherein the raw material sources of cerium oxide are in cerous nitrate and cerous carbonate, and in cerium oxide, cerous nitrate: the weight ratio of cerous carbonate is 0.5～30: 1.
6. the preparation method of catalyst for phenylethylene dehydrogenation according to claim 5, is characterized in that the Fe in catalyst
2o
3formed by iron oxide red and iron oxide yellow, K used with its salt or hydroxide form add, Mo used with its salt or oxide form add, alkaline-earth metal adds with its salt or oxide form.
7. the preparation method of catalyst for phenylethylene dehydrogenation according to claim 5, it is characterized in that in catalyst, perforating agent is selected from least one in graphite, polystyrene microsphere, methylcellulose, hydroxyethylcellulose or carboxymethyl cellulose, its addition is total catalyst weight 2～7%.
8. the preparation method of catalyst for phenylethylene dehydrogenation according to claim 5, the baking temperature that it is characterized in that catalyst is 50～120 ℃, be 2～24 hours drying time.
9. the preparation method of catalyst for phenylethylene dehydrogenation according to claim 4, the sintering temperature that it is characterized in that catalyst is 600～870 ℃, roasting time is 4～15 hours.
10. catalyst for phenylethylene dehydrogenation claimed in claim 1 is for the reaction of ethyl benzene dehydrogenation preparation of styrene, and reaction condition is: reaction pressure is normal pressure, and reaction temperature is 580～640 ℃, and liquid air speed is 0.5～2.0 hour
-1, steam/ethylbenzene weight ratio is 1.0～3.0.
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| CN105478132A (en) * | 2014-10-13 | 2016-04-13 | 中国石油化工股份有限公司 | Low-carbon ethylbenzene dehydrogenation catalyst, and preparation method and application thereof |
| CN105478132B (en) * | 2014-10-13 | 2018-07-17 | 中国石油化工股份有限公司 | Catalyst for phenylethylene dehydrogenation of low-carbon type and its preparation method and application |
| CN108722430A (en) * | 2018-04-19 | 2018-11-02 | 天津理工大学 | Using nano-sized iron oxide as catalyst for phenylethylene dehydrogenation of source of iron and preparation method thereof |
| CN111054369A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of alkyl aromatic hydrocarbon |
| CN111054369B (en) * | 2018-10-16 | 2021-05-11 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of alkyl aromatic hydrocarbon |
| CN113877595A (en) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | Dehydrogenation catalyst, preparation method and application thereof, and mixed diethylbenzene dehydrogenation method |
| CN113877595B (en) * | 2020-07-01 | 2024-02-02 | 中国石油化工股份有限公司 | Dehydrogenation catalyst, preparation method and application thereof and method for dehydrogenating mixed diethylbenzene |
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| CN103769141B (en) | 2016-08-24 |
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