CN107537463B - Propane dehydrogenation catalyst and its method in the presence of carbon dioxide mild oxidizing agent - Google Patents
Propane dehydrogenation catalyst and its method in the presence of carbon dioxide mild oxidizing agent Download PDFInfo
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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
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- 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
Abstract
The present invention relates to a kind of methods of dehydrogenating propane in the presence of carbon dioxide mild oxidizing agent, mainly solve prior art reaction temperature height, the lower problem of catalyst activity.The present invention is used for propane dehydrogenation catalyst by using one kind, based on parts by weight, including following components: a) active constituent is with Cr2O3It is calculated as 0.1-30.0 parts；B) rare-earth oxide modified agent dosage is 0.1-10.0 parts；C) catalyst carrier ZrO2For 60.0-99.5 parts of technical solution, above-mentioned problem is preferably solved, can be used in the industrial production of dehydrogenating propane.
Description
Technical field
The present invention relates to a kind of carbon dioxide mild oxidizing agent, there are propane dehydrogenation catalyst and its methods.
Background technique
Low-carbon alkene is often referred to the alkene that carbon atom number is less than or equal to 4, is very important Organic Chemicals, especially
It is ethylene, propylene, butylene etc., it is considered to be the basic material of modern petrochemical, to produce polyethylene, polypropylene, propylene
Nitrile, ethylene oxide, propylene oxide, butanol, isopropylbenzene etc..Wherein propylene dosage is only second to ethylene etc., in recent years global propylene
Consumption figure is increased with average annual 4.8% rate, more than the amplification of same period propylene yield.China's propylene demand is quite big, and long
Phase relies on import, it is predicted that China needs 5,000,000 tons of propylene of import every year during 12.The production of low-carbon alkene mainly uses
Ethylene coproduction and catalytic pyrolysis (cracking such as naphtha, light diesel fuel) by-product, due to the growing lack and routine of Global Oil resource
The limitation of propylene means is obtained, exploitation new technology substitution conventional olefin production method seems particularly significant.Utilize abundance, valence
It is one of most promising method that the cheap dehydrogenating low-carbon alkane of lattice, which prepares low-carbon alkene,.Dehydrogenating low-carbon alkane is one highly endothermic
Reaction, only can just obtain comparatively ideal olefin yields under low pressure, hot conditions, and reacts under hot conditions and easily occur to gather
The side reactions such as conjunction, cyclisation, charing, make the quick carbon distribution of catalyst surface, inactivation, catalyst performance are caused to be deteriorated, and selectivity is lower
The problems such as, therefore, it is necessary to the excellent dehydrogenations of processability, improve alkane conversion and olefine selective.
The current research in relation to individual Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane is more, and it is de- to have more than 10 set propane in the world
Hydrogen production device is being run, and main De-hydrogen Technology has the Oleflex technique of UOP, the Catofin technique of Lummus, the STAR work of Uhde
Skill, the PDH technique of Linde, FBD technique etc. of Snamprogetti-Yarsintez cooperative development, wherein industrialized unit is most
More is Oleflex technology and Catofin technology, and the catalyst of the two application is Pt system and Cr series catalysts, dehydrogenation work respectively
Skill is substantially the same, and different only dehydrogenation and catalyst regeneration part, Oleflex technique use moving-burden bed reactor, in vitro again
It is raw；Catofin uses fixed bed reactors, carries out hot-air and burns carbon cycle regeneration.In recent years, related dehydrating alkanes Cr system is catalyzed
There are more document report and patent application in terms of agent, for CN 101940922 using chromium as active component, alkali metal is co-catalyst
Component, aluminium oxide containing Cr are that carrier is prepared for alkane dehydrogenating catalyst, and propane maximum conversion is 57.8% when reacting 10 minutes,
Propylene Selectivity 91.5%.Takahara etc. is published in catalysis Today, 1998,45 (1-4): 55 research paper, will
SiO2Load 5wt%tCr2O3Catalyst be used for CO2Dehydrogenating propane under atmosphere achieves 9.1% propylene production at 550 DEG C
Rate.
Dehydrogenating low-carbon alkane catalysis reaction carries out under high temperature, lower pressure, and catalyst carbon deposit inactivation is serious, develops high living
Property, highly selective and high stability catalyst become the technology key.Chinese patent (CN200710025372.X) is open
Catalyst, alumina modified mesoporous molecular sieve be carrier on platinum-impregnated tin component preparation method, conversion of propane is only
It is 17%, Propylene Selectivity 93%；Chinese patent (CN200710023431.X) is drawn tin using using the method for hydrothermal synthesis
Enter ZSM-5 molecular sieve carrier, and with infusion process Supported Pt Nanoparticles component, after which runs 100 hours, conversion of propane is higher than
30%, Propylene Selectivity 99%, but the patent does not provide the stability data of coke-burning regeneration process.Chinese patent
(CN200710020064.8) and (CN200710133324.2) discloses a kind of platinum-tin catalyst and reacts for dehydrogenating propane, adopts
With the preparation method of tin component and platinum component co-impregnation, carrier is the molecular sieves containing Na such as Y type, ZSM-5, catalyst continuous operation
After 720 hours, conversion of propane 30.5%, Propylene Selectivity 96.4%, but active drop by half after coke-burning regeneration twice.The U.S.
Patent discloses the aluminium for using zinc aluminate spinel to promote for auxiliary agents such as the Pt catalyst (US5430220) of carrier and Au, Ag
Hydrochlorate carrier Pt catalyst (US3957688；US4041099；US5073662), it is low all to there is conversion ratio in catalyst, was using
The problem of selectively declining in journey.
Catalyst with noble metal platinum element for main active component, which is that one kind of dehydrogenating low-carbon alkane catalysis reaction is important, urges
Agent.Dehydrogenating low-carbon alkane catalysis reaction carries out under high temperature, lower pressure, and catalyst carbon deposit inactivation is serious, exploitation high activity,
Highly selective and high stability catalyst becomes the key of the technology.Chinese patent (CN200710025372.X) is disclosed to urge
Agent, in the preparation method that alumina modified mesoporous molecular sieve is platinum-impregnated tin component on carrier, conversion of propane is only
17%, Propylene Selectivity 93%；Catalyst use disclosed in United States Patent (USP) (US4438288) is carried on γ-Al2O3、SiO2、
The shortcomings that platinum tin metal on MgO, and alkali or alkaline earth metal is added into carrier, the catalyst, is activity and selectivity
Low, iso-butane conversion ratio is 39%~44%.
Above-mentioned catalyst, which has been all made of, loads to PtSn on carrier using infusion process, is catalyzed during applied at elevated temperature
Agent is easy coking deactivation, and the stability of catalyst is poor, service life is not grown.The present invention is used and is activated to catalyst,
The redisperse that the water in chlorine process/chlorine balance effectively improves active component Pt is mended in control, to improve catalytic activity.Another party
Face, research is it has also been found that mix hydrogen with trace hydrogen sulfide during catalyst reduction, while carrying out at vulcanization to catalyst
Reason can effectively inhibit the performances such as the cracking of catalyst and advantageously reduce side reaction and occur, promote dehydrogenation activity and maintain length
Phase stability, while enhance catalyst to the adsorption capacity of hydrogen at high temperature, inhibit the formation of carbon deposit under the conditions of pyroreaction,
The result of study (Chinese patent consistent with the effect of vulcanizing treatment in the dehydrating alkanes catalyst containing Pt that the strict we of woods disclose
CN87101513)。
Although preparing propylene by dehydrogenating propane technique has been realized in industrialization, the main problem of the technique is by thermodynamic condition
Limitation, need higher reaction temperature, energy consumption is high, while catalyst inactivation is quickly.CO2Introducing equilibrium conversion can be improved
Rate reduces reaction temperature；CO simultaneously2Area carbon can be eliminated, the stability of catalyst is improved；And CO2As weak oxide
Agent can prevent deep oxidation, guarantee the highly selective of target product propylene.CO2Dehydrogenating propane under atmosphere has preferably application
Prospect.
Summary of the invention
The technical problem to be solved by the present invention is to the height of reaction temperature present in conventional art, and catalyst activity is low, mentions
For the catalyst and its method of dehydrogenating propane in the presence of a kind of mild oxidizing agent.The catalyst and its method are used for mild oxidizing agent
There are when producing propylene by propane dehydrogenation reaction, have reaction temperature low, catalyst activity is high, the good advantage of selectivity.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows: a kind of carbon dioxide mild oxidizing agent is deposited
In lower dehydrogenating propane method, it is characterised in that by weight percentage, contain following composition:
A) active constituent is with Cr2O3It is calculated as 0.01-50.0 parts；
B) rare-earth oxide modified agent is 0.1-20.0 parts；
C) catalyst carrier ZrO2It is 30.0-99.5 parts.
In above-mentioned technical proposal, active constituent is based on parts by weight with Cr2O3The dosage preferred scope of meter is 0.1-30 parts.
The dosage preferred scope of rare-earth oxide modified agent is 0.1-10 parts based on parts by weight.Rare-earth oxide modified agent is CeO2With
La2O3One or two.The dosage preferred scope of catalyst carrier is 60-99 parts based on parts by weight.
In above-mentioned technical proposal, it is preferred that carrier further includes Al2O3, Al2O3With ZrO2Weight ratio be (1:20)~(1:
5)。
In above-mentioned technical proposal, it is furthermore preferred that Al2O3With ZrO2Weight ratio be (1:10)~(1:5).
In above-mentioned technical proposal, it is preferred that active component further includes molybdenum oxide, molybdenum oxide and Cr2O3Weight ratio be (1:
10)~(1:1).
In above-mentioned technical proposal, it is furthermore preferred that molybdenum oxide and Cr2O3Weight ratio be (1:5)~(1:1).
Above-mentioned catalyst is used for dehydrogenating propane, and reaction raw materials are propane, reaction atmosphere CO2；Reaction condition are as follows: pressure
Power is normal pressure, and reaction temperature is 500~600 DEG C, C3H8:CO2(volume ratio)=5:1-1:5, reaction raw materials and the catalyst
Haptoreaction obtains propylene.
In above-mentioned technical proposal, it is preferred that reaction temperature is 550~600 DEG C.
Catalyst obtained carries out activity rating in isotherm formula fixed bed reactors according to the above method, to dehydrogenating propane system
For propylene evaluation, summary process is as follows:
Unstrpped gas propane and carbon dioxide are adjusted into flow by mass flowmenter respectively, mixed into pre-add hot-zone
It closes, subsequently into reaction zone, the pre-add hot-zone of reactor and reaction zone are all made of electric-heating-wire-heating, predetermined temperature is made up to,
The internal diameter of reactor is the stainless steel sleeve pipe of Ф 9mm-Ф 6mm, is about 400mm.After gas after reaction passes through drainer, into
Enter its composition of gas chromatographic analysis.
Evaluating catalyst condition is as follows in isotherm formula fixed bed reactors: 0.5 gram or so of catalyst, which is packed into internal diameter, is
In the isothermal reactor of Ф 9mm-Ф 6mm (catalyst bed layer height about 17mm), catalyst is small by nitrogen activation 1 at 560 DEG C
When.Reaction pressure is normal pressure, and temperature is 500~600 DEG C, C3H8:CO2=5:1-1:5, gas overall flow rate 50mL/min.Reaction
Product is analyzed by gas-chromatography.
During dehydrogenating low-carbon alkane, CO2Introducing conversion ratio and selectivity, while CO can be improved2Surface can be eliminated
Carbon distribution improves the stability of catalyst.The addition of rare earth oxide is conducive to catalyst and keeps more during the reaction
Cr6+, while the acidity of catalyst can be partially reduced, reduce the generation of carbon distribution.Using above-mentioned evaluation condition by catalysis of the invention
Agent is in dehydrogenating propane reaction, Activity evaluation to show catalyst alkane conversion with higher, compared with low reaction
At a temperature of conversion of propane reach 60% or more, Propylene Selectivity reaches 93% or more.Achieve preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
Weigh 84.21 grams of Cr (NO3)3·9H2O, 615.38 grams of Zr (NO3)4·5H2O, 25.0 grams of Ce (NO3)3·6H2O adds
Enter into 500 milliliters of deionized water, stirs, after being completely dissolved.Under stirring, above-mentioned mixed solution is added dropwise in 6mol/L ammonium hydroxide
In, control whole process in pH it is constant continue after 10 or more, completion of dropwise addition stirring 1 hour.Obtained sediment ageing 24
Hour.By its filtration washing after ageing, 120 DEG C drying 12 hours, then in Muffle furnace 600 DEG C roast 4 hours.It obtains
Required propane dehydrogenation catalyst.
Catalyst breakage is sieved, 40~60 mesh are taken, by nitrogen activation 2 hours at 560 DEG C on fixed bed reactors.Drop
In 550 DEG C of reaction temperature after temperature, C3H8:CO2=1:2, under the reaction condition of gas overall flow rate 50mL/min, dehydrogenating propane one way
Conversion ratio 58.5%, Propylene Selectivity 93.2%.
[embodiment 2]
Weigh 315.78 grams of Cr (NO3)3·9H2O, 419.58 grams of Zr (NO3)4·5H2O, 62.5 grams of Ce (NO3)3·6H2O adds
Enter into 500 milliliters of deionized water, stirs, after being completely dissolved.Remaining preparation method and evaluation condition are the same as embodiment 1, propane
Dehydrogenation conversion per pass 58.6%, Propylene Selectivity 91.6%.
[embodiment 3]
Weigh 84.21 grams of Cr (NO3)3·9H2O, 706.91 grams of Zr (NO3)4·5H2O, 0.625 gram of Ce (NO3)3·6H2O adds
Enter into 500 milliliters of deionized water, stirs, after being completely dissolved.Remaining preparation method and evaluation condition are the same as embodiment 1, propane
Dehydrogenation conversion per pass 56.2%, Propylene Selectivity 90.6%.
[embodiment 4]
Weigh 315.78 grams of Cr (NO3)3·9H2O, 461.54 grams of Zr (NO3)4·5H2O, 25.0 grams of Ce (NO3)3·6H2O adds
Enter into 500 milliliters of deionized water, stirs, after being completely dissolved.Remaining preparation method and evaluation condition are the same as embodiment 1, propane
Dehydrogenation conversion per pass 57.1%, Propylene Selectivity 92.3%.
[embodiment 5]
Weigh 84.21 grams of Cr (NO3)3·9H2O, 615.38 grams of Zr (NO3)4·5H2O, 10.638 grams of La (NO3)3·6H2O
It is added in 500 milliliters of deionized water, stirs, after being completely dissolved.Remaining preparation method and evaluation condition are with embodiment 1, and third
Alkane dehydrogenation conversion per pass 57.8%, Propylene Selectivity 93.0%.
[embodiment 6]
By the preparation method of the catalyst of embodiment 1, Aluminum sol is only added in catalyst preparation process, finally obtains
Catalyst in Al2O3With ZrO2Weight ratio be 1:20.
Catalyst breakage is sieved, 40~60 mesh are taken, by nitrogen activation 2 hours at 560 DEG C on fixed bed reactors.Drop
In 550 DEG C of reaction temperature after temperature, C3H8:CO2=1:2, under the reaction condition of gas overall flow rate 50mL/min, dehydrogenating propane one way
Conversion ratio 60.5%, Propylene Selectivity 94.0%.
[embodiment 7]
By the preparation method of the catalyst of embodiment 1, Aluminum sol is only added in catalyst preparation process, finally obtains
Catalyst in Al2O3With ZrO2Weight ratio be 1:1.
Catalyst breakage is sieved, 40~60 mesh are taken, by nitrogen activation 2 hours at 560 DEG C on fixed bed reactors.Drop
In 550 DEG C of reaction temperature after temperature, C3H8:CO2=1:2, under the reaction condition of gas overall flow rate 50mL/min, dehydrogenating propane one way
Conversion ratio 60.2%, Propylene Selectivity 94.2%.
[embodiment 8]
By the preparation method of the catalyst of embodiment 1, Aluminum sol is only added in catalyst preparation process, finally obtains
Catalyst in Al2O3With ZrO2Weight ratio be 1:10.
Catalyst breakage is sieved, 40~60 mesh are taken, by nitrogen activation 2 hours at 560 DEG C on fixed bed reactors.Drop
In 550 DEG C of reaction temperature after temperature, C3H8:CO2=1:2, under the reaction condition of gas overall flow rate 50mL/min, dehydrogenating propane one way
Conversion ratio 62.2%, Propylene Selectivity 95.2%.
[embodiment 9]
By the preparation method of the catalyst of embodiment 1, Aluminum sol is only added in catalyst preparation process, finally obtains
Catalyst in Al2O3With ZrO2Weight ratio be 1:5.
Catalyst breakage is sieved, 40~60 mesh are taken, by nitrogen activation 2 hours at 560 DEG C on fixed bed reactors.Drop
In 550 DEG C of reaction temperature after temperature, C3H8:CO2=1:2, under the reaction condition of gas overall flow rate 50mL/min, dehydrogenating propane one way
Conversion ratio 62.4%, Propylene Selectivity 95.0%.
[embodiment 10]
By the preparation method of the catalyst of embodiment 2, ammonium molybdate is only added in catalyst preparation process, finally obtains
Catalyst in molybdenum oxide and Cr2O3Weight ratio be 1:10.
Catalyst breakage is sieved, 40~60 mesh are taken, by nitrogen activation 2 hours at 560 DEG C on fixed bed reactors.Drop
In 550 DEG C of reaction temperature after temperature, C3H8:CO2=1:2, under the reaction condition of gas overall flow rate 50mL/min, dehydrogenating propane one way
Conversion ratio 60.4%, Propylene Selectivity 92.4%.
[embodiment 11]
By the preparation method of the catalyst of embodiment 2, ammonium molybdate is only added in catalyst preparation process, finally obtains
Catalyst in molybdenum oxide and Cr2O3Weight ratio be 1:1.
Catalyst breakage is sieved, 40~60 mesh are taken, by nitrogen activation 2 hours at 560 DEG C on fixed bed reactors.Drop
In 550 DEG C of reaction temperature after temperature, C3H8:CO2=1:2, under the reaction condition of gas overall flow rate 50mL/min, dehydrogenating propane one way
Conversion ratio 60.1%, Propylene Selectivity 92.2%.
[embodiment 12]
By the preparation method of the catalyst of embodiment 2, ammonium molybdate is only added in catalyst preparation process, finally obtains
Catalyst in molybdenum oxide and Cr2O3Weight ratio be 1:8.
Catalyst breakage is sieved, 40~60 mesh are taken, by nitrogen activation 2 hours at 560 DEG C on fixed bed reactors.Drop
In 550 DEG C of reaction temperature after temperature, C3H8:CO2=1:2, under the reaction condition of gas overall flow rate 50mL/min, dehydrogenating propane one way
Conversion ratio 62.0%, Propylene Selectivity 94.2%.
[embodiment 13]
By the preparation method of the catalyst of embodiment 2, ammonium molybdate is only added in catalyst preparation process, finally obtains
Catalyst in molybdenum oxide and Cr2O3Weight ratio be 1:2.
Catalyst breakage is sieved, 40~60 mesh are taken, by nitrogen activation 2 hours at 560 DEG C on fixed bed reactors.Drop
In 550 DEG C of reaction temperature after temperature, C3H8:CO2=1:2, under the reaction condition of gas overall flow rate 50mL/min, dehydrogenating propane one way
Conversion ratio 62.2%, Propylene Selectivity 94.0%.
[comparative example 1]
Weigh 84.21 grams of Cr (NO3)3·9H2O, 643.35 grams of Zr (NO3)4·5H2O is added to 500 milliliters of deionized water
In, stirring, after being completely dissolved.Remaining preparation method and evaluation condition are with embodiment 1, dehydrogenating propane conversion per pass 29.3%,
Propylene Selectivity 57.2%.
[comparative example 2]
Weigh 25.0 grams of Ce (NO3)3·6H2O, 671.32 grams of Zr (NO3)4·5H2O is added to 500 milliliters of deionized water
In, stirring, after being completely dissolved.Remaining preparation method and evaluation condition are with embodiment 1, dehydrogenating propane conversion per pass 35.3%,
Propylene Selectivity 78.2%.
[embodiment 14~17]
The catalyst that embodiment 1 is prepared is used for dehydrogenating low-carbon alkane, reaction raw materials are propane, and reaction raw materials are one
Propylene is obtained with catalyst haptoreaction under fixed condition；Reaction condition and evaluation results are shown in Table 1.
Table 1
Claims (9)
1. propane dehydrogenation catalyst in the presence of a kind of carbon dioxide mild oxidizing agent, it is characterised in that by weight percentage, contain
It is made of following:
A) active constituent is with Cr2O3It is calculated as 0.01-50.0 parts；
B) rare-earth oxide modified agent is 0.1-20.0 parts；
C) catalyst carrier ZrO2It is 30.0-99.5 parts；
Carrier further includes Al2O3, Al2O3With ZrO2Weight ratio be (1:20)~(1:1).
2. propane dehydrogenation catalyst in the presence of carbon dioxide mild oxidizing agent according to claim 1, it is characterised in that with
Parts by weight meter active constituent is with Cr2O3The dosage of meter is 0.1-30 parts.
3. propane dehydrogenation catalyst in the presence of carbon dioxide mild oxidizing agent according to claim 1, it is characterised in that with
The dosage of parts by weight meter rare-earth oxide modified agent is 0.1-10 parts.
4. propane dehydrogenation catalyst in the presence of carbon dioxide mild oxidizing agent according to claim 1, it is characterised in that dilute
Native oxide modifier is CeO2And La2O3One or two.
5. propane dehydrogenation catalyst in the presence of carbon dioxide mild oxidizing agent according to claim 1, it is characterised in that with
Parts by weight meter catalyst carrier ZrO2Dosage be 60-99 parts.
6. propane dehydrogenation catalyst in the presence of carbon dioxide mild oxidizing agent according to claim 1, it is characterised in that
Al2O3With ZrO2Weight ratio be (1:10)~(1:5).
7. propane dehydrogenation catalyst in the presence of carbon dioxide mild oxidizing agent according to claim 1, it is characterised in that living
Property component further includes molybdenum oxide, molybdenum oxide and Cr2O3Weight ratio be (1:10)~(1:1).
8. propane dehydrogenation catalyst in the presence of carbon dioxide mild oxidizing agent according to claim 7, it is characterised in that oxygen
Change molybdenum and Cr2O3Weight ratio be (1:8)~(1:2).
9. any one of claim 1~8 propane dehydrogenation catalyst is used for dehydrogenating propane, reaction raw materials are propane, reaction
Atmosphere is CO2；Reaction condition are as follows: pressure is normal pressure, and temperature is 500~600 DEG C, with volume basis C3H8:CO2=5:1-1:5,
Reaction raw materials and the catalyst haptoreaction obtain propylene.
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| CN101003458A (en) * | 2006-01-19 | 2007-07-25 | 中国石油化工股份有限公司 | Method for preparing propylene by dehydrogenating propane |
| CN101165031A (en) * | 2006-10-16 | 2008-04-23 | 罗门哈斯公司 | Integrated catalytic process for converting alkanes to alkenes and catalysts useful for same |
| CN101940922A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN103157460A (en) * | 2013-03-10 | 2013-06-19 | 复旦大学 | Rare earth oxide modified Cr2O3-ZrO2 catalyst, preparation method and application |
| CN103769079A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Low carbon alkane dehydrogenation catalyst and its preparation method and application |
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- 2016-06-29 CN CN201610498189.0A patent/CN107537463B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003458A (en) * | 2006-01-19 | 2007-07-25 | 中国石油化工股份有限公司 | Method for preparing propylene by dehydrogenating propane |
| CN101165031A (en) * | 2006-10-16 | 2008-04-23 | 罗门哈斯公司 | Integrated catalytic process for converting alkanes to alkenes and catalysts useful for same |
| CN101940922A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN103769079A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Low carbon alkane dehydrogenation catalyst and its preparation method and application |
| CN103157460A (en) * | 2013-03-10 | 2013-06-19 | 复旦大学 | Rare earth oxide modified Cr2O3-ZrO2 catalyst, preparation method and application |
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