CN104525194B - Catalyst used for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof - Google Patents
Catalyst used for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a catalyst used for preparing isobutene through isobutane dehydrogenation and a preparation method and application of the catalyst. The preparation method comprises the following steps that Pt@MgAl2O4 core-shell type nanoparticles are loaded on Al2O3 carriers based on an ultrasonic oscillation method, so that a Pt@MgAl2O4/Al2O3 catalyst is obtained; next, precursors of addition agents are prepared into a solution in proportion, step-by-step treatment is performed based on an incipient-wetness impregnation method, the addition agents are added into the Pt@MgAl2O4/Al2O3 catalyst, so the catalyst used for preparing the isobutene through isobutane dehydrogenation is obtained. The invention further provides the catalyst obtained based on the preparation method and the application of the catalyst in the field of preparing isobutene through isobutane dehydrogenation. The catalyst has high activity, high isobutane conversion rate high isobutene selectivity and high yield; moreover the catalyst has good high-temperature stability; meanwhile the catalyst can effectively lower the amount of deposited carbon during reaction, and therefore side reactions can be effectively inhibited.
Description
Technical field
The invention provides a kind of preparing isobutene through dehydrogenation of iso-butane catalyst and preparation method and application, relate to chemical industry
Technical field, particularly catalytic dehydrogenation technical field.
Background technology
Isobutene. has another name called 2-metering system, is a kind of very important Organic Chemicals, is widely used in butyl
The production of the chemical products such as rubber, polyisobutylene, methacrylonitrile, antioxidant, tertiary butyl phenol, tertbutyl ether and preparation
In the middle of process.Past isobutene. is mainly by high-temperature steam cracking, the side-product of catalytic cracking and dehydrogenation of isobutane etc.
Approach obtains.Along with increase to isobutene. demand in global range in the last few years, traditional isobutene. mode of production
The demand of people can not be met the most far away.And China's iso-butane aboundresources, it is present in liquefied gas in a large number, and
Current liquefied gas is primarily used to domestic fuel and burns, and the utilization rate causing iso-butane is extremely low.Therefore, exploitation isobutyl
Alkane dehydrogenation is prepared the technology of isobutene. and is had great economic benefit and social meaning.At present, develop in the world more
Ripe dehydrogenation of isobutane prepares isobutene catalyst and catalytic dehydrogenation process mainly includes American UOP company
Oleflex technique, the Star technique of Phillips company, the Catofin technique of ABB Lummus company, Italy
The FBD-4 technique of Snamprogetti SPA company and the Linde technique of Linde company of Germany.These techniques are made
Catalyst mainly include two big classes: one is that chromium oxide is supported on alumina catalyst support, and also your gold is one be by
Belong to Pt to be supported on aluminium oxide or other carriers.Although chromium-based catalysts is cheap, but to ingredient requirement relatively
High and there is more Heavy environmental pollution, the use to such catalyst in recent years is limited by very large.When
When Pt base catalyst is as the catalyst of preparation of olefin through light alkane dehydrogenation, although environmentally friendly, activity is higher, right
Ingredient requirement is relatively low, but this catalyst the most easily occurs that Pt component assembles the phenomenon of sintering, and activity reduces
Rapidly, catalyst stability is poor, and carbon distribution situation is serious in course of reaction.Therefore, exploitation one can be
The dehydrogenation of isobutane catalyst of the higher reaction temperatures preferable stability of holding and reactivity is significant.
Patent CN1185994A uses the elements such as co-precipitation, Slurry mixing load C r, Pt, V, uses infusion process to bear
Carry the elements such as La, Zr, Sn, Fe, obtain loaded catalyst, and preferably Al2O3As carrier；Prepare urges
The features such as the anti-carbon performance that agent has high activity, high selectivity is become reconciled.Patent CN102000593A is with heat-resisting oxygen
Compound is carrier, with platinum group metal as major catalyst, is the first auxiliary agent with the IVth race's metal element, with alkali metal
Being the second auxiliary agent, halogen is modifying agent, uses equi-volume impregnating that above-mentioned active component is loaded to resistance to thermal oxide
Thing carrier prepares catalyst and has higher iso-butane conversion ratio, selective isobutene and excellent stability.Patent
CN101623633A uses aluminium silicophosphate molecular sieve to be carrier, with group VIII or vib element for activity group
Point, with group iva element as auxiliary agent, the catalyst using infusion process to prepare has the shape-selective effect of aperture, moderate
The features such as acidity, high olefin selectivity.Catalyst obtained by patent CN101862669A is Jie stanniferous with skeleton
Porous aluminum oxide molecular sieve is carrier, is support modification agent with alkalinous metal auxiliary agent, co-impregnation H2PtCl6And SnCl4's
Mixed aqueous solution, and drying activation is prepared.Alkalinous metal is in group ia, group iia, rare earth metal
Plant or the combination of several metal.This catalyst has higher iso-butane conversion ratio, different under conditions of high temperature, low pressure
Butylene selectivity and reaction stability.S.H.Joo et al. (S.H.Joo, C.K Tsung, Yusuke.Yamada, P.D.
Yang.G.A.Somorjai.Thermally stable Pt/mesoporous silica core–shell nanocatalysts for
High-temperature reactions.Nature materials, 2008,8 (2), 126-131.) by mesoporous SiO2It is wrapped in
(i.e. Pt@mSiO outside Pt nanoparticle2) make high-temperature catalyst.Due to the mesoporous SiO of inorganic shell2Parcel,
On the one hand reactant molecule can pass freely through shell SiO2Through " core " the Pt nanoparticle in flourishing duct and send out
Raw catalytic reaction；On the other hand SiO2The high-temperature stability of material makes Pt particle still remain after 750 DEG C of calcinations
Original pattern, the most mesoporous SiO2It is the protectiveness shell possessing high-temperature stability, serves stable internal nano-particle
Effect.T.Montini et al. (T.Montini, A.M.Condo, N.Hickey, F.C.Lovey, L.De.Rogatis,
P.Fornasiero, M.Graziani.Embedded Rh (1wt%)@Al2O3:Effects of high temperature and
prolonged aging under methane partial oxidation conditions.Applied Catalysis B:
Environmental, 2007,73,84 97.) the hollow porous Al synthesized2O3The Rh core nanoparticle of parcel also obtains
Relatively conventional load type Rh/Al2O3The most excellent activity and resistance to elevated temperatures.
At present, industrial used dehydrogenation of isobutane prepares isobutene catalyst mainly by tradition infusion process load
Pt component, then (includes adding various auxiliary element or using the load that heat stability is high by the various preparation conditions of optimization
Body such as ZnAl2O4, SBA-15 and ZSM-5 molecular sieve) obtain.Dehydrogenation of isobutane course of reaction is due to by thermodynamics
Balance controls, high temperature, the carrying out of harsh conditions beneficially dehydrogenation reaction of low pressure, but too high reaction temperature is easily led
Causing Pt active center sintering, not only make Deposition During Propane Pyrolysis reaction and deep dehydrogenation aggravation, selectivity declines；Also add simultaneously
The fast carbon deposit of catalyst surface, makes rapid catalyst deactivation.Generally, prior art mainly includes following deficiency:
(1) dispersion of Pt metal component, particle diameter distribution and the microstructure such as surface topography are difficult to control；(2) activity
Sintering and the active sites of component Pt microgranule are covered by carbon deposit；(3) change of auxiliary agent Sn valence state causes oxidation state Sn to turn
Turn to zeroth order Sn, generate Pt-Sn alloy, cause Pt to be poisoned.Therefore, how to improve the anti-caking power of Pt component,
Maintain the Sn state of oxidation in strongly reducing atmosphere, develop high stability, high activity and the selective catalysis dehydrogenation of height
Agent becomes the key problem in technology of the present invention.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of preparing isobutene through dehydrogenation of iso-butane catalysis
Agent.The catalyst of the present invention has higher catalytic dehydrogenation of isobutane and prepares the activity of isobutene., and higher iso-butane turns
Rate, higher selective isobutene and yield；And this catalyst has good high-temperature stability, can be higher
At a temperature of carry out catalytic dehydrogenation of isobutane and prepare the reaction of isobutene.；This catalyst can effectively reduce course of reaction simultaneously
Middle carbon deposition quantity, and then the generation of side reaction can be suppressed.
The present invention also aims to provide the preparation method of above-mentioned catalyst.
The present invention also aims to the application providing above-mentioned catalyst in preparing isobutene through dehydrogenation of iso-butane field.
For reaching above-mentioned purpose, the invention provides the preparation method of a kind of preparing isobutene through dehydrogenation of iso-butane catalyst,
This preparation method comprises the following steps:
A, employing ultrasonic wave concussion method are by Pt@MgAl2O4Nuclear shell type nano meter particle loads to Al2O3On carrier, super
The time of sound wave shock is 2-6 hour, and through filtering, 90-200 DEG C dry 6-16 hour, 500-800 DEG C of roasting 2-6
Hour, obtain Pt@MgAl2O4/Al2O3Catalyst；
B, by the presoma of auxiliary agent wiring solution-forming in proportion, use equi-volume impregnating to carry out step-by-step processing, by auxiliary agent
Add described Pt@MgAl to2O4/Al2O3Catalyst, 90-200 DEG C dry 6-16 hour, 500-800 DEG C of roasting
2-6 hour, obtain preparing isobutene through dehydrogenation of iso-butane catalyst.
According to preparation method of the present invention, described auxiliary agent includes a Group IA element, IVA race element and iv B
Race's element；
The most described a Group IA element includes the combination of one or more in lithium, sodium, potassium；
The most described group iva element includes one or both the combination in stannum, germanium；
The most described group ivb element includes one or both the combination in zirconium, titanium.
According to preparation method of the present invention, it is preferable that in the presoma of described auxiliary agent, the presoma of potassium includes
Potassium chloride and/or potassium nitrate；
The presoma of stannum includes stannous chloride (SnCl2·2H2O), one or more in stannous methide, tributyl tin
Combination；
The presoma of zirconium includes zirconium chloride and/or zirconium nitrate.
According to preparation method of the present invention, it is preferable that described Pt@MgAl2O4Nuclear shell type nano meter particle is to pass through
Prepared by following steps:
A, the presoma of platinum is mixed homogeneously with stabilizer, at 30-90 DEG C, with the stirring speed of 800-1400 rev/min
Rate stirs 30 minutes, adds reducing agent and reduces, stirs 0.5-5 hour, stand 12-24 hour, obtain platinum and receive
Rice colloidal sol；
B, the platinum Nano sol obtained in step a add the presoma of magnesium and the presoma of aluminum, 30-90 DEG C of stirring
30min, under the stir speed (S.S.) of 800-1400 rev/min, dropping volume fraction is the ammonia of 50%, by the pH of solution
Value is adjusted to 9-10, continues reaction 2-6h, be then passed through 90-200 DEG C dry 6-16 hour, grind, 500-800 DEG C
Roasting 2-6 hour, obtains Pt@MgAl2O4Nuclear shell type nano meter particle.
According to preparation method of the present invention, it is preferable that in step a, the presoma of described platinum includes chloroplatinic acid
(H2PtCl6), potassium chloroplatinate (K2PtCl4), acetylacetone,2,4-pentanedione platinum (Pt (acac)2The combination of one or more in)；
Described stabilizer include polyvinylpyrrolidone (PVP), Tetradecyl Trimethyl Ammonium Bromide (CTAB), ten
The combination of one or more in six alkyl trimethyl ammonium bromides (TTAB)；
Described reducing agent includes sodium borohydride (NaBH4), hydrazine (N2H4), potassium borohydride (KBH4One in)
Or several combinations.
According to preparation method of the present invention, it is preferable that in step a, the load capacity (mass fraction) of described platinum
For 0.2-0.6wt%；
The presoma of described platinum and the mol ratio of described reducing agent are 1:2-1:30.
According to preparation method of the present invention, it is preferable that in step b, the presoma of described magnesium includes magnesium nitrate
(Mg(NO3)2) and/or magnesium chloride (MgCl2)；
The presoma of the aluminum used includes aluminum nitrate (Al (NO3)3) and/or aluminum chloride (AlCl3)。
According to preparation method of the present invention, it is preferable that in step b, the presoma of described magnesium and the presoma of aluminum
Mol ratio be 1:10-20:1.
Present invention also offers the preparing isobutene through dehydrogenation of iso-butane catalyst using above-mentioned preparation method to obtain, this catalysis
Agent is with Al2O3For carrier, with Pt@MgAl2O4Nuclear shell type nano meter particle is active component, with group ia, iv A
Race, group ivb element are auxiliary agent；With described Al2O3The weight meter of carrier, the load capacity of described platinum is 0.2-0.6wt%；
The load capacity of described auxiliary agent is 0.5-2wt%；The load capacity of above-mentioned auxiliary agent calculates with the amount of the oxide of auxiliary agent,
Such as, auxiliary agent stannum, potassium, zirconium load capacity respectively with SnO2、K2O、ZrO2Load capacity calculate.
Present invention also offers above-mentioned preparing isobutene through dehydrogenation of iso-butane catalyst in preparing isobutene through dehydrogenation of iso-butane
Application, it is preferable that described preparing isobutene through dehydrogenation of iso-butane comprises the following steps:
With the mixture of iso-butane or iso-butane and hydrogen as raw material, carrying out dehydrogenation reaction in the reactor, this dehydrogenation is anti-
The operating condition answered is as follows: the consumption of catalyst is 0.5-2g, reaction temperature is 400-700 DEG C, volume space velocity is
1000-6000h-1, reaction pressure be normal pressure；During with the mixture of iso-butane and hydrogen for raw material, in raw material hydrogen with
The mol ratio of iso-butane is 0.01:1-10:1.
The present invention is with the Pt@MgAl of high-temperature stable2O4Nuclear shell type nano meter particle is active component, and it is successfully born
It is downloaded to carrier Al2O3On；This special coreshell type structure of this catalyst active center, can be effectively prevented gold
Belong to the reunion at high temperature of nanometer nuclear particle and the formation of alloy, improve the high-temperature stability of catalyst, and oxidation
Thing integument and the interparticle interaction of metal core, improve the activity of catalyst.Meanwhile, shell MgAl2O4's
Introduce, it is possible to resolve tradition dehydrogenation of isobutane catalyst platinum component under severe conditions assembles sintering and the difficulty of carbon distribution
Topic, such that it is able to suppression side reaction generation, improve catalyst stability, and by infusion process load group ia,
Group iva, group ivb auxiliary element improve the activity of catalyst.
The preparing isobutene through dehydrogenation of iso-butane catalyst of the present invention has higher catalytic dehydrogenation of isobutane and prepares isobutene.
Activity, there is higher iso-butane conversion ratio, higher selective isobutene and yield.This catalyst isobutyl
Alkane dehydrogenation preparing isobutene reacts, and after reaction terminates, the conversion per pass of iso-butane can reach more than 48%, product isobutyl
The selectivity of alkene is up to more than 96%, and the yield of isobutene. is about 46%.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing skill to the present invention
Art scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.
Embodiment 1
Present embodiments providing a kind of preparing isobutene through dehydrogenation of iso-butane catalyst, it is through the following steps that prepare
:
Sodium borohydride reduction is used to prepare platinum Nano sol:
It is 7.723 × 10 by 10mL concentration-3The H of mol/L2PtCl6Aqueous solution fills with 0.02252g stabilizer CTAB
Mixing, 40 DEG C of constant temperature is divided to stir 30 minutes, it is ensured that stabilizer CTAB adsorbs at Pt4+Around；Strongly stir
Mix down and be slowly added to 0.0352g NaBH4Solution reduces, and stands 12 hours, obtains platinum Nano sol.
Sol-gel process is used to prepare Pt@MgAl2O4Coreshell type structure:
0.0634g Mg (NO is added in above-mentioned platinum Nano sol3)2·6H2O and 0.1854g Al (NO3)3·9H2O,
60 DEG C of stirring 30min, being stirred vigorously down (rotating speed 800-1400 rev/min) dropping volume fraction is the ammonia of 50%,
The pH value of solution is adjusted to 10, and 60 DEG C are continued reaction 3h, the hot plate in ventilated chamber add thermosol with 120 DEG C
Glue sample, is dried 6 hours, grinds, and 500 DEG C of roastings 4 hours in Muffle furnace, obtain Pt@MgAl subsequently2O4
Coreshell type structure.
Prepare preparing isobutene through dehydrogenation of iso-butane catalyst:
It is 0.5wt% according to the load capacity of noble metal platinum, weighs 3.0g activated alumina, by alumina support with above-mentioned
Pt@MgAl2O4Coreshell type structure mixes, and ultrasonic wave concussion loads 6 hours, is then passed through filtering, and 120 DEG C are dried
12 hours, 500 DEG C of roastings 4 hours, obtain Pt@MgAl2O4/Al2O3Catalyst；
The employing equi-volume impregnating various auxiliary elements of load:
According to SnO2、K2O、ZrO2Load capacity be respectively 1.0wt%, 1.2wt%, 1.5wt% (with Carriers Active
The quality meter of aluminium oxide), accurately weigh 0.0449g SnCl2·2H2O、0.0773g KNO3With 0.1568g Zr (NO3)4
Respectively wiring solution-forming, then uses equi-volume impregnating step impregnation to 3.0g above-mentioned Pt@MgAl2O4/Al2O3Catalysis
In agent, 120 DEG C are dried 12 hours, and 500 DEG C of roastings obtain preparing isobutene through dehydrogenation of iso-butane catalyst in 4 hours.
Embodiment 2
Present embodiments provide preparing isobutene through dehydrogenation of iso-butane catalyst that embodiment 1 obtains in dehydrogenation of isobutane system
Application in isobutene., this application comprises the following steps:
With the mixture of iso-butane and hydrogen as raw material, carry out dehydrogenation reaction, the operating condition of this reaction in the reactor
As follows: in raw material the mol ratio of hydrogen and iso-butane be 1:1, the consumption of catalyst be 1.5g, reaction temperature be 590 DEG C,
Reaction pressure be normal pressure, volume space velocity be 1350h-1。
After reaction terminates, use gas chromatograph (model is hp5830) that reaction end gas is carried out on-line analysis, carry
Gas is nitrogen, and detector is flame ionization ditector, uses chromatographic work station to carry out data process (Zhejiang University
Intelligence reaches Information Technology Co. Ltd N-2000 type).By analysis result: the conversion ratio of iso-butane is 48%,
The selectivity generating isobutene. is 96%, and the yield of isobutene. is 46.08%.
Claims (14)
1. a preparation method for preparing isobutene through dehydrogenation of iso-butane catalyst, it comprises the following steps:
A, employing ultrasonic wave concussion method are by Pt@MgAl2O4Nuclear shell type nano meter particle loads to Al2O3On carrier, ultrasound wave
The time of concussion is 2-6 hour, and through filtering, 90-200 DEG C is dry 6-16 hour, 500-800 DEG C of roasting 2-6 hour,
Obtain Pt@MgAl2O4/Al2O3Catalyst；
B, by the presoma of auxiliary agent wiring solution-forming in proportion, use equi-volume impregnating to carry out step-by-step processing, auxiliary agent added
It is added to described Pt@MgAl2O4/Al2O3Catalyst, 90-200 DEG C dry 6-16 hour, 500-800 DEG C of roasting 2-6
Hour, obtain preparing isobutene through dehydrogenation of iso-butane catalyst.
Preparation method the most according to claim 1, wherein, described auxiliary agent includes a Group IA element, group iva
Element and group ivb element.
Preparation method the most according to claim 2, wherein, described a Group IA element includes in lithium, sodium, potassium
The combination of one or more.
Preparation method the most according to claim 2, wherein, described group iva element includes in stannum, germanium
Plant or the combination of two kinds.
Preparation method the most according to claim 2, wherein, described group ivb element includes in zirconium, titanium
Plant or the combination of two kinds.
6. according to the preparation method described in any one of claim 1-5, wherein, in the presoma of described auxiliary agent, potassium
Presoma include potassium chloride and/or potassium nitrate；
The presoma of stannum includes the combination of one or more in stannous chloride, stannous methide, tributyl tin；
The presoma of zirconium includes zirconium chloride and/or zirconium nitrate.
Preparation method the most according to claim 1, wherein, described Pt@MgAl2O4Nuclear shell type nano meter particle is
Prepared by following steps:
A, the presoma of platinum is mixed homogeneously with stabilizer, at 30-90 DEG C, stir with the stir speed (S.S.) of 800-1400 rev/min
Mix 30 minutes, add reducing agent and reduce, stir 0.5-5 hour, stand 12-24 hour, obtain platinum Nano sol；
B, the platinum Nano sol obtained in step a add the presoma of magnesium and the presoma of aluminum, 30-90 DEG C of stirring
30min, under the stir speed (S.S.) of 800-1400 rev/min, dropping volume fraction is the ammonia of 50%, by the pH value of solution
Being adjusted to 9-10, continue reaction 2-6h, 90-200 DEG C is dry 6-16 hour, grinds, 500-800 DEG C of roasting 2-6 hour,
Obtain Pt@MgAl2O4Nuclear shell type nano meter particle.
Preparation method the most according to claim 7, wherein, in step a, the presoma of described platinum includes chlorine platinum
The combination of one or more in acid, potassium chloroplatinate, acetylacetone,2,4-pentanedione platinum；
Described stabilizer includes polyvinylpyrrolidone, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide
In the combination of one or more；
Described reducing agent includes the combination of one or more in sodium borohydride, hydrazine, potassium borohydride.
Preparation method the most according to claim 7, wherein, in step a, the presoma of described platinum and described surely
The mol ratio determining agent is 1:1-1:20；The presoma of described platinum and the mol ratio of described reducing agent are 1:2-1:30.
Preparation method the most according to claim 7, wherein, in step b, the presoma of described magnesium includes nitric acid
Magnesium and/or magnesium chloride；The presoma of described aluminum includes aluminum nitrate and/or aluminum chloride.
11. preparation methoies according to claim 7, wherein, in step b, the presoma of described magnesium and described aluminum
The mol ratio of presoma be 1:10-20:1.
The preparing isobutene through dehydrogenation of iso-butane catalyst that preparation method described in 12. any one of claim 1 to 11 obtains,
This catalyst is with Al2O3For carrier, with Pt@MgAl2O4Nuclear shell type nano meter particle is active component, with group ia,
Group iva, group ivb element are auxiliary agent；With described Al2O3The weight meter of carrier, the load capacity of described platinum is
0.2-0.6wt%；The load capacity of described auxiliary agent is 0.5-2wt%.
Preparing isobutene through dehydrogenation of iso-butane catalyst described in 13. claim 12 is in preparing isobutene through dehydrogenation of iso-butane
Application.
14. application according to claim 13, wherein, described preparing isobutene through dehydrogenation of iso-butane comprises the following steps:
With the mixture of iso-butane or iso-butane and hydrogen as raw material, carry out dehydrogenation reaction, this dehydrogenation reaction in the reactor
Operating condition as follows: the consumption of catalyst is 0.5-2g, reaction temperature is 400-700 DEG C, volume space velocity is
1000-6000h-1, reaction pressure be normal pressure；During with the mixture of iso-butane and hydrogen for raw material, in raw material, hydrogen is with different
The mol ratio of butane is 0.01:1-10:1.
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| CN106607025B (en) * | 2015-10-22 | 2020-01-03 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst and preparation method thereof |
| CN106607022B (en) * | 2015-10-22 | 2020-08-07 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of isobutane |
| CN106607023B (en) * | 2015-10-22 | 2019-11-08 | 中国石油化工股份有限公司 | For catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof |
| CN106607026B (en) * | 2015-10-22 | 2020-06-09 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by dehydrogenating isobutane and preparation method thereof |
| CN108325523B (en) * | 2018-02-02 | 2021-01-08 | 华东理工大学 | Propane dehydrogenation catalyst and preparation method thereof |
| CN110496618B (en) * | 2018-05-17 | 2021-11-19 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
| CN108840802B (en) * | 2018-07-08 | 2020-12-08 | 兰州卓雅生物科技有限公司 | Synthesis method of intermediate 4-aminophenylethanol |
| CN111468101B (en) * | 2019-01-24 | 2024-03-01 | 中国石油天然气股份有限公司 | Chromium catalyst and preparation method and application thereof |
| CN112717918A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene by dehydrogenating isobutane |
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