CN102909099A - Method for the reductive activation of dehydrogenation catalyst by using gas mixture of hydrocarbon/hydrogen - Google Patents
Method for the reductive activation of dehydrogenation catalyst by using gas mixture of hydrocarbon/hydrogen Download PDFInfo
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Abstract
The present invention discloses a method for the reductive activation of a dehydrogenation catalyst by using a gas mixture of hydrocarbon/hydrogen. The dehydrogenation catalyst is a platinum group metal-supported catalyst. The reductive activation of the dehydrogenation catalyst is performed before use. The gas mixture of hydrocarbon/hydrogen is used as a reducing gas for the reductive activation, a reductive activation temperature is from 300 DEG C to 600 DEG C, the reductive activation time is from 0.5 hours to 10.0 hours, preferably 1-5 hours, and the volume hourly space velocity of the reducing gas during the reductive activation is 500- 5000h<-1>. Compared with the prior art, the method of the present invention can further improve the activity and the activity stability of the dehydrogenation catalyst for light alkanes, and raises the yield of target products within a certain temperature range.
Description
Technical field
The invention relates to the reduction activation method of a kind of reduction activation method of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, particularly C3 ~ C5 dehydrating alkanes alkene catalyst processed.
Background technology
Entered since the new century, world's petrochemical material and petroleum chemicals demand will sustainable growths, demand as petrochemical industry basic material propylene and butylene will continue to increase, and the demand that conventional steam cracking and FCC technology production capacity can not satisfy rapid growth its market occurred global in short supply.And day by day deficient along with petroleum resources, the production of propylene has been that raw material changes to the diversified technology path of raw material sources from simple dependence oil, particularly take the technology path of low-carbon alkanes as waste alkene.In recent years, the technology that dehydrogenating propane is produced propylene had obtained large development, and it is very fast that particularly the technology of dehydrogenating propane (PDH) propylene processed had the regional development of resources advantage in recent years in the Middle East etc., becomes the third-largest propylene production.
The propane catalytic dehydrogenating reaction is subjected to thermodynamics equilibrium limit, must carry out under the harsh conditions of high temperature, low pressure.Too high reaction temperature makes Deposition During Propane Pyrolysis reaction and degree of depth dehydrogenation aggravation, selective decline; Accelerate simultaneously the catalyst surface carbon deposit, make rapid catalyst deactivation.Because the shortening of catalyst life is restricted the PDH method under lower conversion of propane and the harsh reaction condition when commercial Application.Therefore, exploitation has the catalyst for preparing propylene with propane dehydrogenation of high selectivity and high stability and the key that supporting technique becomes this technology.At present the dehydrogenating propane technology is take the Catafin technique of the Oleflex technique of Uop Inc. and U.S. Air Product company as representative.Oleflex technique is mainly catalyst based as main take Pt, and Catafin technique is mainly with Cr
2O
3/ Al
2O
3Be main.
Load type platinum is catalyst based to be an important class in the alkane dehydrogenating catalyst, and the production method of such catalyst is also open in the art.USP4914075, USP4353815, USP4420649, USP4506032, USP4595673, EP562906, EP98622 etc. have reported for propane and other dehydrogenating low-carbon alkane Pt catalyst based, have high alkane conversion and olefine selective.USP3897368 and CN87108352 disclose a kind of method of producing hud typed catalyst, and Pt optionally concentrates and is deposited on the outer surface of catalyst carrier, and the inner Pt content of catalyst carrier is lower, can improve the utilization rate of reactive metal.This above-mentioned class catalyst must be used hydrogen reducing before use, and the catalyst after the reduction is used for dehydrogenation reaction.In this class catalyst, the constant temperature reduction is adopted in reduction, and temperature is at 400 ~ 650 ℃.CN101138734A, CN101015802A be constant temperature reductase 12 ~ 10h in 400 ~ 600 ℃ of hydrogen streams, and CN1844324A is at 400 ℃ of lower constant temperature reduction 7h, and CN101108362A is preferably at 450 ~ 550 ℃ of lower constant temperature reduction 4 ~ 6h.Reduction can make the active component of catalyst become the elemental metals attitude, can also guarantee that the metal component particle disperses, but constant temperature fast restore under higher temperature, easily cause the sintering of metallic particles, make the catalyst metal particles after the reduction bigger than normal, cause the surface area of the simple substance Pt that comes out less than normal, finally make the activity and selectivity of catalyst lower.The water or the OH that use the pure hydrogen reduction to generate
-Increase the transfer ability of metallic atom or metallic compound, easily caused the catalyst activity accumulation of metal.CN200410096308.7 is under 240 ~ 550 ℃ of conditions in temperature, molecular sieve, noble metal catalyst are contacted 5～30 hours with the gaseous mixture of hydrogen and ammonia, in reduction, strong acid center conductively-closed in the molecular sieve, this method is not suitable for the reduction process of lower carbon number hydrocarbons dehydrogenation yet.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of reduction activation method of catalyst for dehydrogenation of low-carbon paraffin, further improve on the basis of existing technology initial activity and the activity stability of catalyst, and in certain temperature range, improve the yield of purpose product.
The present invention comprises following content take the method for hydrocarbon/hydrogen gaseous mixture reduction activation dehydrogenation: dehydrogenation is as the platinum family loaded catalyst, dehydrogenation carries out reduction activation before use, reduction activation is take hydrocarbon/hydrogen gaseous mixture as reducing gases, the reduction activation temperature is 300 ~ 600 ℃, be preferably 350～550 ℃, the reduction activation time is 0.5 ~ 10.0 hour, is preferably 1～5 hour, and the volume space velocity of reducing gases during reduction activation (the reducing gases volume under standard state calculates) is as 500 ~ 5000h
-1
In the inventive method, hydrocarbon/hydrogen gaseous mixture is the gaseous mixture of hydrocarbon and hydrogen, and hydrocarbon wherein is CH
4, namely hydrocarbon/hydrogen gaseous mixture is for containing CH
4Hydrogen, CH
4Generally account for 5% ~ 70%, preferred 10% ~ 50% of hydrocarbon/hydrogen gaseous mixture cumulative volume.
In the inventive method, reduction activation can be adopted one of following dual mode: (1) constant temperature reduction activation process, (2) first temperature programmed reduction then adopt constant temperature reduction in conjunction with the reduction activation process.In the mode (1), directly be warmed up to the reduction of reduction temperature constant temperature, reduction temperature is 350 ~ 600 ℃, and preferred 400 ~ 550 ℃, the preferred recovery time is 0.5 ~ 10.0 hour.In the mode (2), temperature programmed reduction is the operation of arbitrary temp section in 300 ~ 600 ℃, preferably arbitrary temp section operation in 350 ~ 550 ℃, 0.5 ~ 10 ℃/min of heating rate, preferred 0.5 ~ 5 ℃/min, the temperature programming time is 15 ~ 90min, is preferably 20 ~ 40min; Then the constant temperature reduction is 0.2 ~ 5.0 hour, and the constant temperature reduction temperature is 350 ~ 600 ℃.Temperature programmed reduction refers to heat up by the programming rate of control, passes into the reduction activation method that reducing gases is carried out catalyst in the time of intensification.
Dehydrogenation after the reduction activation generally needs to use the mist of hydrogen, hydrogen sulfide and nitrogen to vulcanize, and can carry out dehydrogenation reaction after the sulfuration, and vulcanization process can adopt this area routine techniques.The dehydrogenation reaction raw material is generally propane or butane, obtains propylene or butylene through dehydrogenation, and the dehydrogenation reaction temperature is 500 ~ 600 ℃, feed volume air speed 500 ~ 5000h
-1, absolute pressure 0.1 ~ 0.5MPa, hydrogen in the unstripped gas: the molar ratio of low-carbon alkanes is between 1:1 ~ 6:1.
In the dehydrogenation method of reducing of the present invention, dehydrogenation is the platinum family loaded catalyst, and one or more in platinum, palladium, iridium, rhodium or the osmium in the platinum family are as active component, and 0.01% ~ 2% of vehicle weight is counted with simple substance in the platinum group metal in catalyst.Simultaneously can contain suitable auxiliary agent in the dehydrogenation, such as IV A family element, alkali metal, thulium etc.IV A family element is preferably Sn, and its content is counted 0.1% ~ 10% of vehicle weight with element, and alkali metal content is counted 0.1% ~ 10% of vehicle weight with element.Reactive metal and auxiliary agent preferably exist with the form of oxidation state in the finished catalyst, dehydrogenation can adopt the method preparation of this area routine, as adopt infusion process load dehydrogenation active component, auxiliary agent can and/or adopt infusion process to introduce in the carrier preparation process.
Catalyst carrier of the present invention is selected from high-temperature inorganic oxide, is generally the material that a kind of porous has adsorptivity.The composition of porous carrier should be uniformly, and is infusibility under the condition of using.Resistant to elevated temperatures inorganic oxide comprises: aluminium oxide, magnesia, chromium oxide, boron oxide, titanium oxide, zinc oxide, zirconia, perhaps following two kinds of hopcalites; And various potteries, various alumina, silica, synthetic or naturally occurring various silicate or clay.Preferred inorganic oxide carrier is Al
2O
3Its crystal habit can be γ-Al
2O
3, θ-Al
2O
3, η-Al
2O
3, preferred crystal habit is γ-Al
2O
3
Platinum group metal in the catalyst can adopt co-precipitation, ion-exchange or impregnating mode to introduce carrier.Preferred method is to adopt water-soluble decomposable platinum group metal compounds impregnated carrier.Adoptable water soluble compound or complex are: chloroplatinic acid, chloro-iridic acid, the acid of chlorine palladium, ammonium chloroplatinate, bromoplatinic acid, tri-chlorination platinum, palladium nitrate, diaminourea palladium hydroxide, chlorine four ammonia palladiums, chlorine six ammonia palladiums, rhodium chloride hydrate, rhodium nitrate, tribromide iridium, iridochloride, iridic chloride, potassium hexachloroiridate or iridium sodium chloride etc.The chlorine-containing compound of preferred platinum, palladium, iridium, rhodium or osmium.
IV A family elemental constituent in the catalyst can be adopted any mode to introduce in the catalyst and reach component and evenly distribute.Suitable soluble compound is its oxide, chloride, nitrate or alkoxide, such as stannous chloride, butter of tin, butter of tin pentahydrate, stannous bromide, germanium dioxide, germanium tetrachloride etc.Preferred butter of tin, germanium tetrachloride, most preferably butter of tin.In addition, IV A family metal component also can be introduced in the process of carrier preparation.
Alkali and alkaline earth metal ions in the catalyst can any known mode be introduced in the catalyst, preferably with the method for the solution impregnating carrier of the water-soluble decomposable compound of alkali metal or alkaline-earth metal.Described alkali metal is preferably K, Na or Li.
Existing dehydrogenation is taked traditional pure H when reduction
2Reduction, and constant temperature reduction under the higher temperature are although this activation method has the sufficient advantage of dehydrogenation activity metallic reducing, but the reduction after metallic particles bigger than normal cause selectively relatively relatively poor, and, along with the reaction carrying out, active decline comparatively fast, and required reaction temperature is higher.In the activation method of dehydrogenation of the present invention, select CH
4With the mist of hydrogen as reducing atmosphere.Improved the reduction degree of catalyst, the initial activity after the catalyst reduction is high, and (500 ℃ ~ 600 ℃) yield of purpose product is higher than the catalyst of pure hydrogen reduction under the uniform temp at a certain temperature.The reducing process that adopts simultaneously temperature programming to combine with constant temperature is carried out reduction activation to catalyst, catalyst metal particles after the reduction is disperseed more even, and granular size is more appropriate, and the surface area of the simple substance Pt that comes out increases.Avoid under violent reducing condition Al
2O
3Pt bunch of quick formation and the easy large Pt particle of formation of assembling on surface, also can avoid some adjuvant component of not wishing to reduce by drastic reduction, affected synergism of additives (the particularly synergy between active component Pt and the adjuvant component Sn), and then improved the serviceability of catalyst, particularly improved the stability of the selective and long-time reaction of purpose product.
The specific embodiment
Dehydrogenation method of reducing of the present invention adopts CH
4With the mist of hydrogen be reducing gases, the reducing process that is combined by temperature programming and constant temperature has replaced the constant temperature reduction under traditional higher temperature.
Dehydrogenation of the present invention is counted 0.01% ~ 2% of vehicle weight preferably take Pt as active component with simple substance; Take Sn as auxiliary agent, the content of Sn is counted 0.1% ~ 10% of vehicle weight with simple substance, and auxiliary agent can also comprise K, rare earth metal etc. simultaneously.
Example 1
Preparation contains the alumina support of Sn.Behind the aluminum trichloride solution and the mixing of 0.01M butter of tin solution with a certain amount of 0.98M, add an amount of mass concentration and be 8% ammoniacal liquor, under 60 ~ 80 ℃, in neutralizing tank, mix, control pH value 7.0 ~ 9.0, after filtration, washing, the acidifying, the balling-up of pressurizeing in the oil ammonia column is through super-dry, aging, 650 ~ 750 ℃ of roastings 4 hours, namely get the alumina globule that contains Sn 0.3wt%.
To contain the alumina globule carrier of 0.3% Sn at 800 ℃ of roasting 3h, with the carrier after the roasting and the aqueous solution that contains chloroplatinic acid dipping 6h under 70 ℃, at 120 ℃ of oven dry 2h, 500 ℃ of lower roasting 4h.Then in containing the air of water vapour, activate 4h.Then descend and contain KNO at 70 ℃
3Aqueous solution dipping 2h, dry, roasting under the same condition.The load capacity of each component is in the catalyst: Pt 0.5wt%, Sn 0.3wt%, K 0.5wt%.
Reducing condition:At 350 ~ 470 ℃ of scope internal program heating reductions, heating rate is 2 ℃/min, then at 470 ℃ of constant temperature reduction 30min.The volume space velocity of reducing gases is 1500h in the reduction process
-1, reducing gases CH
4Account for 10% of gaseous mixture gas volume.
Conditions of vulcanization: the mass velocity 900h of the mixed gas of hydrogen sulfide, hydrogen and nitrogen
-1, molar ratio is 1:9:5,470 ℃ of temperature, cure time 40min.
Appreciation condition: volume space velocity 2000 h of mist charging
-1, reaction pressure 0.1MPa, reaction temperature is 550 ℃, hydrogen in the charging: the molar ratio of propane is 1:1.Evaluation result sees Table 1.
Comparative example
The preparation of catalyst is with example 1.
Reducing condition: volume space velocity is 1500h
-1, 470 ℃ the reduction 90min, with pure hydrogen as reducing gases.
Conditions of vulcanization:The volume space velocity of the mixed gas of hydrogen sulfide, hydrogen and nitrogen is 900h
-1, molar ratio is 1:9:5,470 ℃ of temperature, soak time 40min.
Appreciation condition:Feed volume air speed 2000 h
-1, reaction pressure 0.1MPa, reaction temperature is 550 ℃, hydrogen in the charging: the mol ratio of propane is 1:1.Evaluation result sees Table 1.
Example 2
The preparation of catalyst is with example 1.
Reducing condition:At 320 ~ 450 ℃ of scope internal program heating reductions, heating rate is 3.0 ℃/min, then at 450 ℃ of constant temperature reduction 60min.The volume space velocity of reducing gases is 2500h in the reduction process
-1, reducing gases CH4 accounts for 15% of gaseous mixture gas volume.
Conditions of vulcanization: the mass velocity 900h of the mixed gas of hydrogen sulfide, hydrogen and nitrogen
-1, molar ratio is 1:9:5,470 ℃ of temperature, cure time 40min.
Appreciation condition: volume space velocity 2000 h of mist charging
-1, reaction pressure 0.1MPa, reaction temperature is 550 ℃, hydrogen in the charging: the molar ratio of propane is 1:1.Evaluation result sees Table 1.
Example 3
The preparation of catalyst is with example 1.
Reducing condition:At 400 ~ 500 ℃ of scope internal program heating reductions, heating rate is 2.0 ℃/min, then at 470 ℃ of constant temperature reduction 30min.The volume space velocity of reducing gases is 800h in the reduction process
-1, reducing gases CH
4Account for 20% of gaseous mixture gas volume.
Conditions of vulcanization: the mass velocity 900h of the mixed gas of hydrogen sulfide, hydrogen and nitrogen
-1, molar ratio is 1:9:5,470 ℃ of temperature, cure time 40min.
Appreciation condition: volume space velocity 2000 h of mist charging
-1, reaction pressure 0.1MPa, reaction temperature is 550 ℃, hydrogen in the charging: the molar ratio of propane is 1:1.Evaluation result sees Table 1.
Example 4
The preparation of catalyst is with example 1.
Reducing condition:At 350 ~ 470 ℃ of scope internal program heating reductions, heating rate is 1 ℃/min, then at 470 ℃ of constant temperature reduction 50min.The volume space velocity of reducing gases is 1500h in the reduction process
-1, reducing gases CH
4Account for 30% of gaseous mixture gas volume.
Conditions of vulcanization: the mass velocity 900h of the mixed gas of hydrogen sulfide, hydrogen and nitrogen
-1, molar ratio is 1:9:5,470 ℃ of temperature, cure time 40min.
Appreciation condition: volume space velocity 2000 h of mist charging
-1, reaction pressure 0.1MPa, reaction temperature is 550 ℃, hydrogen in the charging: the molar ratio of propane is 1:1.Evaluation result sees Table 1.
Example 5
The preparation of catalyst is with example 1.
Reducing condition:At 350 ~ 500 ℃ of scope internal program heating reductions, heating rate is 1 ℃/min, then at 500 ℃ of constant temperature reduction 40min.The volume space velocity of reducing gases is 1500h in the reduction process
-1, reducing gases CH
4Account for 40% of gaseous mixture gas volume.
Conditions of vulcanization: the mass velocity 900h of the mixed gas of hydrogen sulfide, hydrogen and nitrogen
-1, molar ratio is 1:9:5,470 ℃ of temperature, cure time 40min.
Appreciation condition: volume space velocity 2000 h of mist charging
-1, reaction pressure 0.1MPa, reaction temperature is 550 ℃, hydrogen in the charging: the molar ratio of propane is 1:1.Evaluation result sees Table 1.
Table 1 dehydrogenation evaluation result.
| ? | Initial stage conversion of propane % | Latter stage conversion of propane % | Initial stage Propylene Selectivity % | Latter stage Propylene Selectivity % |
| Embodiment 1 | 23.0 | 19.2 | 93.9 | 93.6 |
| Embodiment 2 | 23.9 | 20.5 | 94.0 | 93.8 |
| Embodiment 3 | 24.4 | 21.3 | 94.1 | 93.9 |
| Embodiment 4 | 24.7 | 21.9 | 94.3 | 94.1 |
| Embodiment 5 | 23.6 | 21.3 | 94.3 | 94.2 |
| Comparative example | 21.5 | 17.4 | 93.1 | 92.5 |
The initial reaction time: 1 hour
Reaction time in latter stage: 30 hours
Conversion ratio and selectively in mole.
Evaluation result by table 1 can be found out, adopt method of reducing provided by the invention to process dehydrogenation, dehydrogenation has preferably initial activity and activity stability, and at a certain temperature, and the yield of purpose product is higher than under the uniform temp catalyst with hydrogen reducing.
Claims (10)
1. method with hydrocarbon/hydrogen gaseous mixture reduction activation dehydrogenation, dehydrogenation is the platinum family loaded catalyst, dehydrogenation carries out reduction activation before use, it is characterized in that: reduction activation is take hydrocarbon/hydrogen gaseous mixture as reducing gases, the reduction activation temperature is 300 ~ 600 ℃, the reduction activation time is 0.5 ~ 10.0 hour, is preferably 1～5 hour, and the volume space velocity of reducing gases is 500 ~ 5000h during reduction activation
-1
2. it is characterized in that in accordance with the method for claim 1: the reduction activation temperature is 350～550 ℃.
3. according to claim 1 or 2 described methods, it is characterized in that: the reduction activation time is 1～5 hour.
4. in accordance with the method for claim 1, it is characterized in that: hydrocarbon/hydrogen gaseous mixture is the gaseous mixture of hydrocarbon and hydrogen, and hydrocarbon wherein is CH
4, CH
4Account for 5% ~ 70% of hydrocarbon/hydrogen gaseous mixture cumulative volume.
5. it is characterized in that in accordance with the method for claim 4: CH
4Account for 10% ~ 50% of hydrocarbon/hydrogen gaseous mixture cumulative volume.
6. in accordance with the method for claim 1, it is characterized in that: constant temperature reduction activation process is adopted in reduction activation, directly is warmed up to the reduction of reduction temperature constant temperature, and reduction temperature is 350 ~ 600 ℃, and preferred 400 ~ 550 ℃, the preferred recovery time is 0.5 ~ 10.0 hour.
7. in accordance with the method for claim 1, it is characterized in that: reduction activation adopt first temperature programmed reduction then constant temperature reduction in conjunction with the reduction activation process, temperature programmed reduction is the operation of arbitrary temp section in 300 ~ 600 ℃, preferably arbitrary temp section operation in 350 ~ 550 ℃, 0.5 ~ 10 ℃/min of heating rate, preferred 0.5 ~ 5 ℃/min, the temperature programming time is 15 ~ 90min, is preferably 20 ~ 40min; Then the constant temperature reduction is 0.2 ~ 5.0 hour, and the constant temperature reduction temperature is 350 ~ 600 ℃; Temperature programmed reduction refers to heat up by the programming rate of control, passes into the reduction activation method that reducing gases is carried out catalyst in the time of intensification.
8. in accordance with the method for claim 7, it is characterized in that: temperature programmed reduction is the operation of arbitrary temp section in 350 ~ 550 ℃, and heating rate is 0.5 ~ 5 ℃/min, and the temperature programming time is 20 ~ 40min.
9. in accordance with the method for claim 1, it is characterized in that: the dehydrogenation after the reduction activation, use the mist of hydrogen, hydrogen sulfide and nitrogen to vulcanize, can carry out dehydrogenation reaction after the sulfuration, dehydrogenation reaction low-carbon alkanes raw material is propane or butane, obtain propylene or butylene through dehydrogenation, the dehydrogenation reaction temperature is 500 ~ 600 ℃, feed volume air speed 500 ~ 5000h
-1, absolute pressure 0.1 ~ 0.5MPa, hydrogen in the unstripped gas: the molar ratio of low-carbon alkanes is between 1:1 ~ 6:1.
10. in accordance with the method for claim 1, it is characterized in that: dehydrogenation is the platinum family loaded catalyst, in platinum, palladium, iridium, rhodium or the osmium in the platinum family one or more are as active component, 0.01% ~ 2% of vehicle weight is counted with simple substance in the platinum group metal in catalyst, contain simultaneously auxiliary agent Sn, auxiliary agent Sn content is counted 0.1% ~ 10% of vehicle weight with element.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108607551A (en) * | 2018-05-17 | 2018-10-02 | 福州大学 | One kind is for dehydrogenating low-carbon alkane metallic catalyst and its preparation method and application |
| CN109796294A (en) * | 2019-02-22 | 2019-05-24 | 西南化工研究设计院有限公司 | Using the preparing propylene by dehydrogenating propane reaction system and methods and applications of platinum group catalyst |
| CN112237929A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenating light alkane and method for preparing olefin |
| CN115779894A (en) * | 2022-12-27 | 2023-03-14 | 黄河三角洲京博化工研究院有限公司 | Pt-based catalyst taking bimetallic oxide as carrier, preparation method and application |
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| CN1541139A (en) * | 2001-06-28 | 2004-10-27 | Isis | Processfor activation of catalyst comprising cobalt compound and support |
| CN101108362A (en) * | 2006-07-19 | 2008-01-23 | 中国石化集团金陵石油化工有限责任公司 | Catalyzer used for low carbon alkane catalytic dehydrogenation and method of manufacturing propylene by paraffin hydrocarbons catalytic dehydrogenation with the same as catalyzer |
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| US4914075A (en) * | 1988-12-05 | 1990-04-03 | Uop | Dehydrogenation catalyst composition |
| CN1226462A (en) * | 1998-02-20 | 1999-08-25 | 中国科学院大连化学物理研究所 | Alkyl aromatic hydrocarbon dehydrogenation catalyst and preparation thereof |
| CN1541139A (en) * | 2001-06-28 | 2004-10-27 | Isis | Processfor activation of catalyst comprising cobalt compound and support |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108607551A (en) * | 2018-05-17 | 2018-10-02 | 福州大学 | One kind is for dehydrogenating low-carbon alkane metallic catalyst and its preparation method and application |
| CN108607551B (en) * | 2018-05-17 | 2021-04-27 | 福州大学 | Metal catalyst for dehydrogenation of low-carbon alkane and preparation method and application thereof |
| CN109796294A (en) * | 2019-02-22 | 2019-05-24 | 西南化工研究设计院有限公司 | Using the preparing propylene by dehydrogenating propane reaction system and methods and applications of platinum group catalyst |
| CN112237929A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenating light alkane and method for preparing olefin |
| CN115779894A (en) * | 2022-12-27 | 2023-03-14 | 黄河三角洲京博化工研究院有限公司 | Pt-based catalyst taking bimetallic oxide as carrier, preparation method and application |
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|---|---|
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