CN103785384A - Preparation method of catalyst for low carbon alkane dehydrogenation to prepare alkene - Google Patents
Preparation method of catalyst for low carbon alkane dehydrogenation to prepare alkene Download PDFInfo
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Abstract
The invention discloses a preparation method of a catalyst for low carbon alkane dehydrogenation. The method comprises the following steps: (1) preparing an alumina carrier containing Sn and an alkali metal additive, wherein Sn and alkali metal additive are introduced in a gelation process, and the alkali metal accounts for 10-70 wt% preferably 20-50 wt% of the total amount of the alkali metal in the final catalyst; (2) loading active metal Pt by using the alumina containing Sn and alkali metal additive prepared in the step (1) as a carrier, reintroducing alkali metal or alkali metal additive, and co-dipping the alkali metal or alkali metal additive together with a dehydrogenation active component into the carrier; and (3) carrying out vapor dechlorination on the catalyst obtained in the step (2). The catalyst prepared by the method can reduce the carbon deposition and reduce alkali metal loss in a long period dehydrogenation reaction process, and has greatly improved stability.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, particularly the preparation method of a kind of C2 ~ C5 dehydrating alkanes alkene catalyst processed, belongs to the catalyst preparation technology in Industrial Catalysis technical field.
Background technology
Along with further perfect, the exploitation in gas field, the East Sea and the application of coal bed gas of engineering are sent in transfering natural gas from the west to the east and gas east, river, cause original civil liquefied gas to steam again to refinery gradually.And the continuous expansion of China's ethene production capacity and oil refining scale, the total amount of liquefied gas is also among sustainable growth.Therefore, effective utilization of liquefied gas more and more receives people's concern, has now become the hot issue of petrochemical industry.
At present, preparing propylene by dehydrogenating propane is one of important channel of liquefied gas production industrial chemicals, and it will become the emphasis that new century petrochemical technology is researched and developed.Preparing propylene by dehydrogenating propane not only can be alleviated the propylene disparities between supply and demand of increasingly sharpening, and is also the key point of propane comprehensive utilization.Propane catalytic dehydrogenating reaction is subject to thermodynamics equilibrium limit, must under the harsh conditions of high temperature, low pressure, carry out.Too high reaction temperature, makes Deposition During Propane Pyrolysis reaction and degree of depth dehydrogenation aggravation, selectively declines; Accelerate catalyst surface carbon deposit simultaneously, make rapid catalyst deactivation.Due to the shortening of catalyst life under lower conversion of propane and harsh reaction condition, PDH method is restricted in the time of commercial Application.Therefore the catalyst for preparing propylene with propane dehydrogenation that, exploitation has high activity, high selectivity and a high stability becomes the key of this technology.CN1201715 patent discloses the Pt-Sn-K/Al for dehydrogenating low-carbon alkane
2o
3the preparation method of catalyst.USP4,914,075, USP4,353,815, USP4,420,649, USP4,506,032, USP4,595,673, EP562,906, EP98,622 grades have all been reported for propane and other dehydrogenating low-carbon alkane Pt catalyst based, have high alkane conversion and olefine selective.Although alkane conversion and the olefine selective of these catalyst under some reaction condition is high, due to the easy carbon distribution inactivation of catalyst under hot conditions, cause the poor stability of catalytic reaction, the service life of catalyst is shorter.Alkali-metal interpolation can catalyst neutralisation carrier surface part acid site, the precursor of carbon distribution is suppressed in the conversion on acidity of catalyst surface and the deposition on catalyst surface, thereby strengthen the carbon accumulation resisting ability of catalyst, improve the stability of catalyst.The final step that in prior art, alkali-metal allotment is often prepared at catalyst is flooded, active force between alkali metal and carrier a little less than, in actual commercial Application, can produce alkali-metal loss, and then along with the increase of the duration of runs and regeneration times, the carbon accumulation resisting ability of catalyst and stability all can be affected.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin.Catalyst prepared by the method can reduce carbon distribution in long period dehydrogenation reaction process, alkali metal is difficult for running off, and the stability of catalyst is largely increased.
A preparation method for catalyst for dehydrogenation of low-carbon paraffin, comprises the steps:
(1) preparation is containing the alumina support of Sn and alkali metal promoter, and wherein Sn and alkali metal promoter are introduced in plastic process, and the alkali-metal amount of introducing accounts for 10 ~ 70wt% of alkali metal total amount in final catalyst, is preferably 20 ~ 50wt%;
(2) aluminium oxide containing Sn and alkali metal promoter of preparing take step (1), as carrier, is introduced alkali metal or alkali metal promoter component and dehydrogenation active component total immersion to carrier again after supported active Pt metal;
(3) catalyst of step (2) gained is carried out to steam dechlorination.
In the inventive method step (1), be added in plastic cans by ammonia spirit with containing aluminum salt solution the stream of Sn, alkali metal promoter, under the condition that is 0.4 ~ 0.6M at ammonium concentration after cemented into bundles, stir aging 0.2～4h, preferably ageing time 0.5～2h.Wherein, alkali metal promoter is generally selected from one or more elements in Li, Na, K.Aluminium salt comprises aluminum sulfate, aluminum nitrate, alchlor, preferably alchlor, and the chlorion of introducing can be removed by follow-up steam dechlorination step, without washing.Be 0.5 ~ 1.6M containing aluminum ions concentration in the aluminum salt solution of Sn, alkali metal promoter, preferably 0.8 ~ 1.2M, flow velocity 0.1～20ml/min, preferably 0.1～5ml/min.Ammonia concn is 8～15wt%.60 ~ 80 ℃ of plastic temperature, pH value is 7.0 ~ 12.0, is preferably 8.0 ~ 10.0.After aging, by slurries filtration, vacuum drying, moulding, roasting, also can directly carry out vacuum drying, moulding, roasting without filtering.Baking temperature is 60 ~ 150 ℃, and be 8h ~ 48h drying time, is preferably dry 16 ~ 32h at 80 ~ 120 ℃.Sintering temperature is 400 ℃ ~ 800 ℃, and roasting time 2 ~ 24h is preferably roasting 4 ~ 8h at 500 ~ 700 ℃.Carrier forming method is the method that those skilled in the art is known, as dripped ball forming, extrusion modling etc.Above-mentioned alumina support can be spherical, bar shaped, microballoon or abnormity, and particle equivalent diameter is 0.1 ~ 5mm, is preferably 0.5 ~ 2mm.The carrying alumina surface area per unit volume of preparation is 200 ~ 240 m
2/ g, 0.60 ~ 0.80 cm
3/ g.
In the inventive method step (2), by Pt element wt content meter in final catalyst, take the appropriate chloroplatinic acid configuration aqueous solution or configuration containing Pt and alkali-metal mixed aqueous solution.Under 60 ~ 80 ℃ of conditions, flood 4 ~ 8h, baking temperature is 60 ~ 150 ℃, and be 1h ~ 24h drying time, is preferably dry 4 ~ 8h at 80 ~ 120 ℃.Sintering temperature is 400 ℃ ~ 800 ℃, and roasting time 2 ~ 24h is preferably roasting 4 ~ 8h at 500 ~ 700 ℃.
In the inventive method step (3), described steam dechlorination, for to process 1 ~ 20h at 300 ~ 800 ℃, is preferably at 500 ~ 700 ℃ and processes 4 ~ 8h, and the atmosphere of dechlorination, for the air containing 10v% ~ 30v% water vapour, makes chlorinity in catalyst be less than 0.15wt%.
A kind of catalyst for dehydrogenation of low-carbon paraffin, adopts above method preparation, by weight percentage, contains 0.2 ~ 0.8wt%Pt in catalyst, 0.5 ~ 3.0wt% alkali metal, 0.3 ~ 2.0wt%Sn.
Compared with prior art, preparation method's tool of a kind of catalyst for dehydrogenation of low-carbon paraffin of the present invention has the following advantages:
(1) catalyst for dehydrogenation of low-carbon paraffin that prepared by the inventive method has additive alkali metal and Sn is evenly distributed, and anti-carbon is strong, and alkali metal is difficult for running off, and the activity stability of catalyst long-term operation obviously improves;
(2) the inventive method is particularly in the aging process of plastic, can be by dripping ammoniacal liquor or the suitable concentration of distilled water control ammonium ion, adjust the isoelectric point of plastic carrier, further strengthen the strong interaction between plastic carrier and alkali metal ion, the particularly effect between meta-aluminic acid root and alkali metal ion, make potassium ion filtering, even washing, be difficult in long period course of reaction running off, and improved the dispersion effect of alkali metal ion;
(3) method for preparing catalyst is simple, and technology maturation is conducive to the industrial production of catalyst.
The specific embodiment
Enforcement below by dehydrogenating propane is described further technology of the present invention.
Example 1
Configuration concentration is the aluminum trichloride solution of 0.98M, is added in aluminum trichloride solution by every liter of solution 0.0013mol butter of tin and 0.0026mol potassium nitrate.Under stirring condition, slow the ammoniacal liquor of above-mentioned solution and concentration 8wt% and stream are added in plastic cans.Control temperature 70 C in plastic cans, above-mentioned aluminum trichloride solution coutroi velocity 2ml/min, controls ammoniacal liquor and adds speed, and maintaining material pH value in plastic cans is 8.0 ~ 10.0.After cemented into bundles, under the condition that makes slurries be 0.4M at ammonium concentration, stir aging 0.5h, then by slurries filtration, vacuum drying, moulding, roasting.Baking temperature is 80 ℃, and be 32h drying time.Sintering temperature is 700 ℃, roasting time 6h.Obtain the alumina support containing Sn 0.3wt% and K0.2 wt %.
By Pt content 0.4wt% in final catalyst, take the appropriate chloroplatinic acid configuration aqueous solution.Above-mentioned carrier floods 6h under 70 ℃ of conditions in the aqueous solution that contains chloroplatinic acid, then at 120 ℃ of dry 2h, and roasting 4h at 500 ℃.By K content 0.8wt% in final catalyst, cut contained 0.2wt%K in carrier, take the appropriate potassium nitrate configuration aqueous solution, at 70 ℃, flood 2h, and soak after Pt that similarity condition is dry, roasting.Gained material is containing activating 4h in the air of 20v% water vapour.In final catalyst, the load capacity of each component is: Pt 0.4wt%, Sn 0.3wt%, K 0.8wt%.Before reaction, gained catalyst is 500 ℃ of reduction 4h under hydrogen atmosphere.
Appreciation condition: catalyst quality 3.53g, the mass space velocity of propane is 3h
-1, reaction pressure 0.1MPa, reaction temperature is 620 ℃, adjusts response parameter according to actual response situation.
Result shows: the catalyst after 5 regeneration is being evaluated 72h continuously, and conversion of propane is 31.7%, and Propylene Selectivity is 96.4%.Coke content is only 4.42%.Catalyst after 10 regeneration is evaluated after 72h continuously, and conversion of propane is 29.8%, and Propylene Selectivity is 96.3%, and in catalyst, the weight content of potassium element is 0.8wt%.
Example 2
Configuration concentration is the aluminum trichloride solution of 1.18M, is added in aluminum trichloride solution by every liter of solution 0.0051mol butter of tin and 0.035mol lithium nitrate.Under stirring condition, slow the ammoniacal liquor of above-mentioned solution and concentration 10wt% and stream are added in plastic cans.80 ℃ of temperature in control plastic cans, above-mentioned aluminum trichloride solution coutroi velocity 5ml/min, controls ammoniacal liquor and adds speed, and maintaining material pH value in plastic cans is 8.0 ~ 10.0.Under the condition that makes slurries be 0.5M at ammonium concentration, stir aging 1h, then by slurries filtration, vacuum drying, moulding, roasting.Baking temperature is 100 ℃, and be 24h drying time.Sintering temperature is 600 ℃, roasting time 8h.Obtain the alumina support containing Sn 1.0wt% and Li 0.4wt %.
By Pt content 0.5wt% in final catalyst, take the appropriate chloroplatinic acid configuration aqueous solution.Above-mentioned carrier floods 8h under 60 ℃ of conditions in the aqueous solution that contains chloroplatinic acid, then at 100 ℃ of dry 4h, and roasting 4h at 600 ℃.By Li content 0.7wt% in final catalyst, cut contained 0.4wt%Li in carrier, take the appropriate lithium nitrate configuration aqueous solution, at 60 ℃, flood 8h, and soak after Pt that similarity condition is dry, roasting.Gained material is containing activating 4h in the air of 30v% water vapour.In the agent of gained catalyst, the load capacity of each component is: Pt 0.5wt%, Sn 1.0wt%, Li0.7wt%.Before reaction, gained catalyst is 500 ℃ of reduction 4h under hydrogen atmosphere.
Appreciation condition: catalyst quality 3.53g, the mass space velocity of propane is 3h
-1, reaction pressure 0.1MPa, reaction temperature is 620 ℃, adjusts response parameter according to actual response situation.
Result shows: the catalyst after 5 regeneration is being evaluated 72h continuously, and conversion of propane is 31.2%, and Propylene Selectivity is 95.2%.Coke content is only 5.46%.Catalyst after ten regeneration is evaluated after 72h continuously, and conversion of propane is 30.6%, and Propylene Selectivity is 96.1%, and in catalyst, the weight content of elemental lithium is 0.7wt%.
Example 3
Configuration concentration is the aluminum trichloride solution of 1.08M, is added in aluminum trichloride solution by every liter of solution 0.007mol butter of tin and 0.0085mol potassium nitrate.Under stirring condition, slow the ammoniacal liquor of above-mentioned solution and concentration 15wt% and stream are added in plastic cans.Control temperature 60 C in plastic cans, above-mentioned aluminum trichloride solution coutroi velocity 5ml/min, controls ammoniacal liquor and adds speed, and maintaining material pH value in plastic cans is 8.0 ~ 10.0.Under the condition that makes slurries be 0.5M at ammonium concentration, stir aging 2h, then by slurries vacuum drying, moulding, roasting.Baking temperature is 120 ℃, and be 16h drying time.Sintering temperature is 500 ℃, roasting time 8h.Obtain the alumina support containing Sn 1.5wt% and K0.6 wt %.
By Pt content 0.7wt% in final catalyst, take the appropriate chloroplatinic acid configuration aqueous solution.Above-mentioned carrier floods 6h under 70 ℃ of conditions in the aqueous solution that contains chloroplatinic acid, then at 120 ℃ of dry 4h, and roasting 4h at 700 ℃.By K content 1.5wt% in final catalyst, cut contained 0.6wt%K in carrier, take the appropriate potassium nitrate configuration aqueous solution, at 70 ℃, flood 6h, and soak after Pt that similarity condition is dry, roasting.Gained material is containing activating 4h in the air of 20v% water vapour.In gained catalyst, the load capacity of each component is: Pt 0.7wt%, Sn 1.5wt%, K 1.5wt%.Before reaction, gained catalyst is 500 ℃ of reduction 4h under hydrogen atmosphere.
Appreciation condition: catalyst quality 3.0g, the mass space velocity of propane is 3h
-1, reaction pressure 0.1MPa, reaction temperature is 620 ℃, adjusts response parameter according to actual response situation.
Result shows: the catalyst after 5 regeneration is being evaluated 72h continuously, and conversion of propane is 31.8%, and Propylene Selectivity is 96.6%.Coke content is only 5.08%.Catalyst after ten regeneration is evaluated after 50h continuously, and conversion of propane is 31.1%, and Propylene Selectivity is 96.1%, and in catalyst, the weight content of potassium element is 1.5wt%.
Example 4
Configuration concentration is the aluminum trichloride solution of 1.08M, is added in aluminum trichloride solution by every liter of solution 0.007mol butter of tin and 0.02mol sodium nitrate.Under stirring condition, slow the ammoniacal liquor of above-mentioned solution and concentration 8wt% and stream are added in plastic cans.Control temperature 70 C in plastic cans, above-mentioned aluminum trichloride solution coutroi velocity 2ml/min, controls ammoniacal liquor and adds speed, and maintaining material pH value in plastic cans is 8.0 ~ 10.0.After cemented into bundles, under the condition that makes slurries be 0.6 at ammonium concentration, stir aging 2h, then by slurries vacuum drying, moulding, roasting.Baking temperature is 100 ℃, and be 24h drying time.Sintering temperature is 700 ℃, roasting time 6h.Obtain the alumina support containing Sn 1.5wt% and Na0.8 wt %.
By Pt content 0.8wt% in final catalyst, take the appropriate chloroplatinic acid configuration aqueous solution.Above-mentioned carrier floods 6h under 70 ℃ of conditions in the aqueous solution that contains chloroplatinic acid, then at 120 ℃ of dry 4h, and roasting 4h at 700 ℃.By Na content 1.8wt% in final catalyst, cut contained 0.8wt%Na in carrier, take the appropriate sodium nitrate configuration aqueous solution, at 70 ℃, flood 6h, and soak after Pt that similarity condition is dry, roasting.Gained material is containing activating 4h in the air of 20v% water vapour.In gained catalyst, the load capacity of each component is: Pt 0.8wt%, Sn 1.5wt%, Na 1.8wt%.Before reaction, gained catalyst is 500 ℃ of reduction 4h under hydrogen atmosphere.
Appreciation condition: catalyst quality 3.53g, the mass space velocity of propane is 3h
-1, reaction pressure 0.1MPa, reaction temperature is 620 ℃, adjusts response parameter according to actual response situation.
Result shows: the catalyst after 5 regeneration is being evaluated 72h continuously, and conversion of propane is 31.4%, and Propylene Selectivity is 96.3%.Coke content is only 5.12%.Catalyst after five regeneration is evaluated after 72h continuously, and conversion of propane is 31.2%, and Propylene Selectivity is 96.0%, and in catalyst, the weight content of sodium element is 1.8wt%.
Comparative example
By patent, 201010272305.X prepares dehydrogenation.
Configuration concentration is the aluminum trichloride solution of 0.98M, is added in aluminum trichloride solution by every liter of solution 0.0013mol butter of tin.Under stirring condition, slow the ammoniacal liquor of above-mentioned solution and concentration 8wt% and stream are added in plastic cans.Control temperature 70 C in plastic cans, above-mentioned aluminum trichloride solution coutroi velocity 2ml/min, controls ammoniacal liquor and adds speed, and maintaining material pH value in plastic cans is 8.0 ~ 10.0.After cemented into bundles, slurries are aging 0.5h under stirring, then slurries is filtered, dry, moulding, roasting.Baking temperature is 80 ℃, and be 4h drying time.Sintering temperature is 700 ℃, roasting time 6h.Obtain the alumina support containing Sn 0.3wt%.
By Pt content 0.4wt% in final catalyst, take the appropriate chloroplatinic acid configuration aqueous solution.Above-mentioned carrier floods 6h under 70 ℃ of conditions in the aqueous solution that contains chloroplatinic acid, then at 120 ℃ of dry 2h, and roasting 4h at 500 ℃.Gained material is containing activating 4h in the air of 20v% water vapour.By K content 0.8wt% in final catalyst, take the appropriate potassium nitrate configuration aqueous solution, at 70 ℃, flood 2h, and soak after Pt that similarity condition is dry, roasting.In gained catalyst, the load capacity of each component is: Pt 0.4wt%, Sn 0.3wt%, K0.8wt%.Before reaction, gained catalyst is 500 ℃ of reduction 4h under hydrogen atmosphere.
Appreciation condition: catalyst quality 3.53g, the mass space velocity of propane is 3h
-1, reaction pressure 0.1MPa, reaction temperature is 620 ℃, adjusts response parameter according to actual response situation.
Result shows: the catalyst after 5 regeneration is being evaluated 72h continuously, and conversion of propane is 29.2%, and Propylene Selectivity is 95.8%.Coke content is 7.52%.Catalyst after 10 regeneration is evaluated after 72h continuously, and conversion of propane is 27.18%, and Propylene Selectivity is 94.4%, and in catalyst, the weight content of potassium element is 0.7wt%.Compared with embodiment 1, all there is a certain distance in the activity of the stability of coke content, catalyst and circulation rear catalyst.
Claims (11)
1. a preparation method for catalyst for dehydrogenation of low-carbon paraffin, is characterized in that: comprise the steps:
(1) preparation is containing the alumina support of Sn and alkali metal promoter, and wherein Sn and alkali metal promoter are introduced in plastic process, and the alkali-metal amount of introducing accounts for 10 ~ 70wt% of alkali metal total amount in final catalyst;
(2) aluminium oxide containing Sn and alkali metal promoter of preparing take step (1), as carrier, is introduced alkali metal or alkali metal promoter component and dehydrogenation active component total immersion to carrier again after supported active Pt metal;
(3) catalyst of step (2) gained is carried out to steam dechlorination.
2. method according to claim 1, it is characterized in that: in step (1), be added in plastic cans by ammonia spirit with containing aluminum salt solution the stream of Sn, alkali metal promoter, under the condition that is 0.4 ~ 0.6M at ammonium concentration after cemented into bundles, stir aging 0.2～4h.
3. method according to claim 1 and 2, is characterized in that: alkali metal promoter is selected from one or more in Li, Na, K, and aluminium salt comprises aluminum sulfate, aluminum nitrate, alchlor.
4. method according to claim 2, is characterized in that: be 0.5 ~ 1.6M containing aluminum ions concentration in the aluminum salt solution of Sn, alkali metal promoter, and flow velocity 0.1～20ml/min, ammonia concn is 8～15wt%.
5. method according to claim 4, is characterized in that: be 0.8 ~ 1.2M containing aluminum ions concentration in the aluminum salt solution of Sn, alkali metal promoter, and flow velocity 0.1～5ml/min.
6. method according to claim 1 and 2, is characterized in that: 60 ~ 80 ℃ of plastic temperature, pH value is 7.0 ~ 12.0.
7. method according to claim 2, is characterized in that: after aging, directly carry out vacuum drying, moulding, roasting by slurries filtration, vacuum drying, moulding, roasting or without filtering.
8. method according to claim 7, is characterized in that: baking temperature is 60 ~ 150 ℃, and be 8h ~ 48h drying time, and sintering temperature is 400 ℃ ~ 800 ℃, roasting time 2 ~ 24h.
9. method according to claim 1, it is characterized in that: in step (2), by Pt element wt content meter in final catalyst, take the appropriate chloroplatinic acid configuration aqueous solution or the configuration mixed aqueous solution containing Pt, K, carrier 4 ~ 8h that under 60 ~ 80 ℃ of conditions, impregnation steps (1) makes, baking temperature is 60 ~ 150 ℃, be 1h ~ 24h drying time,, sintering temperature is 400 ℃ ~ 800 ℃, roasting time 2 ~ 24h.
10. method according to claim 1, is characterized in that: in step (3), described steam dechlorination is for process 1 ~ 20h at 300 ~ 800 ℃, and the atmosphere of dechlorination is the air containing 10v% ~ 30v% water vapour.
11. 1 kinds of catalyst for dehydrogenation of low-carbon paraffin, is characterized in that: adopt arbitrary described method preparation in claim 1 to 10, by weight percentage, contain 0.2 ~ 0.8wt%Pt in catalyst, 0.5 ~ 3.0wt% alkali metal, 0.3 ~ 2.0wt%Sn.
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| CN107213919A (en) * | 2016-03-22 | 2017-09-29 | 北京安耐吉能源工程技术有限公司 | A kind of alumina support and its preparation method and application |
| CN107213909A (en) * | 2016-03-22 | 2017-09-29 | 北京安耐吉能源工程技术有限公司 | A kind of dehydrogenation and its preparation method and application |
| CN107216230A (en) * | 2016-03-22 | 2017-09-29 | 北京安耐吉能源工程技术有限公司 | Dehydrogenation of isobutane method |
| CN107213909B (en) * | 2016-03-22 | 2020-05-12 | 北京安耐吉能源工程技术有限公司 | Dehydrogenation catalyst and preparation method and application thereof |
| CN107213919B (en) * | 2016-03-22 | 2020-05-12 | 北京安耐吉能源工程技术有限公司 | Alumina carrier, preparation method and application thereof |
| CN107216230B (en) * | 2016-03-22 | 2020-10-27 | 北京安耐吉能源工程技术有限公司 | Isobutane dehydrogenation method |
| CN108067227A (en) * | 2017-03-29 | 2018-05-25 | 天津大学 | A kind of high dispersive is in platinum based catalyst of carrier alundum and its preparation method and application |
| CN108067227B (en) * | 2017-03-29 | 2020-08-18 | 天津大学 | Platinum-based catalyst highly dispersed in carrier aluminum oxide and preparation method and application thereof |
| CN112007639A (en) * | 2020-09-01 | 2020-12-01 | 辽宁石油化工大学 | Preparation method of dehydrogenation catalyst with low carbon deposition rate |
| CN112007639B (en) * | 2020-09-01 | 2023-03-21 | 辽宁石油化工大学 | Preparation method of dehydrogenation catalyst with low carbon deposition rate |
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