CN104226307A - Platinum-based catalyst, preparation method and application thereof, and preparation method for propylene - Google Patents
Platinum-based catalyst, preparation method and application thereof, and preparation method for propylene Download PDFInfo
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- CN104226307A CN104226307A CN201310229758.8A CN201310229758A CN104226307A CN 104226307 A CN104226307 A CN 104226307A CN 201310229758 A CN201310229758 A CN 201310229758A CN 104226307 A CN104226307 A CN 104226307A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 34
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000001294 propane Substances 0.000 claims abstract description 43
- 238000001035 drying Methods 0.000 claims abstract description 38
- 238000001354 calcination Methods 0.000 claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 30
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 17
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 16
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 16
- 239000001119 stannous chloride Substances 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 19
- 230000003197 catalytic effect Effects 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 238000013329 compounding Methods 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract 5
- 238000002156 mixing Methods 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000011259 mixed solution Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 206010013786 Dry skin Diseases 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 8
- 230000009467 reduction Effects 0.000 description 5
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GOQFGEHFZBDYEC-UHFFFAOYSA-N [AlH2+] Chemical class [AlH2+] GOQFGEHFZBDYEC-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- -1 isopropyl alkene Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a platinum-based catalyst, a preparation method and an application thereof, and a preparation method for propylene. The preparation method of the platinum-based catalyst comprises the following steps of (1) mixing activated aluminium oxide with an auxiliary agent solution uniformly to obtain a mixed solution, vibrating for 1-6 hours under ultrasonic assistant at a temperature of 30-50 DEG C, drying and calcining to obtain a precursor, wherein the auxiliary agent solution is a stannous chloride solution and/or indium nitrate solution and a mass ratio of activated aluminium oxide to the auxiliary agent is (10:1)-(450:1); and (2) mixing the precursor with a chloroplatinic acid solution uniformly, vibrating for 1-6 hours under ultrasonic assistant at a temperature of 30-50 DEG C, drying and calcining, wherein a mass ratio of activated aluminium oxide to chloroplatinic acid is (40:1)-(500:1). The preparation method is simple in process and short in time; the prepared platinum-based catalyst can catalyze propane dehydrogenation to prepare propylene; active components are uniformly dispersed on carrier surfaces; and the prepared platinum-based catalyst has relatively high activity, propylene selectivity and stability.
Description
Technical field
The present invention relates to a kind of platinum based catalyst and preparation method thereof, application and the preparation method of propylene.
Background technology
Propylene is the basic chemical raw materials of three large synthetic materials, mainly for the production of acrylonitrile, isopropyl alkene, acetone and expoxy propane etc.So the world today is to the trend of the demand of propylene in growth fast.Traditional propylene supply is mainly from the byproduct of petroleum cracking ethene and petroleum catalytic cracking process, and its output can't be met the need of market, and expanding propylene source is a kind of trend.Preparing propylene by dehydrogenating propane technique causes the great interest of people, the technique of Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane is developed at the end of last century, current industrialized technique mainly contains Oleflex technique (the preparing propylene by dehydrogenating propane technique of Uop Inc.'s exploitation), Catofin technique (the preparing propylene by dehydrogenating propane technique of ABB Lummus company exploitation) etc., and domestic still do not have autonomous production technology.
Propane catalytic dehydrogenation is thermodynamically the reversible reaction that heat absorption, molecule increase, and conversion ratio depends on the thermodynamical equilibrium of this reaction, and in order to obtain good yield, reaction normally improves temperature and reacts under reducing pressure.At high temperature, propane is easily cracked into Small molecular thus makes selective reduction, and carbon distribution causes catalysqt deactivation simultaneously.
Catalyst is a kind of material changing the reaction rate of chemical reaction.In recent years, along with propane catalytic dehydrogenation research deepens continuously, people's interest widely be also result in the research of this catalysts.Catalyst about this reaction has a series of patent, as: Chinese patent CN101162690A report a kind of by traditional infusion process preparation containing Pt, Sn, Ce(or Zn) three-way catalyst; Chinese patent CN101066532A reports the preparation method of a kind of skeleton containing the ZSM-5 molecular sieve catalyst of Sn; US Patent No. P4506032 reports a kind of preparation process of Pt, Zn, K and Cl catalyst for dehydrating alkanes.
Although the preparation method of Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane catalyst has large quantifier elimination report, but the dispersiveness of active component is undesirable in catalyst preparation process, and complicated process of preparation, preparation time is very long, greatly constrain the development of preparing propylene by dehydrogenating propane, this phenomenon is urgently to be resolved hurrily.
Summary of the invention
Technical problem to be solved by this invention is the complicated process of preparation overcoming existing platinum based catalyst, preparation time is long, the defects such as obtained catalyst activity component disperses is bad, provide the preparation method of a kind of platinum based catalyst and preparation method thereof, application and propylene.The preparation method of platinum based catalyst of the present invention is simple, and preparation time is short, and obtained catalyst has good dispersiveness, activity and Propylene Selectivity.
An object of the present invention is, provides a kind of preparation method of platinum based catalyst, and described preparation method comprises the following steps:
(1) by activated alumina (γ-Al
2o
3) mix to obtain mixed liquor with compounding agent solution, ultrasonic vibration 1 hour-6 hours under 30 DEG C of-50 DEG C of conditions, dry, calcining, obtained catalyst precursor; Described compounding agent solution is stannous chloride (SnCl
22H
2o) solution and/or indium nitrate (In (NO
3)
34.5H
2o) solution; Described activated alumina (γ-Al
2o
3) be (10:1)-(450:1) with the mass ratio of the auxiliary agent in described compounding agent solution;
(2) catalyst precursor obtained in step (1) is mixed with platinum acid chloride solution, ultrasonic vibration 1 hour-6 hours under 30 DEG C of-50 DEG C of conditions, dry, calcining; Described activated alumina and the mass ratio of chloroplatinic acid are (40:1)-(500:1).
In step (1), described activated alumina (Activated Alumina or Reactive alumina; Activated alumin (I) um oxide) be the catalyst carrier of this area routine.Those skilled in the art all know: the aluminium oxide used in the catalyst is specially called " activated alumina " usually, it is the solid material of a kind of porous, high degree of dispersion, there is very large surface area, its micropore surface possesses the characteristic required by catalytic action, as absorption property, surface-active, excellent heat endurance etc., so be used as catalyst and the catalyst carrier of chemical reaction widely.Preferably, the particle diameter of described activated alumina is 80-100 order.
In step (1), the mass ratio of described activated alumina and described auxiliary agent is preferably (10:1)-(100:1).
In step (1), preferably, when described compounding agent solution is stannous chloride solution, described activated alumina and the mass ratio of stannous chloride are preferably (80:1)-(100:1), and that better is 90:1.
In step (1), preferably, when described compounding agent solution is indium nitrate solution, described activated alumina and the mass ratio of indium nitrate are preferably (10:1)-(60:1), and that better is (10:1)-(50:1).
In step (1), preferably, when described compounding agent solution be stannous chloride solution and indium nitrate solution time, described activated alumina: stannous chloride: the mass ratio of indium nitrate is preferably (100-80): (3-1.5): 1, and that better is 90:(3-1.5): 1.
In step (1), the method for described drying is the method for this area routine.Described drying is preferably dry in an oven; The temperature of described drying is preferably 100 DEG C-150 DEG C, and better is 110 DEG C; The time of described drying is preferably 2 hours-5 hours, and better is 2 hours.
In step (1), the method for described calcining is the method for this area routine.The temperature of described calcining is preferably 450 DEG C-700 DEG C; The time of described calcining is preferably 3 hours-8 hours, and better is 5 hours.The heating rate of described calcining is preferably 1 DEG C/min-10 DEG C/min, better is 5 DEG C/min-10 DEG C/min, and that better is 2 DEG C/min further.
In step (1), the concentration of described stannous chloride solution is the concentration of this area routine; The concentration of described stannous chloride solution is preferably 0.005g/mL-0.02g/mL, and that better is 0.01338g/mL.
In step (1), the concentration of described indium nitrate solution is the concentration of this area routine; The concentration of described indium nitrate solution is preferably 0.009g/mL-0.1g/mL, and that better is 0.021g/mL-0.0124g/mL.
In step (1), temperature during described ultrasonic vibration is preferably 40 DEG C.
In step (1), the time of described ultrasonic vibration is preferably 4 hours.
In step (2), described activated alumina and the mass ratio of chloroplatinic acid are preferably (125:1)-(250:1).
In step (2), the method for described drying is the method for this area routine.Described drying is preferably dry in an oven; The temperature of described drying is preferably 100 DEG C-150 DEG C, and better is 110 DEG C; The time of described drying is preferably 2 hours-5 hours, and better is 2 hours.
In step (2), the method for described calcining is the method for this area routine.The temperature of described calcining is preferably 450 DEG C-700 DEG C; The time of described calcining is preferably 3 hours-8 hours, and better is 5 hours; The heating rate of described calcining is preferably 1 DEG C/min-10 DEG C/min, better is 5 DEG C/min-10 DEG C/min, and that better is 2 DEG C/min further.
In step (2), the concentration of described platinum acid chloride solution is preferably 0.001-0.02g/mL, and that better is 0.01g/mL.
In step (2), temperature during described ultrasonic vibration is preferably 40 DEG C.
In step (2), the time of described ultrasonic vibration is preferably 4 hours.
A preferred embodiments of the present invention can be: in step (1), and the quality of described activated alumina is 3g; The volume of described mixed liquor is 2.4mL; The concentration of described stannous chloride solution is 0.0126g/mL; The concentration of described indium nitrate solution is 0.0544g/mL; In step (2), the concentration of described platinum acid chloride solution is 0.01g/mL, and the volume of described platinum acid chloride solution is 2.4mL.
Two of object of the present invention is, provides the platinum based catalyst that the preparation method of above-mentioned platinum based catalyst obtains.
Three of object of the present invention is, provides the application in Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane reaction of above-mentioned platinum based catalyst.
Four of object of the present invention is, provides a kind of preparation method of propylene.Described preparation method is: use above-mentioned obtained platinum based catalyst catalysis dehydrogenating propane to react propylene processed.
The preparation method of described propylene is preferably: temperature 550 DEG C-650 DEG C, under pressure 0.1atm-1.2atm condition, is contacted by reacting gas with described platinum based catalyst; Wherein, described reacting gas is propane and hydrogen.
Preferably, the cumulative volume air speed of described reacting gas is 800-1600h
-1, wherein the volume ratio of propane and hydrogen is (0.1:1)-(2:1); The consumption of described platinum based catalyst is: when the flow of propane is 9.6 × 10
-5-9 × 10
-4m
3during/h, the amount of the platinum based catalyst of use is 0.1g-1g.
In the present invention, described volume space velocity is the catalyst treatment volume of material amount of unit interval unit volume, unit h
-1.
Preferably, described reacting gas also comprises inert gas.Described inert gas is preferably nitrogen and/or argon gas, and better is argon gas.Preferably, volume ratio (1:1)-(1:10) of described propane and inert gas.
The temperature of described reaction is preferably 600 DEG C.
The pressure of described reaction is preferably 1atm.
The time of described reaction is preferably 2-80 hour, and better is 2 hours.
Preferably, before described platinum based catalyst catalysis dehydrogenating propane reaction, described platinum based catalyst is activated.Described activation is that the platinum of the oxidation state in platinum based catalyst is reduced into simple substance platinum.Described activation is preferably for activating facing under hydrogen atmosphere; Preferably, the step of described activation is: by described platinum based catalyst under pure hydrogen atmosphere with the heating rate of 10-30 DEG C/min from room temperature to 450-600 DEG C, under the hydrogen flow rate of 5mL-30mL, reduce 3-5 hour.
In the step of described activation, the temperature of described room temperature is preferably 20 DEG C-30 DEG C; Described heating rate is preferably 20 DEG C/min; Described intensification is preferably for rise to 500 DEG C from room temperature; The flow velocity of described hydrogen is preferably 12mL/min; The time of described activation is preferably 3 hours.
On the basis meeting this area general knowledge, above-mentioned each optimum condition, can be combined, obtain the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is: preparation process of the present invention is simple, and preparation time is short, and obtained platinum based catalyst can catalysis preparing propylene by dehydrogenating propane, and active component in carrier surface dispersion evenly, there is greater activity, Propylene Selectivity and stability.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) photo of the platinum based catalyst that embodiment 1 obtains.
Fig. 2 is transmission electron microscope (TEM) photo of the platinum based catalyst that embodiment 4 obtains.
Fig. 3 is transmission electron microscope (TEM) photo of the platinum based catalyst that embodiment 10 obtains.
Fig. 4 is transmission electron microscope (TEM) photo of the platinum based catalyst that comparative example 1 obtains.
Detailed description of the invention
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
Embodiment 1
(1) SnCl of 0.0341g is taken
22H
2o is dissolved in 2.4mL deionized water, wiring solution-forming, takes the γ-Al of 3g simultaneously
2o
3add above-mentioned solution.Put into ultrasonic instrument again, regulate water temperature to be 40 DEG C, ultrasonic vibration 2 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, roasting 5 hours, is cooled to room temperature under air.
(2) the platinum acid chloride solution 2.4mL getting 0.01g/mL is dissolved in the sample after calcining, then puts into ultrasonic instrument, regulates water temperature to be 40 DEG C, then ultrasonic oscillation is opened ultrasonic 2 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, roasting 5 hours, is cooled to room temperature under air.
Obtained catalyst Cat#1.
Platinum based catalyst catalysis preparing propylene by dehydrogenating propane reacts:
(1) reduction of catalyst: get catalyst 0.2g and be loaded on quartz reactor, reaction procatalyst rises to 500 DEG C with the speed of 20 DEG C/min from room temperature under pure hydrogen atmosphere, reduces 3 hours under the hydrogen flow rate of 12mL/min;
(2) platinum based catalyst catalysis preparing propylene by dehydrogenating propane reaction: be warming up to the reaction of 600 DEG C of incision reaction gases; Volume of gas air speed is 1300h
-1, the flow of propane is 3.6 × 10
-4m
3/ h, reactor feed gas total flow 30mL/min, wherein propane 6mL/min, hydrogen 6mL/min, all the other are argon gas.Reaction pressure is 1atm.
Obtained catalyst Cat#1.
Transmission electron microscope (TEM) photo of catalyst Cat#1 as shown in Figure 1.Wherein, marking by white circle, is all platinum based catalyst monomers.
Its evaluation result is as shown in table 1.
The evaluation of table 1 catalytic dehydrogenation performance
Embodiment 2
(1) In (NO of 0.0499g is taken
3)
34.5H
2o is dissolved in 2.4mL deionized water, wiring solution-forming, takes the γ-Al of 3g simultaneously
2o
3add above-mentioned solution.Put into ultrasonic instrument again, regulate water temperature to be 40 DEG C, ultrasonic vibration 1 hour.Sample after ultrasonic is placed in baking oven in 150 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 700 DEG C with the heating rate of 10 DEG C/min, roasting 1 hour, is cooled to room temperature under air.
(2) the platinum acid chloride solution 2.4mL getting 0.01g/mL is dissolved in the sample after calcining, then puts into ultrasonic instrument, regulates water temperature to be 40 DEG C, ultrasonic vibration 6 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, roasting 5 hours, is cooled to room temperature under air.
Obtained catalyst Cat#2.
Platinum based catalyst catalysis preparing propylene by dehydrogenating propane reacts:
(1) reduction of catalyst: get catalyst 0.1g and be loaded on quartz reactor, reaction procatalyst rises to 450 DEG C with the speed of 10 DEG C/min from room temperature (20 DEG C) under pure hydrogen atmosphere, reduces 5 hours under the hydrogen flow rate of 5mL/min;
(2) platinum based catalyst catalysis preparing propylene by dehydrogenating propane reaction: be warming up to the reaction of 650 DEG C of incision reaction gases.Volume of gas air speed is 800h
-1, the flow of propane is 3.6 × 10
-4m
3/ h, reactor feed gas total flow 15mL/min, wherein propane 6mL/min, hydrogen 3mL/min, all the other are argon gas.Reaction pressure is 0.1atm.
Its evaluation result is as shown in table 2.
Table 2 catalytic dehydrogenation performance
Embodiment 3
(1) In (NO of 0.0998g is taken
3)
34.5H
2o is dissolved in 2.4mL deionized water, wiring solution-forming, takes the γ-Al of 3g simultaneously
2o
3add above-mentioned solution.Put into ultrasonic instrument again, regulate water temperature to be 30 DEG C, ultrasonic vibration 6 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 5 DEG C/min, roasting 5 hours, is cooled to room temperature under air.
(2) the platinum acid chloride solution 2.4mL getting 0.01g/mL is dissolved in the sample after calcining, then puts into ultrasonic instrument, regulates water temperature to be 40 DEG C, ultrasonic vibration 1 hour.Sample after ultrasonic is placed in baking oven in 100 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, roasting 5 hours, is cooled to room temperature under air.
Obtained catalyst Cat#3.
Platinum based catalyst catalysis preparing propylene by dehydrogenating propane reacts:
(1) reduction of catalyst: get catalyst 1g and be loaded on quartz reactor, reaction procatalyst rises to 600 DEG C with the speed of 30 DEG C/min from room temperature 30 DEG C under pure hydrogen atmosphere, reduces 3 hours under the hydrogen flow rate of 30mL/min;
(2) platinum based catalyst catalysis preparing propylene by dehydrogenating propane reaction: cut reaction gas reaction under 650 DEG C of conditions.Volume of gas air speed is 800h
-1, the flow of propane is 9 × 10
-4m
3/ h, reactor feed gas total flow 80mL/min, wherein the volume ratio of propane and hydrogen is the volume ratio 1:3 of 3:2, propane and argon gas, and reaction pressure is 1.2atm.
Evaluation result is as described in Table 3.
The evaluation of table 3 catalytic dehydrogenation performance
Embodiment 4
(1) In (NO of 0.1497g is taken
3)
34.5H
2o is dissolved in 2.4mL deionized water, wiring solution-forming, takes the γ-Al of 3g simultaneously
2o
3add above-mentioned solution.Put into ultrasonic instrument again, regulate water temperature to be 50 DEG C, ultrasonic vibration 6 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, roasting 5 hours, is cooled to room temperature under air.
(2) the platinum acid chloride solution 2.4mL getting 0.01g/mL is dissolved in the sample after calcining, then puts into ultrasonic instrument, regulates water temperature to be 40 DEG C, ultrasonic vibration 2 hours.Sample after ultrasonic is placed in baking oven in 150 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 450 DEG C with the heating rate of 5 DEG C/min, roasting 3 hours, is cooled to room temperature under air.
Obtained catalyst Cat#4.
Transmission electron microscope (TEM) photo of catalyst Cat#4 as shown in Figure 2.Wherein, marking by white circle, is all platinum based catalyst monomers.
Platinum based catalyst catalysis preparing propylene by dehydrogenating propane reacts:
(1) reduction of catalyst: get catalyst 0.5g and be loaded on quartz reactor, reaction procatalyst rises to 500 DEG C with the speed of 20 DEG C/min from room temperature 30 DEG C under pure hydrogen atmosphere, reduces 4 hours under the hydrogen flow rate of 25mL/min;
(2) platinum based catalyst catalysis preparing propylene by dehydrogenating propane reaction: be warming up to the reaction of 550 DEG C of incision reaction gases.Volume of gas air speed is 900h
-1, the flow of propane is 4.1 × 10
-4m
3/ h, reactor feed gas total flow 50mL/min, wherein the volume ratio of propane and hydrogen is the volume ratio 3:7 of 2:1, propane and argon gas, and reaction pressure is 1atm.
Evaluation result is as shown in table 4.
The evaluation of table 4 catalytic dehydrogenation performance
Embodiment 5
(1) In (NO of 0.1996g is taken
3)
34.5H
2o is dissolved in 2.4mL deionized water, wiring solution-forming, takes the γ-Al of 3g simultaneously
2o
3add above-mentioned solution.Put into ultrasonic instrument again, regulate water temperature to be 30 DEG C, ultrasonic vibration 4 hours.Sample after ultrasonic is placed in baking oven in 140 DEG C of dryings 3 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, roasting 5 hours, is cooled to room temperature under air.
(2) the platinum acid chloride solution 2.4mL getting 0.01g/mL is dissolved in the sample after calcining, then puts into ultrasonic instrument, regulates water temperature to be 40 DEG C, ultrasonic vibration 2 hours.Sample after ultrasonic is placed in baking oven in 130 DEG C of dryings 4 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 5 DEG C/min, roasting 8 hours, is cooled to room temperature under air.
Obtained catalyst Cat#5.Appreciation condition is with embodiment 1.Evaluation result is as shown in table 5.
The evaluation of table 5 catalytic dehydrogenation performance
Embodiment 6
(1) In (NO of 0.2495g is taken
3)
34.5H
2o is dissolved in 2.4mL deionized water, wiring solution-forming, takes the γ-Al of 3g simultaneously
2o
3add above-mentioned solution.Put into ultrasonic instrument again, regulate water temperature to be 50 DEG C, ultrasonic vibration 5 hours.Sample after ultrasonic is placed in baking oven in 120 DEG C of dryings 4 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, roasting is cooled to room temperature in 3 hours under air.
(2) platinum acid chloride solution getting the 0.01g/mL of 2.4mL is dissolved in the sample after calcining, then puts into ultrasonic instrument, regulates water temperature to be 30 DEG C, ultrasonic vibration 6 hours.Sample after ultrasonic is placed in baking oven in 150 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, roasting 3 hours, is cooled to room temperature under air.
Obtained catalyst Cat#6.Appreciation condition is with embodiment 1.Evaluation result is as shown in table 6.
The evaluation of table 6 catalytic dehydrogenation performance
Embodiment 7
(1) In (NO of 0.2994g is taken
3)
34.5H
2o is dissolved in 2.4mL deionized water, wiring solution-forming, takes the γ-Al of 3g simultaneously
2o
3add above-mentioned solution.Put into ultrasonic instrument again, regulate water temperature to be 40 DEG C, ultrasonic vibration 2 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, roasting 8 hours, is cooled to room temperature under air.
(2) platinum acid chloride solution getting the 0.01g/mL of 2.4mL is dissolved in the sample after calcining, then puts into ultrasonic instrument, regulates water temperature to be 50 DEG C, ultrasonic vibration 6 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 5 DEG C/min, roasting 5 hours, is cooled to room temperature under air.
Obtained catalyst Cat#7.Appreciation condition is with embodiment 1.Evaluation result is as described in Table 7.
The evaluation of table 7 catalytic dehydrogenation performance
Embodiment 8
(1) In (NO of 0.0499g is taken
3)
34.5H
2the SnCl of O and 0.0341g
22H
2o is dissolved in 2.4mL deionized water simultaneously, wiring solution-forming, takes the γ-Al of 3g simultaneously
2o
3add above-mentioned solution.Put into ultrasonic instrument again, regulate water temperature to be 40 DEG C, ultrasonic vibration 3 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, under air roasting 5 hours, within 5 hours, be cooled to room temperature.
(2) the platinum acid chloride solution 2.4mL getting 0.01g/mL is dissolved in the sample after calcining, then puts into ultrasonic instrument, regulates water temperature to be 30 DEG C, ultrasonic vibration 1 hour.Sample after ultrasonic is placed in baking oven in 100 DEG C of dryings 5 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, under air roasting 5 hours, within 5 hours, be cooled to room temperature.
Obtained catalyst Cat8#.Appreciation condition is with embodiment 1.Evaluation result is as shown in table 8.
The evaluation of table 8 catalytic dehydrogenation performance
Embodiment 9
(1) In (NO of 0.0998g is taken
3)
34.5H
2the SnCl of O and 0.0341g
22H
2o is dissolved in 2.4mL deionized water simultaneously, wiring solution-forming, takes the γ-Al of 3g simultaneously
2o
3add above-mentioned solution.Put into ultrasonic instrument again, regulate water temperature to be 40 DEG C, ultrasonic vibration 3 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, under air roasting 5 hours, within 5 hours, be cooled to room temperature.
(2) the platinum acid chloride solution 2.4mL getting 0.01g/mL is dissolved in the sample after calcining, then puts into ultrasonic instrument, regulates water temperature to be 40 DEG C, ultrasonic vibration 4 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, under air roasting 5 hours, within 5 hours, be cooled to room temperature.
Obtained catalyst Cat9#.Appreciation condition is with embodiment 1.Evaluation result is as shown in table 9.
The evaluation of table 9 catalytic dehydrogenation performance
Embodiment 10
(1) In (NO of 0.0998g is taken
3)
34.5H
2the SnCl of O and 0.0341g
22H
2o is dissolved in 2.4mL deionized water simultaneously, wiring solution-forming, takes the γ-Al of 3g simultaneously
2o
3add above-mentioned solution.Put into ultrasonic instrument again, regulate water temperature to be 40 DEG C, ultrasonic vibration 2 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, under air roasting 5 hours, within 5 hours, be cooled to room temperature.
(2) the platinum acid chloride solution 2.4mL getting 0.01g/mL is dissolved in the sample after calcining, then puts into ultrasonic instrument, regulates water temperature to be 40 DEG C, ultrasonic vibration 6 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, under air roasting 5 hours, within 5 hours, be cooled to room temperature.
Obtained catalyst Cat10#.
Transmission electron microscope (TEM) photo of catalyst Cat#10 as shown in Figure 3.Wherein, marking by white circle, is all platinum based catalyst monomers.
Appreciation condition is with embodiment 1.Evaluation result is as table 10.
The evaluation of table 10 catalytic dehydrogenation performance
Embodiment 11
(1) In (NO is taken
3)
34.5H
2o and SnCl
22H
2o is dissolved in 2.4mL deionized water, wiring solution-forming, takes the γ-Al of 3g simultaneously
2o
3add above-mentioned solution, the concentration of the sub-solution of tin of Chlorine in Solutionization is 0.0126g/mL, and the concentration of indium nitrate solution is 0.0544g/mL, and described concentration is the quality of solute and the ratio of liquor capacity.Put into ultrasonic instrument again, regulate water temperature to be 40 DEG C, ultrasonic vibration 3 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, under air roasting 5 hours, within 5 hours, be cooled to room temperature.
(2) the platinum acid chloride solution 2.4mL getting 0.01g/mL is dissolved in the sample after calcining, then puts into ultrasonic instrument, regulates water temperature to be 40 DEG C, ultrasonic vibration 4 hours.Sample after ultrasonic is placed in baking oven in 110 DEG C of dryings 2 hours.Finally dried sample is placed in Muffle furnace and rises to 500 DEG C with the heating rate of 2 DEG C/min, under air roasting 5 hours, within 5 hours, be cooled to room temperature.
Comparative example 1
Ultrasonic step is changed into room temperature immersion 12h, all the other are all with embodiment 1, obtained platinum based catalyst.
Transmission electron microscope (TEM) photo of the platinum based catalyst that the method obtains as shown in Figure 4.The dispersiveness of the platinum based catalyst that the method obtains is not so good as the obtained platinum based catalyst of embodiment 1-10, stability, activity and selectivity etc., also obtained not as embodiment 1-10 platinum based catalyst.
Claims (10)
1. a preparation method for platinum based catalyst, is characterized in that: described preparation method comprises the following steps:
(1) activated alumina is mixed to obtain mixed liquor with compounding agent solution, ultrasonic vibration 1 hour-6 hours under 30 DEG C of-50 DEG C of conditions, dry, calcining, obtained catalyst precursor; Described compounding agent solution is stannous chloride solution and/or indium nitrate solution; The mass ratio of the auxiliary agent in described activated alumina and described compounding agent solution is (10:1)-(450:1);
(2) catalyst precursor obtained in step (1) is mixed with platinum acid chloride solution, ultrasonic vibration 1 hour-6 hours under 30 DEG C of-50 DEG C of conditions, dry, calcining; Described activated alumina and the mass ratio of chloroplatinic acid are (40:1)-(500:1).
2. preparation method as claimed in claim 1, is characterized in that:
In step (1), the particle diameter of described activated alumina is 80-100 order;
In step (1), the mass ratio of described activated alumina and described auxiliary agent is (10:1)-(100:1);
In step (1), when described compounding agent solution is stannous chloride solution, described activated alumina and the mass ratio of stannous chloride are (80:1)-(100:1), are preferably 90:1;
In step (1), when described compounding agent solution is indium nitrate solution, described activated alumina and the mass ratio of indium nitrate are (10:1)-(60:1), are preferably (10:1)-(50:1);
In step (1), when described compounding agent solution be stannous chloride solution and indium nitrate solution time, described activated alumina: stannous chloride: the mass ratio of indium nitrate is (100-80): (3-1.5): 1 is preferably 90:(3-1.5): 1;
In step (1), described drying is dry in an oven; The temperature of described drying is 100 DEG C-150 DEG C, is preferably 110 DEG C; The time of described drying is 2 hours-5 hours, is preferably 2 hours;
In step (1), the temperature of described calcining is 450 DEG C-700 DEG C; The time of described calcining is 3 hours-8 hours, is preferably 5 hours; The heating rate of described calcining is 1 DEG C/min-10 DEG C/min, be preferably 5 DEG C/min-10 DEG C/min, that better is 2 DEG C/min;
In step (1), the concentration of described stannous chloride solution is 0.005g/mL-0.02g/mL, is preferably 0.01338g/mL;
In step (1), the concentration of described indium nitrate solution is 0.009g/mL-0.1g/mL, is preferably 0.021g/mL-0.0124g/mL;
In step (1), temperature during described ultrasonic vibration is 40 DEG C, and the time of described ultrasonic vibration is 4 hours.
3. preparation method as claimed in claim 1 or 2, is characterized in that:
In step (2), described activated alumina and the mass ratio of chloroplatinic acid are (125:1)-(250:1);
In step (2), described drying is dry in an oven; The temperature of described drying is 100 DEG C-150 DEG C, is preferably 110 DEG C; The time of described drying is 2 hours-5 hours, is preferably 2 hours;
In step (2), the temperature of described calcining is 450 DEG C-700 DEG C; The time of described calcining is 3 hours-8 hours, is preferably 5 hours; The heating rate of described calcining is 1 DEG C/min-10 DEG C/min, be preferably 5 DEG C/min-10 DEG C/min, that better is 2 DEG C/min;
In step (2), the concentration of described platinum acid chloride solution is 0.001-0.02g/mL, is preferably 0.01g/mL;
In step (2), temperature during described ultrasonic vibration is 40 DEG C, and the time of described ultrasonic vibration is 4 hours.
4. preparation method as claimed in claim 1, is characterized in that:
In step (1), the quality of described activated alumina is 3g, and the volume of described mixed liquor is 2.4mL, and the concentration of described stannous chloride solution is 0.0126g/mL, and the concentration of described indium nitrate solution is 0.0544g/mL; In step (2), the concentration of described platinum acid chloride solution is 0.01g/mL, and the volume of described platinum acid chloride solution is 2.4mL.
5. the platinum based catalyst that the preparation method according to any one of claim 1-4 obtains.
6. platinum based catalyst as claimed in claim 5 application in Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane reaction.
7. a preparation method for propylene, is characterized in that: described preparation method is: use platinum based catalyst catalysis dehydrogenating propane as claimed in claim 5 to react propylene processed.
8. the preparation method of propylene as claimed in claim 7, is characterized in that: described preparation method is: temperature 550 DEG C-650 DEG C, under pressure 0.1atm-1.2atm condition, is contacted by reacting gas with described platinum based catalyst; Wherein, described reacting gas is propane and hydrogen;
Preferably, the cumulative volume air speed of described reacting gas is 800-1600h
-1, wherein the volume ratio of propane and hydrogen is (0.1:1)-(2:1); The consumption of described platinum based catalyst is: when the flow of propane is 9.6 × 10
-5-9 × 10
-4m
3during/h, the amount of the platinum based catalyst of use is 0.1g-1g;
Preferably, described reacting gas also comprises inert gas; Described inert gas is preferably nitrogen and/or argon gas; Preferably, volume ratio (1:1)-(1:10) of described propane and inert gas.
9. the preparation method of propylene as claimed in claim 7, is characterized in that:
The temperature of described reaction is 600 DEG C; The pressure of described reaction is 1atm; The time of described reaction is 2-80 hour, is preferably 2 hours.
10. the preparation method of propylene as claimed in any one of claims 7-9, is characterized in that:
Before described reaction, described platinum based catalyst is activated; Described activation is preferably for activating facing under hydrogen atmosphere; Preferably, the step of described activation is: by described platinum based catalyst under pure hydrogen atmosphere with the heating rate of 10-30 DEG C/min from room temperature to 450-600 DEG C, under the hydrogen flow rate of 5mL-30mL, reduce 3-5 hour;
In the step of described activation, the temperature of described room temperature is preferably 20 DEG C-30 DEG C; Described heating rate is preferably 20 DEG C/min; Described intensification is preferably for rise to 500 DEG C from room temperature; The flow velocity of described hydrogen is preferably 12mL/min; The time of described activation is preferably 3 hours.
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| CN105032416A (en) * | 2015-08-04 | 2015-11-11 | 宁波海越新材料有限公司 | Four-element platinum-based catalyst and preparation method thereof |
| CN106693993A (en) * | 2016-12-21 | 2017-05-24 | 北京赛诺时飞石化科技有限公司 | Sulfur-containing light alkane dehydrogenation catalyst and preparation method thereof |
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| 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 |
| CN110193365A (en) * | 2019-07-04 | 2019-09-03 | 中国科学院大连化学物理研究所 | A kind of method that technique for atomic layer deposition prepares platinum based catalyst and its application in dehydrogenating propane reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105032416A (en) * | 2015-08-04 | 2015-11-11 | 宁波海越新材料有限公司 | Four-element platinum-based catalyst and preparation method thereof |
| CN106693993A (en) * | 2016-12-21 | 2017-05-24 | 北京赛诺时飞石化科技有限公司 | Sulfur-containing light alkane dehydrogenation catalyst and preparation method thereof |
| CN106693993B (en) * | 2016-12-21 | 2019-04-30 | 北京赛诺时飞石化科技有限公司 | A kind of sulfur-type catalyst for dehydrogenation of low-carbon paraffin and preparation method |
| CN109701520A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | High dispersive dehydrogenation, Preparation method and use method |
| CN109701520B (en) * | 2017-10-26 | 2022-07-12 | 中国石油化工股份有限公司 | High-dispersion dehydrogenation catalyst, preparation method and application method |
| CN109692713A (en) * | 2019-01-25 | 2019-04-30 | 福州大学 | A kind of catalyst for dehydrogenation of low-carbon paraffin and the 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 |
| CN110193365A (en) * | 2019-07-04 | 2019-09-03 | 中国科学院大连化学物理研究所 | A kind of method that technique for atomic layer deposition prepares platinum based catalyst and its application in dehydrogenating propane reaction |
| CN113559853A (en) * | 2021-08-21 | 2021-10-29 | 福州大学 | Catalyst for preparing propylene by direct dehydrogenation of propane |
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