CN116459829A - Pt/gamma-alumina catalyst with nano-sheet stacked flower-like structure and preparation method and application thereof - Google Patents
Pt/gamma-alumina catalyst with nano-sheet stacked flower-like structure and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000002135 nanosheet Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000012298 atmosphere Substances 0.000 claims description 28
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 13
- 239000012716 precipitator Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000003841 chloride salts Chemical class 0.000 claims description 8
- 229910001510 metal chloride Inorganic materials 0.000 claims description 8
- 239000002612 dispersion medium Substances 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000002064 nanoplatelet Substances 0.000 claims 3
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000005470 impregnation Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229910002706 AlOOH Inorganic materials 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 229910018626 Al(OH) Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
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- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 238000010606 normalization Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polyethylene, ethylene propylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 230000005070 ripening Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalysts, and provides a Pt/gamma-alumina catalyst with a nano-sheet stacked flower-shaped structure, and a preparation method and application thereof. The Pt/gamma-alumina catalyst is prepared by adopting cheap and easily available raw materials through a hydrothermal precipitation-impregnation method, and has a nano-sheet stacked flower-like structure; al in alumina support V The sites and Pt atoms have strong electron interaction, so that the Pt species can be effectively anchored, and the high dispersibility and stability of the Pt species can be well maintained; in addition, the co-impregnating agent is adopted to promote the dispersion of the active metal Pt, reduce the acidity of the carrier, prevent the active metal Pt from agglomerating on the surface of the carrier, and further improve the dispersion uniformity of the Pt. The invention effectively solves the problems of uneven dispersion and easy sintering of Pt, and the obtained nano-sheet stackThe Pt/gamma-alumina catalyst with the stacked structure has wide application prospect in ethane dehydrogenation reaction.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a Pt/gamma-alumina catalyst with a nano-sheet stacked flower-shaped structure, and a preparation method and application thereof.
Background
Ethylene (C) 2 H 4 ) Is an important basic organic chemical raw material, can be used for synthesizing polyethylene, ethylene propylene rubber, polyvinyl chloride, ethylene oxide and other materials, can also be used for producing ethanol, acetaldehyde, acetic acid and the like, and can also be used for plant ripening agents. There are 4 main sources of ethylene including naphtha steam cracking, ethane dehydrogenation, fischer-Tropsch olefins (FTO) and Methanol To Olefins (MTO) processes. Naphtha steam cracking is limited by the price of crude oil, and the equipment cost and energy consumption of FTO/MTO processes are very high. The ethane dehydrogenation route benefits from shale gas revolution, has strong competitiveness in raw material cost, and is one of the ways of high-valued low-carbon alkane.
For light alkane dehydrogenation, pt-based (UOP Oleflex Process) and CrO x The base (Lummus Catofin process) catalysts are widely used for their excellent activity and olefin selectivity. However, crO x The base catalyst is highly toxic to biological systems and active sites are gradually lost during coke combustion regeneration. Pt-based catalysts, although non-toxic, have poor dispersibility of active metal Pt and are easily sintered at high temperatures, resulting in deterioration of catalyst performance. How to solve the problems of high dispersion and sintering of Pt is a key for realizing breakthrough of Pt-based catalysts.
Disclosure of Invention
In view of the above, the invention provides a Pt/gamma-alumina catalyst with a nano-sheet stacked flower-like structure, and a preparation method and application thereof. The Pt active component in the Pt/gamma-alumina catalyst provided by the invention has the advantages of high dispersibility, high activity, sintering resistance and long service life.
In order to achieve the above object, the present invention provides the following technical solutions:
the preparation method of the Pt/gamma-alumina catalyst with the nano-sheet stacked flower-like structure comprises the following steps:
mixing an aluminum source, a precipitator, a template agent solution and water, and performing hydrothermal crystallization to obtain a carrier precursor;
preparing a carrier precursor dispersion liquid from the carrier precursor, mixing the carrier precursor dispersion liquid, a co-impregnant and a Pt source, and sequentially carrying out ultrasonic treatment, drying and roasting to obtain a nano-sheet stacked flower-like structure Pt/gamma-alumina catalyst; the co-impregnant includes an acid and/or a metal chloride salt.
Preferably, the acid comprises one or more of hydrochloric acid, citric acid, oxalic acid and tartaric acid; the metal chloride salt comprises potassium chloride and/or sodium chloride; the dosage ratio of the carrier precursor and the co-impregnant is (0.5-3) g (0.5-15) mmol.
Preferably, the aluminium source comprises aluminium chloride and/or aluminium nitrate; the precipitant is urea and/or ammonia water; the molar ratio of the aluminum source to the precipitator is (0.05-2): 1;
the template agent in the template agent solution is P123 and/or F127; the mass ratio of the aluminum source to the template agent in the template agent solution is (1-5): 1.
Preferably, the temperature of the hydrothermal crystallization is 100-200 ℃ and the time is 12-48 h.
Preferably, the dispersion medium for preparing the carrier precursor dispersion liquid is water or an alcohol solvent; the dosage ratio of the carrier precursor to the dispersion medium is 1g (5-20) mL;
the Pt source comprises H 2 PtCl 6 、Na 2 PtCl 4 、Pt(NH 3 ) 4 Cl 2 、Pt(NH 3 ) 2 (NO 2 ) 2 And K 2 PtCl 6 One or more of the following; the mass ratio of the carrier precursor to the Pt source is (500-3000) (0.05-50).
Preferably, the ultrasonic treatment time is 5-30 min; the drying temperature is 30-150 ℃ and the drying time is 8-12 h.
Preferably, the roasting temperature is 300-700 ℃ and the roasting time is 2-6 hours; the roasting atmosphere is one or a mixture of more of air, oxygen and inert atmosphere.
The invention provides the Pt/gamma-alumina catalyst with the nano-sheet stacked flower-like structure, which is prepared by the preparation method; the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is a gamma-alumina catalyst, and the active component is Pt; the carrier exists in a flower-like structure of nano-sheet stacks; the active component exists in the form of nano particles or nano clusters; the mass fraction of active components in the Pt/gamma-alumina catalyst with the nano-sheet stacked flower-like structure is 0.01-2%.
The invention also provides application of the nano-sheet stacked flower-like structure Pt/gamma-alumina catalyst in ethane dehydrogenation reaction.
Preferably, the nano-sheet stacked flower-like structure Pt/gamma-alumina catalyst is reduced before application; the reduction is performed in an atmosphere containing a reducing gas; the reducing gas is hydrogen and/or carbon monoxide; the temperature of the reduction is 80-600 ℃ and the time is 0.5-4 h.
The invention provides a preparation method of a Pt/gamma-alumina catalyst with a nano-sheet stacked flower-shaped structure, which comprises the following steps: mixing an aluminum source, a precipitator, a template agent and water, and performing hydrothermal crystallization to obtain a carrier precursor; preparing a carrier precursor dispersion liquid from the carrier precursor, mixing the carrier precursor dispersion liquid, a co-impregnant and a Pt source, and sequentially carrying out ultrasonic treatment, drying and roasting to obtain a nano-sheet stacked flower-like structure Pt/gamma-alumina catalyst; the co-impregnant includes an acid and/or a metal chloride salt. The Pt/gamma-alumina catalyst is prepared by adopting cheap and easily available raw materials through a hydrothermal precipitation-impregnation method, and has a nano-sheet stacked flower-like structure; al in alumina support V The sites and Pt atoms have strong electron interaction, so that the Pt species can be effectively anchored, and the high dispersibility and stability of the Pt species can be well maintained; in addition, the co-impregnating agent is adopted to promote the dispersion of the active metal Pt, reduce the acidity of the carrier, prevent the active metal Pt from agglomerating on the surface of the carrier, and further improve the dispersion uniformity of the Pt.The invention effectively solves the problems of uneven dispersion and easy sintering of Pt, and the obtained nano-sheet stacked flower-like structure Pt/gamma-alumina catalyst has wide application prospect in ethane dehydrogenation reaction.
The invention also provides the Pt/gamma-alumina catalyst with the nano-sheet stacked flower-like structure, which is prepared by the preparation method of the scheme; the mass fraction of the active component in the catalyst provided by the invention is only 0.01-2%, and the catalyst provided by the invention can ensure excellent catalytic performance under the condition of low active component loading. The results of the examples show that when the catalyst provided by the invention is applied to ethane dehydrogenation reaction, the ethane conversion rate can still reach 24.2% after 480 hours of continuous use, and the ethylene selectivity performance can reach 95.8%.
Drawings
FIG. 1 is a scanning electron microscope image of catalyst C5 prepared in example 5;
FIG. 2 is a transmission electron micrograph of catalyst C5 prepared in example 2;
FIG. 3 is a scanning electron microscope image of catalyst D1 prepared in comparative example 1;
fig. 4 is a transmission electron microscopic image of the catalyst D1 prepared in comparative example 1.
Detailed Description
The invention provides a preparation method of a Pt/gamma-alumina catalyst with a nano-sheet stacked flower-shaped structure, which comprises the following steps:
mixing an aluminum source, a precipitator, a template agent solution and water, and performing hydrothermal crystallization to obtain a carrier precursor;
preparing a carrier precursor dispersion liquid from the carrier precursor, mixing the carrier precursor dispersion liquid, a co-impregnant and a Pt source, and sequentially carrying out ultrasonic treatment, drying and roasting to obtain a nano-sheet stacked flower-like structure Pt/gamma-alumina catalyst; the co-impregnant includes an acid and/or a metal chloride salt.
The invention mixes the aluminum source, the precipitator, the template agent solution and the water and then carries out hydrothermal crystallization to obtain the carrier precursor. In the present invention, the aluminum source preferably includes aluminum chloride and/or aluminum nitrate; the aluminum chloride may be tape crystallizedWater or aluminum chloride without water of crystallization, in particular embodiments of the present invention, the aluminum chloride is preferably AlCl 3 ·6H 2 O; the aluminum nitrate may be aluminum nitrate with or without water of crystallization, and in particular embodiments of the present invention, the aluminum nitrate is preferably Al (NO 3 ) 3 ·9H 2 O; the precipitant is preferably urea (CO (NH) 2 ) 2 ) And/or ammonia (NH) 3 ·H 2 O); the concentration of the ammonia water is not particularly required, and the concentration is well known in the art; the molar ratio of the aluminum source to the precipitant is preferably (0.05 to 2): 1, more preferably (0.06 to 1.8): 1; the template agent in the template agent solution is P123 and/or F127; the mass ratio of the aluminum source to the template in the template solution is preferably (1 to 5): 1, more preferably (1 to 4): 1.
In the present invention, the method of mixing the aluminum source, the precipitant, the template solution and water is preferably: respectively dissolving the aluminum source and the precipitator in water to obtain an aluminum source solution and a precipitator solution, adding the precipitator solution into the aluminum source solution, stirring for 5-30 min at room temperature, adding a template solution, and stirring for 5-30 min at room temperature to obtain a mixed solution; or, the method for mixing the aluminum source, the precipitant, the template agent and the water is also preferably: mixing an aluminum source and a precipitator, dissolving with water to obtain a mixed solution of the aluminum source and the precipitator, and adding a template agent solution into the mixed solution of the aluminum source and the precipitator to obtain a mixed solution; the invention has no special requirement on the water consumption, can dissolve the aluminum source and the precipitant, and ensures that the hydrothermal crystallization is smoothly carried out. In the invention, the preparation method of the template agent solution is preferably as follows: mixing a template agent and a solvent, and performing ultrasonic oscillation to obtain a template agent solution; the solvent is preferably water and/or ethanol; the invention has no special requirement on the ultrasonic vibration, and can fully dissolve the template agent; the concentration of the template solution is preferably 0.5g/mL.
In the present invention, the temperature of the hydrothermal crystallization is preferably 100 to 200 ℃, more preferably 130 to 150 ℃, and the time of the hydrothermal crystallization is preferably 12 to 48 hours, more preferably 24 to 36 hours; the hydrothermal crystallization is preferably carried out in a hydrothermal kettle.
In the present invention, the reactions occurring during the hydrothermal crystallization are represented by the following formulas (1) to (4):
NH 2 CONH 2 +H 2 O→CO 2 +2NH 3 (1)
NH 3 +H 2 O→NH 4 + +OH - (2)
Al 3+ +3OH - →Al(OH) 3 (3)
Al(OH) 3 →AlOOH+H 2 O (4)
under hydrothermal conditions, irregular AlOOH is formed from Al (OH) 3 [ 1) - (3)]Dehydrating. At this time, the amount of AlOOH crystals is small, and the continuous hydrolysis of urea increases the content of AlOOH crystals, and irregular AlOOH particles tend to overflow; twisted hydrogen bonds and solvent molecules and surface OH - The groups interact through hydrogen bonds to produce AlOOH nano rods. The formed nanorods may begin to form petals of the nanoscaled petals through a directional attachment process. As the reaction proceeds, the content of the template agent in the reaction system gradually increases, and the amount of the template agent adsorbed on the surface of the nanoflowers increases, which may cause the nanoflowers to self-assemble to form a spindle-shaped structure. With the extension of the reaction time, the spindle shape finally self-assembles into a new flower shape through Van der Waals force and hydrogen bond, and the new flower shape has lower interface free energy.
After the hydrothermal crystallization is finished, the invention preferably removes supernatant in the product feed liquid, collects solid products at the bottom, and sequentially carries out centrifugal washing and drying on the solid products to obtain a carrier precursor; the centrifugal washing detergent is a mixed solvent of deionized water and ethanol, and the volume ratio of the deionized water to the ethanol in the mixed solvent is preferably 1:1; the drying temperature is preferably 50-150 ℃ and the drying time is preferably 8-12 h; after drying, the present invention preferably grinds the resulting support precursor into a powder before subsequent preparation.
After a carrier precursor is obtained, the carrier precursor is prepared into carrier precursor dispersion liquid, and the carrier precursor dispersion liquid, the co-impregnating agent and the Pt source are mixed and then sequentially subjected to ultrasonic treatment, drying and roasting to obtain the Pt/gamma-alumina catalyst with the nano-sheet stacked flower-like structure. In the present invention, the dispersion medium for preparing the carrier precursor dispersion is preferably water or an alcoholic solvent, and the alcoholic solvent is preferably methanol and/or ethanol; the dosage ratio of the carrier precursor and the dispersion medium is preferably 1g (5-20) mL, more preferably 1g (10-15) mL; the invention preferably adds a dispersion medium into the carrier precursor, and stirs for 5-30 min at room temperature to obtain carrier precursor dispersion liquid.
In the present invention, the co-impregnant includes an acid and/or a metal chloride salt; the acid preferably comprises one or more of hydrochloric acid, citric acid, oxalic acid and tartaric acid; the metal chloride salt preferably comprises potassium chloride and/or sodium chloride; the ratio of the carrier precursor to the co-impregnating agent is preferably (0.5-3) g (0.5-15) mmol, more preferably (1-2.5) g (1-10) mmol; the co-impregnant is preferably used in the form of a co-impregnant solution, the solvent of which is preferably water, at a concentration of preferably 0.5 to 3mol/L, and in particular embodiments of the invention the ratio of the carrier precursor to the co-impregnant solution is preferably (0.5 to 3) g (1 to 5) mL. The invention adopts the co-impregnant to promote the dispersion of the active metal Pt, reduce the acidity of the carrier, prevent the active metal Pt from agglomerating on the surface of the carrier, and further improve the dispersion uniformity of the Pt.
In the present invention, the Pt source preferably comprises H 2 PtCl 6 、Na 2 PtCl 4 、Pt(NH 3 ) 4 Cl 2 、Pt(NH 3 ) 2 (NO 2 ) 2 And K 2 PtCl 6 One or more of the following; the mass ratio of the carrier precursor to the Pt source is preferably (500-3000): (0.05-50), more preferably (1000-2000): (1-35); the Pt source is preferably used in the form of a Pt source solution; the solvent of the Pt source solution is preferablyThe concentration of water is preferably 50-250 mg/mL, more preferably 100-150 mg/mL; in a specific embodiment of the present invention, the ratio of the carrier precursor to the Pt source solution is preferably (0.5-3) g (1-200) μL.
In the specific embodiment of the present invention, it is preferable that the co-impregnant solution is added to the carrier precursor dispersion liquid first, and after standing at room temperature for 10 to 30 minutes, the Pt source solution is added dropwise, and after the addition of the Pt source solution is completed, the mixture is stirred at room temperature for 5 to 30 minutes, and then the ultrasonic treatment is performed.
In the present invention, the time of the ultrasonic treatment is preferably 5 to 30 minutes, more preferably 10 to 20 minutes; the drying temperature is preferably 30-150 ℃, more preferably 50-120 ℃, and the drying time is preferably 8-12 h, more preferably 9-10 h; the drying is preferably carried out under aeration; after drying is completed, the resulting solid product is preferably ground into a powder and then subjected to subsequent calcination.
In the present invention, the temperature of the calcination is preferably 300 to 700 ℃, more preferably 400 to 600 ℃, and the time of the calcination is preferably 2 to 6 hours, more preferably 3 to 5 hours; the roasting atmosphere is preferably one or a mixture of more of air, oxygen and inert atmosphere; the inert atmosphere is preferably nitrogen; the heating rate to the baking temperature is preferably 1 to 20℃per minute, more preferably 1 to 10℃per minute.
The invention also provides the nano-sheet stacked flower-like structure Pt/gamma-alumina catalyst prepared by the preparation method, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is the gamma-alumina catalyst, and the active component is Pt; the carrier exists in a flower-like structure of nano-sheet stacks; the active component exists in the form of nano particles or nano clusters; the mass fraction of the active component in the catalyst is 0.01-2%, preferably 0.05-1%. In a specific embodiment of the present invention, the active component exists in the form of oxide after the calcination is completed, reduction is performed before application, pt exists in the form of coexistence of various valence states (partial reduction to Pt simple substance) after reduction, and specific reduction conditions are described in detail later. In the present invention, the nano-meterThe specific surface area of the Pt/gamma-alumina catalyst with the stacked flower-like structure is preferably 150-190 m 3 /g。
The invention also provides application of the nano-sheet stacked flower-like structure Pt/gamma-alumina catalyst in ethane dehydrogenation reaction; in the invention, the nano-sheet stacked flower-like structure Pt/gamma-alumina catalyst is reduced before application; the reduction is preferably carried out in an atmosphere containing a reducing gas; the reducing gas is preferably hydrogen and/or carbon monoxide; in the atmosphere containing the reducing gas, the volume fraction of the reducing gas is preferably more than or equal to 50%; in particular embodiments of the invention, a pure hydrogen atmosphere or CO-N may be employed 2 A mixed atmosphere of CO-N 2 The volume fraction of CO in the mixed atmosphere is preferably 50%; the temperature of the reduction is preferably 80 to 600 ℃, more preferably 100 to 500 ℃, and the time of the reduction is preferably 0.5 to 4 hours, more preferably 1 to 3 hours.
In the present invention, the ethane dehydrogenation reaction is preferably carried out at a temperature of 590 ℃ and a pressure of normal pressure; the space velocity of ethane is preferably 2 to 4 hours -1 。
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
5g F127 was prepared to give 0.5g/mL F127 aqueous solution, and 6.44g Al (NO) 3 ) 3 ·9H 2 O、9.28g CO(NH 2 ) 2 Adding a proper amount of H into a beaker 2 O, adding 1mL of F127 aqueous solution, stirring for 25min, placing in a 200mL reaction kettle, and placing in a 100 ℃ oven for hydrothermal reaction for 48h; use H after removal 2 O/C 2 H 5 Centrifugal washing with OH (1:1), drying at room temperature for 10h, and grinding into powder. 2.0g of carrier precursor powder is taken and placed in an evaporation dish, 20mL of deionized water is added to the carrier precursor2mL of 1mol/L hydrochloric acid solution was added to the aqueous solution, stirred and allowed to stand for 10min, followed by 132. Mu.L, 200mg/mL K 2 PtCl 6 The solution was stirred ultrasonically for 20min and dried at 60℃for 12h. Heating the obtained dry product to 600 ℃ at a speed of 1 ℃/min under nitrogen atmosphere, and keeping for 2 hours to obtain Pt/Al 2 O 3 Catalyst C1 was subsequently reduced at 500℃under a pure hydrogen atmosphere for 2h for ethane dehydrogenation.
Example 2
5g of F127 is taken to prepare 0.5g/mLF127 aqueous solution for later use, 6.44g of Al (NO 3 ) 3 ·9H 2 O、9.28g CO(NH 2 ) 2 Adding a proper amount of H into a beaker 2 O, adding 1mL of F127 aqueous solution, stirring for 25min, placing in a 200mL reaction kettle, and placing in a 100 ℃ oven for hydrothermal reaction for 48h; use H after removal 2 O/C 2 H 5 And (3) centrifugally washing by OH (1:1), drying at room temperature for 10h, and grinding into powder. 2.0g of precursor powder was taken, placed in an evaporation pan, 20mL of deionized water was added, 1mL of 1mol/L citric acid solution was added to the precursor aqueous solution, and after stirring, the mixture was allowed to stand for 15min, followed by 33. Mu.L of 200mg/mL K 2 PtCl 6 The solution was stirred ultrasonically for 20min and dried at 60℃for 12h. Then heating to 600 ℃ at a rate of 1 ℃/min under nitrogen atmosphere for 2 hours to obtain Pt/Al 2 O 3 Catalyst C2 was subsequently reduced at 500℃under a pure hydrogen atmosphere for 2h for ethane dehydrogenation.
Example 3
5g of F127 is taken to prepare 0.5g/mLF127 aqueous solution for later use, 6.44g of Al (NO 3 ) 3 ·9H 2 O、9.28gNH 3 ·H 2 Placing O in a beaker, adding a proper amount of H 2 O, adding 1mLF127 aqueous solution, stirring for 25min, placing in a 200mL reaction kettle, and placing in a 100 ℃ oven for hydrothermal reaction for 48h; use H after removal 2 O/C 2 H 5 And (3) centrifugally washing by OH (1:1), drying at room temperature for 10h, and grinding into powder. 2.0g of precursor powder was placed in an evaporation dish and 20mL of CH was added 3 OH, adding 2mL of 1mol/L oxalic acid solution to the precursor aqueous solution, stirring, standing for 20min, and then adding 66. Mu.L of 200mg/mL Na 2 PtCl 6 The solution was stirred ultrasonically for 20min and dried at 60℃for 12h. Then heating to 600 ℃ at a speed of 1 ℃/min under the oxygen atmosphere for 2 hours to obtain Pt/Al 2 O 3 Catalyst C3 was subsequently reduced at 500℃under a pure hydrogen atmosphere for 2h for ethane dehydrogenation.
Example 4
5g of P123 was taken to prepare a 0.5g/mLP123 aqueous solution for later use, 18.75g of Al (NO 3 ) 3 ·9H 2 O is dissolved in 100mL of deionized water to prepare solution A; take 6gNH 3 ·H 2 O is dissolved in 30mL deionized water to prepare solution B, the solution B is added into the solution A, 1mLP123 aqueous solution is added and stirred for 15min, the mixed solution is filled into a 200mL reaction kettle and placed into a 200 ℃ oven for hydrothermal reaction for 24h, precipitate is taken out for centrifugal washing, placed into a 60 ℃ oven for overnight drying for 12h, ground into powder, 2g of carrier precursor is taken, placed into an evaporation dish, and 20mL of C is added 2 H 5 OH, adding 0.5mL of 3mol/L NaCl solution to the precursor aqueous solution, stirring, standing for 10min, and then adding 17. Mu.L, 200mg/mL Pt (NH) 3 ) 4 Cl 2 The solution was stirred ultrasonically for 20min and dried at 60℃for 12h. Then heating to 500 ℃ at a speed of 1 ℃/min under the air atmosphere for 5 hours to obtain the Pt/Al 2 O 3 Catalyst C4, followed by 50% CO/50% N at 500 ℃C 2 For 2h in an atmosphere for ethane dehydrogenation.
Example 5
5g of P123 is taken to prepare 0.5g/mL of P123 aqueous solution for standby, 13g of AlCl is taken 3 ·6H 2 O、5g CO(NH 2 ) 2 Dissolving in 50mL deionized water, stirring for 15min, adding 1mL aqueous solution of P123, stirring for 15min, loading into a 100mL reaction kettle, placing in a 120 ℃ oven, performing hydrothermal reaction for 12H, taking out precipitate, centrifugally washing for 4 times by using deionized water, placing in a 70 ℃ oven for overnight drying for 12H, grinding into powder, taking 2g of carrier precursor, placing in an evaporation dish, adding 20mL deionized water, adding 2mL of 1mol/L KCl solution into the precursor aqueous solution, standing for 10min after stirring, and then adding 33 mu L of 200mg/mL H 2 PtCl 6 The solution was stirred ultrasonically for 20min and dried at 60℃for 12h. Then heating to 600 ℃ at a speed of 1 ℃/min under static air atmosphere, and keeping for 4 hours to obtain Pt/Al 2 O 3 Catalyst C5, which was subsequently reduced under a pure hydrogen atmosphere at 500℃for 2h, was used for ethane dehydrogenation.
Comparative example 1
This comparative example uses commercial gamma-alumina 1 as a support (available from general reagents Co., ltd.) to impregnate the same loading of active metal Pt as in example 5, followed by a temperature increase to 600℃at a rate of 1℃per minute under a static air atmosphere for 4 hours to give Pt/Al 2 O 3 Catalyst D1 was subsequently reduced under a pure hydrogen atmosphere at 500℃for 2h for ethane dehydrogenation. Commercial gamma-alumina had a specific surface area of 167m 2 /g。
Comparative example 2
This comparative example uses commercial porous alumina 2 as a support (available from national pharmaceutical agents Co., ltd.) to impregnate the same loading of active metal Pt as in example 5, followed by a temperature increase at a rate of 1 ℃/min to 600 ℃ for 4 hours under static air atmosphere to obtain Pt/Al 2 O 3 Catalyst D2 was subsequently reduced under a pure hydrogen atmosphere at 500℃for 2h for ethane dehydrogenation. The specific surface area of the commercial porous alumina was 233m 2 /g。
Comparative example 3 omits the co-impregnant
5g of P123 is taken to prepare 0.5g/mL of P123 aqueous solution for standby, 13g of AlCl is taken 3 ·6H 2 O、5g CO(NH 2 ) 2 Dissolving in 50mL deionized water, stirring for 15min, adding 1mL aqueous solution of P123, stirring for 15min, loading into 100mL reaction kettle, placing in a 120 ℃ oven, performing hydrothermal reaction for 12H, taking out precipitate, centrifugally washing for 4 times by using deionized water, placing in a 70 ℃ oven for overnight drying for 12H, grinding into powder, taking 2g of carrier precursor, placing in an evaporation dish, adding 20mL deionized water, then adding 33 mu L of 200mg/mL H 2 PtCl 6 The solution was stirred ultrasonically for 20min and dried at 60℃for 12h. Then heating to 600 ℃ at a speed of 1 ℃/min under static air atmosphere, and keeping for 4 hours to obtain Pt/Al 2 O 3 Catalyst D3 was subsequently reduced under a pure hydrogen atmosphere at 500℃for 2h for ethane dehydrogenation.
Performance testing
1. Topography testing
FIG. 1 is a scanning electron microscope image of catalyst C5 prepared in example 5; FIG. 2 is a transmission electron micrograph of catalyst C5 prepared in example 2;
FIG. 3 is a scanning electron microscope image of catalyst D1 prepared in comparative example 1; fig. 4 is a transmission electron microscopic image of the catalyst D1 prepared in comparative example 1.
As can be seen from fig. 1, the catalyst prepared by the present invention has a flower-like structure of nano-sheet stack, and meanwhile, as can be seen from fig. 2, the dispersibility of the active metal Pt is good; while the results in fig. 3 show that the catalyst prepared using commercially available gamma-alumina as a carrier has no flower-like morphology, and fig. 4 shows that the active metal Pt is agglomerated.
2. Catalytic performance test
The evaluation method comprises the following steps: the catalyst evaluation device is a fixed bed micro-reaction device, a quartz tube with the length of 600mm, the outer diameter of 10mm and the inner diameter of 8mm is adopted, and raw materials and products are subjected to GC456 gas chromatography on-line analysis.
Evaluation conditions: the catalyst dosage is 0.2g, the reaction pressure is normal pressure, the reaction temperature is 590 ℃, the ethane flow is 7mL/min, and the nitrogen flow is 21mL/min.
The product analysis and calculation method comprises the following steps: the product after ethane dehydrogenation mainly comprises methane, ethane, ethylene, propane, propylene and trace C 4 The components are subjected to qualitative analysis according to the residence time of the standard substance in the chromatograph, and quantitative analysis is performed by adopting an area normalization method after the peak area is corrected.
Based on the amounts of the respective components obtained by chromatography, the ethane conversion and the ethylene selectivity were calculated, respectively, and the obtained results are shown in Table 1.
TABLE 1 catalytic Performance test results
According to the data in Table 1, it can be seen that the nano-sheet stacked flower-like structure Pt/gamma-alumina catalyst prepared by the invention has excellent catalytic performance, high ethane conversion rate and high ethylene selectivity, and especially the catalyst C5, after 480 hours of continuous use, the ethane conversion rate can still reach 24.2%, and the ethylene selectivity can reach 95.8%. The catalysts prepared in comparative examples 1 to 3, however, had gradually decreased activity after a reaction time of more than 360min, had only 3% and 1% ethane conversion for catalysts D1 and D2 at 480h, had no co-impregnant for catalyst D3, and had only 13.2% ethane conversion after 480h, which was significantly lower than that of catalyst C5.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the Pt/gamma-alumina catalyst with the nano-sheet stacked flower-like structure is characterized by comprising the following steps of:
mixing an aluminum source, a precipitator, a template agent solution and water, and performing hydrothermal crystallization to obtain a carrier precursor;
preparing a carrier precursor dispersion liquid from the carrier precursor, mixing the carrier precursor dispersion liquid, a co-impregnant and a Pt source, and sequentially carrying out ultrasonic treatment, drying and roasting to obtain a nano-sheet stacked flower-like structure Pt/gamma-alumina catalyst; the co-impregnant includes an acid and/or a metal chloride salt.
2. The method of claim 1, wherein the acid comprises one or more of hydrochloric acid, citric acid, oxalic acid, and tartaric acid; the metal chloride salt comprises potassium chloride and/or sodium chloride; the dosage ratio of the carrier precursor and the co-impregnant is (0.5-3) g (0.5-15) mmol.
3. The method of claim 1, wherein the aluminum source comprises aluminum chloride and/or aluminum nitrate; the precipitant is urea and/or ammonia water; the molar ratio of the aluminum source to the precipitator is (0.05-2): 1;
the template agent in the template agent solution is P123 and/or F127; the mass ratio of the aluminum source to the template agent in the template agent solution is (1-5): 1.
4. The method according to claim 1, wherein the hydrothermal crystallization is performed at a temperature of 100 to 200 ℃ for a time of 12 to 48 hours.
5. The method according to claim 1, wherein the dispersion medium for preparing the carrier precursor dispersion is water or an alcohol solvent; the dosage ratio of the carrier precursor to the dispersion medium is 1g (5-20) mL;
the Pt source comprises H 2 PtCl 6 、Na 2 PtCl 4 、Pt(NH 3 ) 4 Cl 2 、Pt(NH 3 ) 2 (NO 2 ) 2 And K 2 PtCl 6 One or more of the following; the mass ratio of the carrier precursor to the Pt source is (500-3000) (0.05-50).
6. The method according to claim 1, wherein the time of the ultrasonic treatment is 5 to 30 minutes; the drying temperature is 30-150 ℃ and the drying time is 8-12 h.
7. The method according to claim 1, wherein the baking temperature is 300 to 700 ℃ for 2 to 6 hours; the roasting atmosphere is one or a mixture of more of air, oxygen and inert atmosphere.
8. The Pt/γ -alumina catalyst of stacked flower-like structure of nanoplatelets prepared by the preparation method of any one of claims 1 to 7; the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is a gamma-alumina catalyst, and the active component is Pt; the carrier exists in a flower-like structure of nano-sheet stacks; the active component exists in the form of nano particles or nano clusters; the mass fraction of active components in the Pt/gamma-alumina catalyst with the nano-sheet stacked flower-like structure is 0.01-2%.
9. Use of the nanoplatelet stacked flower Pt/gamma-alumina catalyst of claim 8 in ethane dehydrogenation reactions.
10. The method of claim 1, wherein the nanoplatelet stacked flower Pt/γ -alumina catalyst is reduced prior to application; the reduction is performed in an atmosphere containing a reducing gas; the reducing gas is hydrogen and/or carbon monoxide; the temperature of the reduction is 80-600 ℃ and the time is 0.5-4 h.
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| CN115155591A (en) * | 2022-07-04 | 2022-10-11 | 中国石油大学(北京) | Co-based catalyst for propane dehydrogenation and preparation method thereof |
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| US5358920A (en) * | 1992-12-21 | 1994-10-25 | China Petro-Chemical Corporation | Dehydrogenating catalyst for saturate hydrocarbons |
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