CN111054383A - Catalyst for dehydrogenation reaction of organic liquid hydrogen storage material and preparation method thereof - Google Patents

Catalyst for dehydrogenation reaction of organic liquid hydrogen storage material and preparation method thereof Download PDF

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CN111054383A
CN111054383A CN201811201433.8A CN201811201433A CN111054383A CN 111054383 A CN111054383 A CN 111054383A CN 201811201433 A CN201811201433 A CN 201811201433A CN 111054383 A CN111054383 A CN 111054383A
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catalyst
hydrogen storage
organic liquid
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dehydrogenation
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CN111054383B (en
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柯俊
童凤丫
孙清
缪长喜
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

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Abstract

The invention discloses a catalyst for dehydrogenation reaction of an organic liquid hydrogen storage material and a preparation method thereof, which solve the technical problems of poor catalyst activity and low dehydrogenation rate in the prior art, and the invention adopts the catalyst that the atomic ratio of Fe to Pt on the surface of the catalyst is 0.14-0.47 in an X-ray photoelectron spectrum; the paint comprises the following components in parts by weight: a) 0.1-10 parts of Pt-Fe nano particles or oxides thereof, b) 0.1-5 parts of alkali metals or oxides thereof, c) 0.1-10 parts of lanthanide Ln or oxides thereof, wherein Ln is selected from at least one of La, Ce, Pr and Nd, and d) 80-99 parts of carrier S, wherein S is selected from at least one of alumina, silicon oxide and titanium oxide.

Description

Catalyst for dehydrogenation reaction of organic liquid hydrogen storage material and preparation method thereof
Technical Field
The invention discloses a catalyst with high activity for dehydrogenation reaction of an organic liquid hydrogen storage material and a preparation method thereof.
Background
Hydrogen energy has been widely spotlighted as a representative of green sustainable new energy. In the beginning of the 21 st century, hydrogen energy development plans were made in china and the united states, japan, canada, european union, etc., and related studies were pursued. Hydrogen energy applications include hydrogen gas production, storage, transportation, and application links, where hydrogen energy storage is a key and difficult point. Hydrogen fuel vehicles are the main approach for hydrogen energy application, and the development of hydrogen storage technology suitable for hydrogen fuel vehicles is the premise of large-scale application of hydrogen energy.
At present, the hydrogen storage technology mainly comprises physical hydrogen storage, adsorption hydrogen storage and chemical hydrogen storage. Physical hydrogen storage technology has met the requirements of vehicles, but its high requirements on equipment and harsh operating conditions have made the contradiction between performance and efficiency of this technology increasingly prominent. Adsorption hydrogen storage and chemical hydrogen storage are the key points of the current research, and certain research results are obtained, but certain differences exist between the technical requirements of vehicle-mounted hydrogen storage. The organic liquid hydrogen storage technology (organic liquid mainly comprises methylcyclohexane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole, perhydrocarbazole and the like) in chemical hydrogen storage realizes the storage of hydrogen energy through catalytic addition and dehydrogenation reversible reaction, the reaction in the process is reversible, reactant products can be recycled, and the hydrogen storage amount is relatively high (about 60-75 kg H)2·m-3The mass fraction is 6-8 percent), the method meets the indexes specified by the International energy agency and the United states department of energy (DOE), and the method can be used for long-distance transportation in the form of organic liquid or can solve the problem of uneven distribution of energy in areas, really meets the requirements of green chemistry, and has a strong application prospect.
The hydrogenation process and the dehydrogenation process exist simultaneously in the organic liquid hydrogen storage technology, the hydrogenation process is relatively simple, the technology is mature, and the dehydrogenation process is a strong endothermic and highly reversible reaction, so that the dehydrogenation reaction is favorably carried out at high temperature from the aspects of dynamics and thermodynamics, but the activity of the catalyst is reduced and even inactivated due to side reactions such as cracking, carbon deposition and the like which are easily generated at high temperature, and the dehydrogenation reaction is not favorably carried out.
Pt/Al is simple and cheap in preparation method2O3Catalysts are widely used as organic liquidsDehydrogenation catalyst for hydrogen storage material, but the catalyst needs to be calcined at high temperature and reduced by hydrogen in the preparation process, because Pt and Al2O3The interaction between the Pt and the Pt is weak, which easily causes Pt atoms to gather in the preparation process, so that the size is enlarged, and finally the activity of the catalyst is low; in addition to Al2O3The weakly acidic nature of the surface allows coking to occur quickly after the start of the catalytic reaction, so that the activity of the catalyst is poor even during the first hours of the reaction, and thus Pt/Al2O3Is not an ideal dehydrogenation catalyst for organic liquid hydrogen storage materials, and the research on high-activity dehydrogenation catalysts is urgently needed. Since the dehydrogenation effect of Pt is the best among all metals, in the research of organic liquid dehydrogenation catalysts, the emphasis is to select a suitable assistant to change the carrier or regulate the surface properties of the carrier, so as to play the roles of regulating the size of Pt, the specific surface area of the carrier, the acidity and alkalinity of the carrier, and the like, or to generate other beneficial effects, so that the catalyst shows higher activity.
CN105102120A discloses a dehydrogenation catalyst for naphthenic hydrocarbons, which is prepared by adding Pt/Al2O3Group 3 metals are introduced into the catalyst as promoters. CN103443060B discloses a method for catalyzing dehydrogenation of saturated cyclic hydrocarbons and five-membered cyclic compounds with a Pt-Sn dehydrogenation catalyst.
The organic liquid dehydrogenation catalytic reaction is usually to convert at least one non-aromatic ring containing or not containing heteroatoms in the raw material into an aromatic ring or an aromatic heterocycle through dehydrogenation reaction, and the structural characteristics, the characteristics of thermodynamic data and the like determine that the organic liquid dehydrogenation catalytic reaction and the catalyst thereof are different from the dehydrogenation of low-carbon alkane, the dehydrogenation of alkyl aromatic hydrocarbon or other dehydrogenation reactions and the catalysts thereof. Therefore, the organic liquid dehydrogenation catalyst, particularly the auxiliary agent therein, needs to be finely designed and regulated, the catalyst and the preparation method thereof proposed in the invention are not reported in documents or patents, and good catalytic activity and good catalytic effect can be achieved.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problems of lower activity and lower dehydrogenation rate of the organic liquid hydrogen storage material dehydrogenation catalyst in the prior art, and provides a novel catalyst for dehydrogenation reaction of the organic liquid hydrogen storage material. The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows:
a catalyst for dehydrogenation reaction of organic liquid hydrogen storage materials is characterized in that in an X-ray photoelectron spectrum, the atomic ratio of Fe to Pt on the surface of the catalyst is 0.14-0.47.
The paint comprises the following components in parts by weight:
1) 0.1-10 parts of Pt-Fe nanoparticles or oxides thereof;
2)0.1 to 5 parts of an alkali metal or an oxide thereof;
3) 0.1-10 parts of lanthanide element Ln or oxide thereof, wherein Ln is selected from at least one of La, Ce, Pr and Nd;
4) 80-99 parts of carrier S, wherein S is at least one of alumina, silica and titanium oxide.
In the technical scheme, the preferable part of the Pt-Fe nano particles or the oxide thereof is 0.1-3.5 parts by weight.
In the technical scheme, the molar ratio of Fe to Pt in the catalyst is preferably (0.08-0.96) to 1.
In the technical scheme, more preferably, the molar ratio of Fe to Pt in the catalyst is (0.2-0.67): 1.
In the above technical solution, the alkali metal element is preferably at least one element selected from the group consisting of K, Na, Rb and Cs.
In the above technical solution, preferably, the alkali metal or the oxide thereof is 0.5 to 2.5 parts by weight.
In the above technical solution, preferably, the lanthanoid is selected from at least one of La, Ce, Pr, and Nd elements.
In the above technical solution, it is more preferable that the lanthanoid is selected from La and Nd, or from Ce and Nd.
In the above technical solution, preferably, the lanthanide element or the oxide thereof is 0.5 to 5 parts by weight.
In the above technical solution, preferably, the carrier is selected from γ -Al2O3Or SiO2One kind of (1).
In the above technical solution, more preferably, the carrier is selected from γ -Al2O3。
In the technical scheme, preferably, in an X-ray photoelectron spectrum, the atomic ratio of Fe to Pt on the surface of the catalyst is 0.16-0.47, and the atomic ratio of Fe to Pt on the surface of the catalyst is 0.19-0.38.
The method for measuring the surface atomic ratio Fe to Pt comprises the following steps of pre-reducing a catalyst in a hydrogen atmosphere at 350 ℃, and then testing an X-ray photoelectron spectrum on an X-ray photoelectron spectrometer by taking K α rays of Al as a light source, wherein the calculation formula of the surface atomic ratio Fe to Pt of the catalyst is as follows:
surface atomic ratio of catalyst Fe Pt (A) (Fe)/(S) (Fe))/(A (Pt))/(S) (Pt))
Wherein, A (Fe) and A (Pt) are peak areas of a 2p peak of Fe and a 4f peak of Pt in an X-ray photoelectron spectrum respectively, and S (Fe) and S (Pt) are sensitivity factors of the 2p peak of Fe and the 4f peak of Pt of an instrument used respectively. The catalyst surface here refers to the atoms on the catalyst within the depth of probing of the instrument in this test, which is usually expressed in terms of the inelastic mean free path, with Fe and Pt on the catalyst surface having an inelastic mean free path of 1.3 and 1.6nm, respectively, under the test conditions described above.
To solve the second technical problem, the invention adopts the following technical scheme:
a method for preparing a catalyst for dehydrogenation of an organic liquid hydrogen storage material, which corresponds to one of the technical problems solved, comprising the steps of:
a) dissolving soluble compounds of Pt and Fe in water, contacting with a reducing agent, a nano-particle coating reagent and soluble halide, and treating to obtain Pt-Fe nano-particles;
b) dissolving soluble salts of alkali metal and lanthanide in water, adding the soluble salts into a carrier S, mixing, and treating to obtain a catalyst precursor I;
c) and (b) dispersing the Pt-Fe nano particles obtained in the step (a) in a solvent, adding the solvent selected from at least one of ethanol, propanol and n-butanol into the catalyst precursor I obtained in the step (b), mixing, volatilizing the solvent, and processing to obtain the organic liquid hydrogen storage material dehydrogenation catalyst. Preferably, the preparation process also comprises the steps of dipping, drying and roasting.
The catalyst comprises the following components in parts by weight: 0.1-10 parts of Pt-Fe nanoparticles or oxides thereof; 0.1 to 5 parts of an alkali metal or an oxide thereof; 0.1-10 parts of lanthanide element Ln or oxide thereof, wherein Ln is selected from at least one of La, Ce, Pr and Nd; 80-99 parts of a carrier S, wherein S is at least one selected from alumina, silica and titanium oxide; in an X-ray photoelectron spectrum of the catalyst, the atomic ratio of Fe to Pt on the surface of the catalyst is 0.14-0.47.
In the above technical solution, preferably, the soluble salt of Pt is preferably one of chloroplatinic acid and potassium chloroplatinite, the soluble salt of Fe and the lanthanide is preferably one of nitrate and chloride, and the soluble salt of the alkali metal element is preferably one of nitrate, acetate and carbonate.
In the above technical solution, preferably, in step a), the reducing agent is selected from one of hydrazine hydrate or sodium borohydride, the coating reagent is selected from polyvinylpyrrolidone, and the soluble halide is preferably selected from one of potassium chloride or potassium bromide.
In the technical scheme, preferably, the dipping temperature in the dipping process is 10-80 ℃, the dipping time is 1-24 hours, the drying temperature is 50-150 ℃, and the drying time is 4-24 hours. The roasting process is carried out at 450-650 ℃ for 4-24 hours.
The organic liquid hydrogen storage material dehydrogenation catalyst prepared by the method is subjected to activity evaluation in an isothermal fixed bed reactor, and the reaction conditions are as follows: the reaction pressure is 0-1 MPa, the temperature is 200-450 ℃, and the mass space velocity is 0.1-10 h-1(ii) a The organic liquid hydrogen storage material is contacted with the catalyst to react to generate hydrogen and corresponding aromatic hydrocarbon.
In the above technical solution, preferably, the organic liquid hydrogen storage material is selected from at least one of methylcyclohexane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole, and perhydrocarbazole.
In the above technical solution, preferably, the activation conditions before the catalyst reaction are as follows: the reduction temperature is 300-500 ℃, preferably 300-400 ℃, and the hydrogen flow rate in the reduction process is 100-500 mL/min-1Preferably 200 to 400 mL/min-1The reduction time is 2-8 h, preferably 3-6 h.
The dehydrogenation rate was calculated as follows according to the above evaluation method: the dehydrogenation rate is the amount of species of hydrogen gas produced by the reaction per unit mass of catalyst surface Pt per unit reaction time. The mass of Pt on the surface of the catalyst is measured by a carbon monoxide chemisorption method at 25 ℃ on a chemisorption and desorption instrument, and a sample is pre-reduced by hydrogen at 300 ℃ on the chemisorption and desorption instrument before the test. The dehydrogenation rate is calculated as follows:
dehydrogenation rate ÷ amount of substance of hydrogen gas produced by reaction ÷ reaction time ÷ mass of Pt on the surface of the catalyst
In the dehydrogenation catalysis process of the organic liquid hydrogen storage material, Pt is used as a single active component of the catalyst, the activity of the catalyst is limited by the electronic structure of the catalyst, and the catalytic activity of the Pt catalyst can be improved by adding an auxiliary agent and selecting a proper carrier. The invention adopts Pt-Fe nano particles or oxides thereof, utilizes the synergistic effect between the Pt-Fe nano particles or oxides thereof and alkali metal and lanthanide, and leads the catalytic dehydrogenation rate of the catalyst provided by the invention in the dehydrogenation catalytic reaction of the organic liquid hydrogen storage material to reach 31 mmol-g by a corresponding catalyst preparation method-1·s-1And a better technical effect is generated.
The invention is further illustrated by the following examples, but is not limited thereto.
Detailed Description
[ example 1 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
Grinding the obtained catalyst into particles with the particle size of 12-20 meshes, measuring the surface atomic ratio Fe to Pt of the catalyst on an X-ray photoelectron spectrometer according to the measuring method, measuring the mass of the Pt on the surface of the catalyst by a carbon monoxide chemisorption method on a chemisorption and desorption instrument according to the measuring method, mixing and diluting 0.1g of quartz sand with a proper amount of 20 meshes without catalytic activity, and evaluating in an isothermal fixed bed reactor, wherein the flow is 300 mL-min before evaluation-1The catalyst is reduced by the hydrogen flow at normal pressure and 350 ℃ for 4h, and the temperature is reduced at normal pressure and 320 ℃ after the temperature is reduced, and the space velocity is 4h-1The average dehydrogenation rate in 6 hours of the catalytic dehydrogenation reaction was obtained according to the above-mentioned calculation formula of dehydrogenation reaction by evaluating the catalyst under the conditions of methylcyclohexane as a representative raw material for storing hydrogen in an organic liquid, and the results are shown in table 1.
[ example 2 ]
192mg of potassium chloroplatinite, 18.4mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3Support, impregnation at room temperatureAnd drying for 4h in a 90 ℃ oven, and then putting the dried product into a muffle furnace to roast for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 3 ]
192mg of potassium chloroplatinite, 61.6mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 4 ]
192mg of potassium chloroplatinite, 7.4mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 5 ]
192mg of potassium chloroplatinite, 88.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 6 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 1.1mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 7 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 25.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 8 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 38.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 9 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 103mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 10 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
28.1mg potassium nitrate, 102mg lanthanum nitrate and 99.1mg neodymium nitrate were weighed and dissolved in 3mL water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 11 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
141mg potassium nitrate, 102mg lanthanum nitrate and 99.1mg neodymium nitrate were dissolved in 3mL water, and 2.0g of γ -Al was added with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 12 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
5.6mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 13 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
281mg potassium nitrate, 102mg lanthanum nitrate and 99.1mg neodymium nitrate were weighed, dissolved in 3mL water, and 2.0g of gamma-Al was added with stirring2O3Soaking the carrier at room temperature for 4h, drying in oven at 90 deg.C for 4h, and standingCalcining the precursor in a muffle furnace at 650 ℃ for 4h to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 14 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
80.4mg of sodium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed and dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 15 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
37.5mg of rubidium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate are weighed and dissolved in 3mL of water, and 2.0g of gamma-Al is added under stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 16 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
31.9mg of cesium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were dissolved in 3mL of water, and 2.0g of γ -Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 17 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 128mg of ceric ammonium nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 18 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate and 203mg of lanthanum nitrate were weighed, dissolved in 3mL of water, and 2.0g of γ -Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 19 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg potassium nitrate and 255mg ceric ammonium nitrate were weighed and dissolved in 3mL water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 20 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate and 200mg of praseodymium nitrate were weighed and dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 21 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
Weighing 56.2mg potassium nitrate and 198mg neodymium nitrate, dissolving in 3mL water, adding while stirring2.0g of gamma-Al2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 22 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 16.9mg of lanthanum nitrate and 16.5mg of neodymium nitrate were weighed and dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 23 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 169mg of lanthanum nitrate and 165mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 24 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 3.4mg of lanthanum nitrate and 3.3mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of γ -Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 25 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 339mg of lanthanum nitrate and 330mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 26 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of SiO was added thereto with stirring2The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
[ example 27 ]
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of TiO was added thereto with stirring2The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
Comparative example 1
55.5mg of potassium chloroplatinite was dissolved in 3mL of water, and 2.0g of gamma-Al was added under stirring2O3The carrier is added into the solution, dipped for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then put into a muffle furnace to be roasted for 4h at 650 ℃ to obtain the catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
Comparative example 2
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
Weighing 50.4mg of potassium chloroplatinite and 17.3mg of ferric nitrate, dissolving in 3mL of water, adding the catalyst precursor I under stirring, standing for 4h, drying in a 90 ℃ oven for 4h, and then putting into a muffle furnace to be roasted at 650 ℃ for 4h to obtain the catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
Comparative example 3
Dissolving 192mg of potassium chloroplatinite, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide in 284mL of deionized water in a 500mL hydrothermal kettle, uniformly mixing, adding 16mL of hydrazine hydrate solution with the mass fraction of 85%, reacting for 1h in a 160 ℃ oven, centrifugally separating, washing to obtain Pt-Fe nanoparticles, and dispersing the nanoparticles in ethanol.
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
Comparative example 4
192mg of potassium chloroplatinite, 230mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and Pt-Fe nano particles are obtained after centrifugal separation and washing and are dispersed in ethanol.
56.2mg of potassium nitrate, 102mg of lanthanum nitrate and 99.1mg of neodymium nitrate were weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added thereto with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
Comparative example 5
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
102mg of lanthanum nitrate and 99.1mg of neodymium nitrate are weighed and dissolved in 3mL of water, and 2.0g of gamma-Al is added under stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
Comparative example 6
192mg of potassium chloroplatinite, 32.2mg of ferrous chloride, 500mg of polyvinylpyrrolidone and 5.0g of potassium bromide are dissolved in 284mL of deionized water in a 500mL hydrothermal kettle and uniformly mixed, 16mL of hydrazine hydrate solution with the mass fraction of 85% is added, the mixture is reacted for 1h in a 160 ℃ oven, and after centrifugal separation and washing, Pt-Fe nano particles are obtained and dispersed in ethanol.
56.2mg of potassium nitrate was weighed, dissolved in 3mL of water, and 2.0g of gamma-Al was added with stirring2O3The carrier is soaked for 4h at room temperature, dried for 4h in a 90 ℃ oven, and then placed into a muffle furnace to be roasted for 4h at 650 ℃ to obtain a catalyst precursor I.
1.0g of the above catalyst precursor I was added to ethanol in which 13.0mg of Pt-Fe nanoparticles were dispersed with stirring, left to stand for 4 hours, dried in an oven at 50 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.
The obtained catalyst is ground into particles with the particle size of 12-20 meshes, the quality of Pt on the surface of the catalyst and the determination method of the surface atomic ratio Fe to Pt are the same as those in example 1, 0.1g of the catalyst is mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then is evaluated in an isothermal fixed bed reactor, hydrogen is used for reduction before evaluation, and the reduction conditions and the evaluation conditions are the same as those in example 1, and the results are shown in Table 1.
TABLE 1
Figure BDA0001830094840000221
Figure BDA0001830094840000231
[ examples 28 to 34 ]
The performance of the catalyst prepared in example 1 for dehydrogenation of organic liquid hydrogen storage material was evaluated and the results are shown in table 2.
TABLE 2
Figure BDA0001830094840000241

Claims (11)

1. A catalyst for dehydrogenation reaction of organic liquid hydrogen storage materials is characterized in that in an X-ray photoelectron spectrum, the atomic ratio of Fe to Pt on the surface of the catalyst is 0.14-0.47.
2. The catalyst for dehydrogenation of organic liquid hydrogen storage material according to claim 1, comprising the following components in parts by weight:
1) 0.1-10 parts of Pt-Fe nanoparticles or oxides thereof;
2)0.1 to 5 parts of an alkali metal or an oxide thereof;
3) 0.1-10 parts of lanthanide element Ln or oxide thereof, wherein Ln is selected from at least one of La, Ce, Pr and Nd;
4) 80-99 parts of carrier S, wherein S is at least one of alumina, silica and titanium oxide.
3. The catalyst for dehydrogenation of organic liquid hydrogen storage material according to claim 1, wherein the Pt-Fe nanoparticles or the oxide thereof are present in an amount of 0.1-3.5 parts by weight.
4. The catalyst for dehydrogenation of organic liquid hydrogen storage material according to claim 1, wherein the ratio of Fe to Pt in the catalyst is (0.08-0.96): 1, preferably (0.2-0.67): 1.
5. The catalyst for dehydrogenation of organic liquid hydrogen storage material according to claim 1, wherein the alkali metal element is at least one element selected from K, Na, Rb and Cs, and the part of the alkali metal or its oxide is 0.5-2.5 parts by weight.
6. The catalyst for dehydrogenation of organic liquid hydrogen storage material according to claim 1, wherein the lanthanide is selected from at least one of La, Ce, Pr and Nd, preferably La and Nd, or Ce and Nd, and the part of the lanthanide or its oxide is 0.5-5 parts by weight.
7. The catalyst for dehydrogenation of organic liquid hydrogen storage materials of claim 1, wherein the support is S is γ -Al2O3Or SiO2Preferably gamma-Al2O3。
8. The catalyst for dehydrogenation of light alkane according to claim 1, wherein the atomic ratio Fe to Pt on the surface of the catalyst in X-ray photoelectron spectroscopy is 0.19-0.38.
9. A preparation method of an organic liquid hydrogen storage material dehydrogenation catalyst comprises the following steps:
a) dissolving soluble compounds of Pt and Fe in water, contacting with a reducing agent, a nano-particle coating reagent and soluble halide, and treating to obtain Pt-Fe nano-particles;
b) dissolving soluble salts of alkali metal and lanthanide in water, adding the soluble salts into a carrier S, and mixing to obtain a catalyst precursor I;
c) dispersing the Pt-Fe nano particles obtained in the step a in a solvent, adding the Pt-Fe nano particles into the catalyst precursor I obtained in the step b, mixing, volatilizing the solvent, and processing to obtain an organic liquid hydrogen storage material dehydrogenation catalyst;
d) preferably, the preparation process also comprises the steps of dipping, drying and roasting;
the catalyst comprises the following components in parts by weight: 0.1-10 parts of Pt-Fe nanoparticles or oxides thereof; 0.1 to 5 parts of an alkali metal or an oxide thereof; 0.1-10 parts of lanthanide element Ln or oxide thereof, wherein Ln is selected from at least one of La, Ce, Pr and Nd; 80-99 parts of a carrier S, wherein S is at least one selected from alumina, silica and titanium oxide; in an X-ray photoelectron spectrum of the catalyst, the atomic ratio of Fe to Pt on the surface of the catalyst is 0.14-0.47.
10. A method for dehydrogenating an organic liquid hydrogen storage material comprises the following reaction conditions: the reaction pressure is 0-1 MPa, the temperature is 200-450 ℃, and the mass space velocity is 0.1-10 h-1(ii) a The organic liquid hydrogen storage material is contacted with the catalyst of any one of claims 1 to 9 to react to generate hydrogen and corresponding aromatic hydrocarbon.
11. The method of dehydrogenating an organic liquid hydrogen storage material according to claim 10, characterised in that the organic liquid hydrogen storage material is selected from at least one of methylcyclohexane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole and perhydrocarbazole.
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