CN111054382B

CN111054382B - Catalyst for dehydrogenation of organic liquid hydrogen storage materials

Info

Publication number: CN111054382B
Application number: CN201811201426.8A
Authority: CN
Inventors: 柯俊; 童凤丫; 孙清; 缪长喜
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2018-10-16
Filing date: 2018-10-16
Publication date: 2022-12-09
Anticipated expiration: 2038-10-16
Also published as: CN111054382A

Abstract

The invention discloses a catalyst for dehydrogenation reaction of organic liquid hydrogen storage material and a preparation method thereof, aiming at solving the problems of poor carbon deposition resistance and large carbon deposition amount in the dehydrogenation reaction process in the prior art, the invention adopts a catalyst containing platinum group elements or oxides thereof, wherein the dispersion degree of Pt is not less than 21 percent; the paint comprises the following components in parts by weight: a) 0.1-4.8 parts of platinum group elements or oxides thereof, b) 0.1-6.5 parts of alkali metals or oxides thereof, c) 0.1-9.6 parts of Ba and/or Sc or oxides thereof, d) 80-99 parts of carrier S, wherein S is selected from Fe-Al-O or Fe-Al-Zr-O composite oxides; the catalyst and the preparation method thereof have the advantages of better carbon deposition resistance and smaller carbon deposition amount when being used for dehydrogenation reaction of the organic liquid hydrogen storage material.

Description

Catalyst for organic liquid hydrogen storage material dehydrogenation

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. Organic liquid hydrogen storage technology in chemical hydrogen storage (organic liquid mainly comprises methylcyclohexane, cyclohexane, tetrahydronaphthalene and decahydrogenNaphthalene, perhydroazeethylcarbazole, perhydrocarbazole, etc.) is subjected to reversible catalytic addition and dehydrogenation reactions to store hydrogen energy, the reaction in the process is reversible, reactant products can be recycled, and the hydrogen storage capacity is relatively high (about 60-75 kg of H) ₂ ·m ^-3 The mass fraction is 6-8 percent), meets the indexes specified by the International energy agency and the United states department of energy (DOE), is transported for a long distance 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 stronger application prospect.

The hydrogenation process and the dehydrogenation process exist in the organic liquid hydrogen storage technology at the same time, the hydrogenation process is relatively simple, the technology is mature, and the dehydrogenation process is a strong endothermic and highly reversible reaction, so from the aspects of dynamics and thermodynamics, the high temperature is favorable for the dehydrogenation reaction, but the side reactions such as cracking, carbon deposition and the like are easy to occur at the high temperature, so that the activity of the catalyst is reduced and even inactivated, and the dehydrogenation reaction is not favorably carried out.

Pt/Al is simple and cheap in preparation method ₂ O ₃ The catalyst is widely used as a dehydrogenation catalyst of organic liquid hydrogen storage material, but the catalyst needs to be calcined at high temperature and reduced by hydrogen in the preparation process, because Pt and Al ₂ O ₃ The interaction between the Pt and the Pt belongs to weaker interaction, which easily causes Pt atoms to gather in the preparation process, so that the size is enlarged; in addition to Al ₂ O ₃ The weak acidity of the surface enables carbon deposition to be rapidly generated after the start of the catalytic reaction, so that the activity of the catalyst is poor even in the first few hours of the reaction, and thus Pt/Al ₂ O ₃ The catalyst is not an ideal dehydrogenation catalyst for the organic liquid hydrogen storage material, and the catalyst with better carbon deposition resistance and smaller carbon deposition amount needs to be researched aiming at the defect. Since the dehydrogenation effect of Pt is the best among all metals, in the research of organic liquid dehydrogenation catalyst, the emphasis is to select proper auxiliary agent to change the carrier or regulate the surface property of the carrier, so as to play the role of regulating the size of Pt, the specific surface area of the carrier, the acidity and alkalinity of the carrier, etc., or generate other beneficial effects, so that the catalyst shows higher carbon deposition resistance.

CN105102120A discloses a dehydrogenation catalyst for naphthenic hydrocarbons by reacting with Pt/Al ₂ O ₃ Group 3 metals are introduced into the catalyst as promoters. CN103443060B discloses a method for 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 provided by the invention are not reported in documents or patents, and good carbon deposition resistance and good catalytic effect can be achieved.

Disclosure of Invention

One of the technical problems to be solved by the invention is that the organic liquid hydrogen storage material dehydrogenation catalyst in the prior art has poor carbon deposition resistance and large carbon deposition amount in the process of catalyzing the organic liquid hydrogen storage material dehydrogenation reaction, and a novel catalyst for the organic liquid hydrogen storage material dehydrogenation reaction is provided. 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 material is a catalyst containing platinum group element or its oxide, in which the dispersity of Pt is not less than 21%.

In the technical scheme, the catalyst comprises the following components in parts by weight:

a) 0.1-4.8 parts of platinum group elements or oxides thereof; b) 0.1 to 6.5 parts of alkali metal or an oxide thereof; c) 0.1-9.6 parts of element M or oxide thereof, wherein M is selected from Ba and/or Sc; d) 80 to 99 parts of carrier S, wherein S is selected from Fe-Al-O or Fe-Al-Zr-O composite oxide.

In the above technical solution, preferably, the component a) is selected from Pt or Pt-M, wherein M is other platinum group elements.

In the above technical solution, more preferably, the component a) is selected from Pt or Pt — Pd.

In the above technical solution, preferably, the part of Pt in the platinum group element is 0.1 to 2.4 parts by weight.

In the above technical solution, the molar ratio of Pd to Pt in the platinum group element is preferably (0 to 0.4): 1 in parts by weight.

In the above technical solution, preferably, the alkali metal element is at least one selected from K, na, rb and Cs.

In the above technical solution, the amount of the alkali metal or its oxide is preferably 0.5 to 2.5 parts, more preferably 1.1 to 2.5 parts by weight.

In the above technical solution, preferably, the element M is selected from Ba and Sc.

In the above technical solution, the element M is preferably 0.6 to 4.6 parts, more preferably 2.4 to 4.6 parts.

In the above-mentioned embodiment, it is preferable that Zr to Fe in the carrier is (0 to 0.22) to 1 in terms of molar ratio.

In the above technical solution, it is preferable that the molar ratio of Fe to Al in the carrier is (0.04 to 2.6): 1.

In the above technical solution, the dispersion degree of Pt is preferably not less than 30%, and preferably 30% to 60%.

The Pt dispersion was measured as follows: the dispersity of Pt is the percentage of Pt on the surface of the catalyst to all Pt in the catalyst, and the test method is as follows: taking a proper amount of catalyst, reducing the catalyst by hydrogen at 300 ℃ on a chemical adsorption and desorption instrument, and then obtaining the dispersion degree of Pt by a carbon monoxide chemical adsorption method at 25 ℃.

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 salts of Fe, al and Zr in water, adding an alkaline solution until the pH value is alkaline, and processing to obtain a carrier S;

b) Dissolving soluble salt of alkali metal and M element in water, adding the soluble salt into the carrier S, mixing, and treating to obtain a catalyst precursor I;

c) Dissolving soluble salt of platinum group elements in water, adding the soluble salt into the catalyst precursor I obtained in the step, mixing, and carrying out leaching treatment to obtain the organic liquid hydrogen storage material dehydrogenation catalyst.

d) Preferably, the preparation process also comprises the steps of dipping, drying and roasting;

the catalyst is a catalyst containing a platinum group element or an oxide thereof, wherein the dispersion degree of Pt is not less than 21%; the catalyst contains 0.1 to 4.8 parts of platinum group elements or oxides thereof by weight; 0.1 to 6.5 parts of alkali metal or an oxide thereof; 0.1-9.6 parts of element M or oxide thereof, wherein M is selected from Ba and/or Sc;80 to 99 parts of carrier S, wherein S is selected from Fe-Al-O or Fe-Al-Zr-O composite oxide.

In the above technical solution, preferably, the soluble salt of Pt is preferably selected from one of chloroplatinic acid and potassium chloroplatinite, the soluble salt of Fe, al, zr, ba, sc elements is preferably selected from one of chloride or nitrate, and the alkali metal is preferably selected from one of nitrate, acetate or carbonate.

In the above technical scheme, preferably, the dipping temperature in the dipping process is 10-80 ℃, the dipping time is 1-24 hours, the drying temperature is 80-150 ℃, and the drying time is 4-24 hours. The roasting process is carried out at 450-650 deg.C for 4-24 h.

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 ^-1 Preferably 200 to 400 mL/min ^-1 The reduction time is 2 to 8 hours, preferably 3 to 6 hours.

According to the evaluation method, the calculation method of the carbon deposition amount is as follows: the amount of carbon deposit is the mass of carbon deposit produced per unit mass of the catalyst. The carbon deposition amount measuring method comprises the following steps: the catalyst after the catalytic reaction was heated to a constant weight at 150 ℃ and its mass was recorded as w1, and then the catalyst was continuously heated to a constant weight in 600 ℃ air and its mass was recorded as w2. The calculation formula of the carbon deposition amount is as follows:

carbon deposition amount = (w 1-w 2)/w 2

During the dehydrogenation and catalysis process of the organic liquid hydrogen storage material, carbon deposition is one of important factors for limiting the catalytic capability of the catalyst, and the amount of the carbon deposition reflects the selectivity between the raw material converted into a gas phase or liquid phase product and the carbon deposition converted into a solid phase byproduct in the catalysis process. The Pt is used as a single active component of the catalyst, the optimization of the carbon deposition resistance of the catalyst is limited by the electronic structure of the catalyst, and the carbon deposition amount of the Pt catalyst can be reduced by adding a proper auxiliary agent and selecting a proper carrier. The catalyst provided by the invention has good anti-carbon deposition capability in the dehydrogenation catalytic reaction of the organic liquid hydrogen storage material by adopting the platinum element, the Fe-Al-O or Fe-Al-Zr-O composite oxide, the alkali metal element and the Ba and/or Sc element auxiliary agent and utilizing the synergistic effect among the platinum element, the Fe, the Zr, the alkali metal, the Ba and/or Sc element, so that the carbon deposition amount is reduced to 0.32%, and the catalyst has the advantages of good carbon deposition resistance and small carbon deposition amount, and generates good technical effects.

The invention is further illustrated by the following examples, but is not limited thereto.

Detailed Description

[ example 1 ] A method for producing a polycarbonate

24.2g of ferric nitrate, 2.58g of zirconium nitrate and 37.5g of aluminum nitrate were dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And (3) aging the product for 2h, then carrying out suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

155mg of potassium nitrate, 124mg of barium nitrate and 492mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the carrier S was added thereto with stirring, and the resulting solution was immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

68.5mg of chloroplatinic acid and 10.9mg of palladium chloride were dissolved in 3mL of water, and the catalyst precursor I was added thereto with stirring, immersed at room temperature for 4 hours, dried in a 90 ℃ oven 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, taking 0.1g of the particles to measure the dispersion degree of Pt in the catalyst on a chemical absorption and desorption instrument by using a carbon monoxide chemical adsorption method according to the method, taking 2g of the particles to be mixed and diluted by a proper amount of 20-mesh quartz sand without catalytic activity and then evaluating the mixture in an isothermal fixed bed reactor, wherein the flow rate is 300 mL/min before evaluation ^-1 The 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 1.1h ^-1 The catalyst was evaluated under the conditions of (1), methylcyclohexane was used as a representative raw material for hydrogen storage in an organic liquid, the conversion rate was recorded, and after the catalytic reaction for 70 hours, the amount of carbon deposition was measured by the above-described method for measuring the amount of carbon deposition, and the results are shown in table 1.

[ example 2 ] A method for producing a polycarbonate

24.2g of iron nitrate, 2.58g of zirconium nitrate and 37.5g of aluminum nitrate were dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And aging the product for 2h, performing suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

155mg of potassium nitrate, 124mg of barium nitrate, and 492mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the carrier S was added thereto with stirring, and the resultant was immersed at room temperature for 4 hours, dried in a 90 ℃ oven for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

68.5mg of chloroplatinic acid and 21.7mg of palladium chloride were dissolved in 3mL of water, and the catalyst precursor I was added thereto with stirring, immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.

The obtained catalyst was ground into particles with a particle size of 12-20 mesh, 0.1g of the catalyst was used in a chemisorption and desorption apparatus, the dispersion of Pt in the catalyst was measured by the above-mentioned method using a carbon monoxide chemisorption method, and 2g of the catalyst was mixed and diluted with a suitable amount of 20 mesh quartz sand having no catalytic activity, and then the mixture was evaluated in an isothermal fixed bed reactor, before the evaluation, reduction was carried out with hydrogen, and the reduction conditions and the evaluation conditions were the same as in example 1, and the results are shown in Table 1.

[ example 3 ] A method for producing a polycarbonate

68.5mg of chloroplatinic acid was dissolved in 3mL of water, and the above catalyst precursor I was added thereto with stirring, immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.

[ example 4 ]

24.2g of ferric nitrate, 2.58g of zirconium nitrate and 37.5g of aluminum nitrate were dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And aging the product for 2h, performing suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

11.4mg of chloroplatinic acid and 1.8mg of palladium chloride were dissolved in 3mL of water, and the catalyst precursor I was added thereto with stirring, immersed at room temperature for 4 hours, dried in a 90 ℃ oven for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.

The obtained catalyst was ground into particles having a particle size of 12 to 20 mesh, 0.1g of the dispersion of Pt in the catalyst was measured by carbon monoxide chemisorption on a chemisorption/desorption apparatus by the method described above, and 2g of the catalyst was diluted with an appropriate amount of 20 mesh quartz sand having no catalytic activity and mixed in an isothermal fixed bed reactor and subjected to reduction with hydrogen before the evaluation, the reduction conditions and the evaluation conditions were the same as in example 1, and the results are shown in table 1.

[ example 5 ]

148mg of chloroplatinic acid and 23.5mg of palladium chloride were dissolved in 3mL of water, and the catalyst precursor I was added thereto with stirring, immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.

[ example 6 ] A method for producing a polycarbonate

228mg of chloroplatinic acid and 36.2mg of palladium chloride were dissolved in 3mL of water, and the catalyst precursor I was added thereto with stirring, immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.

[ example 7 ]

457mg of chloroplatinic acid and 72.4mg of palladium chloride are dissolved in 3mL of water, the catalyst precursor I is added thereto with stirring, the mixture is immersed at room temperature for 4 hours, dried in a 90 ℃ oven for 4 hours, and then placed in a muffle furnace to be calcined at 650 ℃ for 4 hours, so that a catalyst is obtained.

[ example 8 ]

221mg of sodium nitrate, 124mg of barium nitrate and 492mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the above-mentioned carrier S was added thereto with stirring, immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

68.5mg of chloroplatinic acid and 10.9mg of palladium chloride were dissolved in 3mL of water, and the catalyst precursor I was added thereto with stirring, immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.

[ example 9 ] A method for producing a polycarbonate

24.2g of iron nitrate, 2.58g of zirconium nitrate and 37.5g of aluminum nitrate were dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And (3) aging the product for 2h, then carrying out suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

103mg of rubidium nitrate, 124mg of barium nitrate and 492mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the carrier S was added thereto with stirring, immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

[ example 10 ]

87.7mg of cesium nitrate, 124mg of barium nitrate and 492mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the carrier S was added thereto with stirring, immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

[ example 11 ]

70.3mg of potassium nitrate, 124mg of barium nitrate and 492mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the carrier S was added thereto with stirring, and the resulting solution was immersed at room temperature for 4 hours, dried in a 90 ℃ oven for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

[ example 12 ]

351mg of potassium nitrate, 124mg of barium nitrate and 492mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the carrier S was added thereto with stirring, and the resulting solution was immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

[ example 13 ] to prepare a suspension

14.1mg of potassium nitrate, 124mg of barium nitrate and 492mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the carrier S was added thereto with stirring, and the resulting solution was immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

[ example 14 ]

913mg of potassium nitrate, 124mg of barium nitrate and 492mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the carrier S was added thereto with stirring, and the resulting solution was immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

[ example 15 ]

155mg of potassium nitrate and 248mg of barium nitrate were dissolved in 5mL of water, and 5.0g of the above-mentioned carrier S was added thereto with stirring, immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

[ example 16 ] A method for producing a polycarbonate

155mg of potassium nitrate and 983mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the above-mentioned carrier S was added thereto with stirring, immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

[ example 17 ] to provide

155mg of potassium nitrate, 31mg of barium nitrate and 123mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the carrier S was added thereto with stirring, and the resulting solution was immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

[ example 18 ] A method for producing a polycarbonate

155mg of potassium nitrate, 238mg of barium nitrate and 942mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the above-mentioned carrier S was added thereto with stirring, immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

[ example 19 ] to provide

155mg of potassium nitrate, 5.2mg of barium nitrate, and 20.5mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the carrier S was added thereto with stirring, and the resulting solution was immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

[ example 20 ] A method for producing a polycarbonate

155mg of potassium nitrate, 496mg of barium nitrate and 1.97g of scandium nitrate were dissolved in 5mL of water, and 5.0g of the carrier S was added thereto with stirring, and the resulting solution was immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

[ example 21 ]

24.2g of ferric nitrate and 37.5g of aluminum nitrate were dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And aging the product for 2h, performing suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

[ example 22 ]

24.2g of iron nitrate, 5.58g of zirconium nitrate and 37.5g of aluminum nitrate were dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And aging the product for 2h, performing suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

[ example 23 ]

1.62g of ferric nitrate, 170mg of zirconium nitrate and 37.5g of aluminum nitrate were dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And (3) aging the product for 2h, then carrying out suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

[ example 24 ]

8.08g of iron nitrate, 0.86g of zirconium nitrate and 37.5g of aluminum nitrate were dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And aging the product for 2h, performing suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

[ example 25 ]

52.5g of ferric nitrate, 5.58g of zirconium nitrate and 37.5g of aluminum nitrate were dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And aging the product for 2h, performing suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

[ example 26 ]

105g of iron nitrate, 11.2g of zirconium nitrate and 37.5g of aluminum nitrate were dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And aging the product for 2h, performing suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

Comparative example 1

68.5mg of chloroplatinic acid was dissolved in 3mL of water, and 5.0g of γ -Al was added with stirring ₂ O ₃ Adding the catalyst, soaking at room temperature for 4h, drying in a 90 ℃ oven for 4h, and then placing in a muffle furnace for roasting at 650 ℃ for 4h to obtain the catalyst.

Comparative example 2

24.2mg of ferric nitrate and 2.58mg of zirconium nitrate were weighed, dissolved in 250mL of deionized water, and 5.1g of gamma-Al was added ₂ O ₃ After stirring the support for 1h, ammonia was added dropwise with continued stirring until the pH was 8.5. And aging the product for 2h, performing suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace to roast at 650 ℃ for 16h to obtain a catalyst precursor I.

155mg of potassium nitrate, 124mg of barium nitrate and 492mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the carrier S was added thereto with stirring, and the resulting solution was immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor II.

68.5mg of chloroplatinic acid and 10.9mg of palladium chloride were dissolved in 3mL of water, and the catalyst precursor II was added thereto with stirring, immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 650 ℃ for 4 hours to obtain a catalyst.

Comparative example 3

124mg of barium nitrate and 492mg of scandium nitrate were dissolved in 5mL of water, and 5.0g of the above-mentioned carrier S was added thereto with stirring, immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

Comparative example 4

155mg of potassium nitrate was dissolved in 5mL of water, and 5.0g of the above-mentioned carrier S was added thereto with stirring, and the resulting solution was immersed at room temperature for 4 hours, dried in an oven at 90 ℃ for 4 hours, and then calcined in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst precursor I.

Comparative example 5

2.58g of zirconium nitrate and 37.5g of aluminum nitrate were dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And aging the product for 2h, performing suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

[ COMPARATIVE EXAMPLE 6 ]

37.5g of aluminum nitrate was dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And aging the product for 2h, performing suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

Comparative example 7

24.2g of iron nitrate, 25.8g of zirconium nitrate and 37.5g of aluminum nitrate were dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And (3) aging the product for 2h, then carrying out suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

Comparative example 8

40.4g of iron nitrate, 4.29g of zirconium nitrate and 3.75g of aluminum nitrate were dissolved in 250mL of deionized water, and ammonia water was added dropwise with stirring to a pH of 8.5. And aging the product for 2h, performing suction filtration, washing with 500mL of water for three times, drying in a 90 ℃ oven for 16h, and then placing in a muffle furnace for roasting at 650 ℃ for 16h to obtain the carrier S.

TABLE 1

[ examples 27 to 33 ]

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

Claims

1. A catalyst for dehydrogenation of an organic liquid hydrogen storage material, the catalyst being a catalyst comprising a platinum group element or an oxide thereof, wherein the degree of dispersion of Pt is not less than 21%;

wherein, the catalyst contains 0.1 to 4.8 parts of platinum group elements or oxides thereof by weight; 0.1 to 6.5 parts of alkali metal or an oxide thereof; 0.1-9.6 parts of element M or oxide thereof, wherein M is selected from Ba and/or Sc; 80-99 parts of carrier S, wherein S is selected from Fe-Al-O or Fe-Al-Zr-O composite oxide;

in terms of molar ratio, zr to Fe in the carrier is (0-0.22) to 1;

the carrier contains 0.04-2.6 parts of Fe and 1 part of Al.

2. The catalyst for dehydrogenation of organic liquid hydrogen storage materials according to claim 1, the platinum group element being selected from Pt or Pt-Pd.

3. The catalyst for dehydrogenation of organic liquid hydrogen storage material according to claim 2, wherein the platinum group elements are Pt and Pd, the part of Pt in the platinum group elements is 0.1-2.4 parts by weight, and the molar ratio of Pd: pt is (0-0.4): 1.

4. 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 the group consisting of K, na, rb, cs, and the alkali metal or its oxide is 0.5-2.5 parts by weight.

5. The catalyst for dehydrogenation of an organic liquid hydrogen storage material according to claim 4, wherein the alkali metal or oxide thereof is present in an amount of 1.1 to 2.5 parts by weight.

6. The catalyst for dehydrogenation of organic liquid hydrogen storage material according to claim 1, wherein the element M is selected from Ba and Sc or their mixed oxides, and the part of the element M is 0.6-4.6 parts by weight.

7. The catalyst for dehydrogenation of organic liquid hydrogen storage material according to claim 6, wherein the element M is present in an amount of 2.4 to 4.6 parts by weight.

8. The catalyst for dehydrogenation of light alkanes according to claim 1, wherein the degree of dispersion of Pt is not less than 30%.

9. The catalyst for dehydrogenation of light alkanes according to claim 1, wherein the degree of dispersion of Pt is comprised between 30% and 60%.

10. A preparation method of an organic liquid hydrogen storage material dehydrogenation catalyst comprises the following steps:

b) Dissolving soluble salts of alkali metal and M element in water, adding the soluble salts into the carrier S in the step, mixing, and treating to obtain a catalyst precursor I;

c) Dissolving soluble salt of platinum group elements in water, adding the soluble salt into the catalyst precursor I obtained in the step, mixing, and processing to obtain an organic liquid hydrogen storage material dehydrogenation catalyst; the catalyst is a catalyst containing a platinum group element or an oxide thereof, wherein the dispersion degree of Pt is not less than 21%;

the catalyst contains 0.1 to 4.8 parts of platinum group elements or oxides thereof by weight; 0.1 to 6.5 parts of alkali metal or an oxide thereof; 0.1-9.6 parts of element M or oxide thereof, wherein M is selected from Ba and/or Sc; 80-99 parts of carrier S, wherein S is selected from Fe-Al-O or Fe-Al-Zr-O composite oxide; zr in the carrier is that Fe is 0-0.22: 1; the molar ratio of Fe to Al in the carrier is (0.04-2.6): 1.

11. The method for preparing a dehydrogenation catalyst for an organic liquid hydrogen storage material according to claim 10, wherein the step of preparing comprises the step d), and the method further comprises the steps of dipping, drying and roasting.

12. 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.

13. The method of dehydrogenating an organic liquid hydrogen storage material according to claim 12, the organic liquid hydrogen storage material being selected from at least one of methylcyclohexane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole and perhydrocarbazole.