Dehydrogenation catalyst as well as preparation method and application thereof

Abstract

The invention provides a dehydrogenation catalyst. The dehydrogenation catalyst comprises a carrier, and an active component element, a metal additive element and a non-metallic element which are loaded on the carrier, the non-metallic element is selected from one or more of sulfur, phosphorus and nitrogen; the molar ratio X of the non-metallic elements to the active component elements and the specific surface area S of the carrier have the following relation: X = a * Sn, a is a natural number between 0.03 and 0.3, and n is a natural number between 0.01 and 0.3. The dehydrogenation catalyst provided by the invention is used for dehydrogenation of hydrogen storage organic liquid, and has good stability and target product selectivity; and the catalyst can be directly used for dehydrogenation of hydrogen storage organic liquid without poisoning pretreatment.

Description

Technical Field

[0001] The invention relates to a dehydrogenation catalyst and a preparation method and application thereof. Background Art

[0002] In recent years, the use of liquid organic hydrogen carrier (LOHC) systems for energy storage has attracted great interest. LOHC is a fuel-like hydrocarbon that can reversibly bind hydrogen and can be safely and economically stored and transported within the existing fuel infrastructure. This provides a good technical solution to the problem of temporal and spatial differences between the production and use of renewable energy.

[0003] LOHC requires a catalyst for the binding and release of hydrogen, i.e., hydrogenation and dehydrogenation reactions. Catalysts for dehydrogenation reactions are currently the focus of research. Existing catalysts, especially precious metal catalysts, inevitably have overly strong active sites, which will hinder the desorption of dehydrogenation products at the active sites, and then produce carbon deposits, resulting in decreased stability, and also increase side reaction products. The method currently used in industry is to pretreat the catalyst online with liquid organic matter containing elements such as sulfur and nitrogen, thereby poisoning highly active sites to reduce side reactions and carbon deposits. However, this will pose a great challenge to the corrosion resistance of the reactor, and is also not conducive to controlling the degree of catalyst poisoning and the centralized treatment of the three wastes. Summary of the invention

[0004] Based on the above reasons, the purpose of the present invention is to overcome the problems encountered by the noble metal catalysts in the dehydrogenation reaction of organic liquids and poisoning pretreatment in the prior art, and to provide a dehydrogenation catalyst and a preparation method and application thereof, wherein the dehydrogenation catalyst has good stability and target product selectivity.

[0005] In order to achieve the above-mentioned object, the first aspect of the present invention provides a dehydrogenation catalyst, which comprises a carrier and an active component element, a metal promoter element and a non-metallic element supported on the carrier;

[0006] The non-metallic element is selected from one or more of sulfur, phosphorus and nitrogen;

[0007] The molar ratio X of the non-metallic element to the active component element and the specific surface area S of the carrier have the following relationship:

[0008] X=a*S n , where a is a natural number between 0.03 and 0.3, and n is a natural number between 0.01 and 0.3.

[0009] A second aspect of the present invention provides a method for preparing the dehydrogenation catalyst of the present invention, the method comprising:

[0010] (1) impregnating a support with a solution containing a metal additive source, and performing a first drying and a first calcination to obtain a modified support;

[0011] (2) The modified carrier is impregnated with a solution containing an active metal source, and after a second drying and a second calcination, a catalyst matrix is ​​obtained.

[0012] (3) The catalyst matrix is ​​impregnated with a solution containing a non-metallic element source, and after drying, the catalyst is reduced in a reducing gas atmosphere to obtain a catalyst; the reducing gas contains 10-30V% of a carbon-containing gas.

[0013] The third aspect of the present invention provides a use of the dehydrogenation catalyst of the present invention in the dehydrogenation of an organic liquid hydrogen storage compound.

[0014] Through the above technical scheme, the dehydrogenation catalyst of the present invention is used for dehydrogenation of hydrogen storage organic liquid, which can improve the selectivity of the reaction and the stability of the catalyst while maintaining a relatively high initial conversion rate.

[0015] The dehydrogenation catalyst of the present invention is used for dehydrogenation of hydrogen storage organic liquid, has good stability and target product selectivity, and does not require poisoning pretreatment, and can be directly used for dehydrogenation of hydrogen storage organic liquid. DETAILED DESCRIPTION

[0016] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0017] A first aspect of the present invention provides a dehydrogenation catalyst, which comprises a carrier and an active component element, a metal promoter element and a non-metallic element supported on the carrier;

[0018] The non-metallic element is selected from one or more of sulfur, phosphorus and nitrogen;

[0019] The molar ratio X of the non-metallic element to the active component element and the specific surface area S of the carrier have the following relationship:

[0020] X=a*S n , where a is a natural number between 0.03 and 0.3, and n is a natural number between 0.01 and 0.3.

[0021] In the present invention, in the catalyst, the specific surface area of ​​the carrier will affect the distribution of the active metal, and then affect the content of the non-metallic element for modification. The introduction of too much non-metallic element for modification through the preparation method will make the initial activity of the catalyst very low, and the introduction of too little will not play the role it should play, resulting in more side reactions and reduced stability. The present invention finds that the molar ratio X of the non-metallic element to the active component element and the specific surface area S of the carrier have the above relationship, which can improve the selectivity of the dehydrogenation reaction and the stability of the catalyst on the basis of maintaining a high initial conversion rate.

[0022] According to one embodiment of the present invention, the content of non-metallic elements is 0.01-0.3% based on the total weight of the catalyst.

[0023] According to one embodiment of the present invention, based on the total weight of the catalyst, the content of the carrier is 96.7%-99.5%, the content of the active component element is 0.1%-1%, the content of the metal auxiliary element is 0.3%-2%, and the content of the non-metallic element is 0.01-0.3%.

[0024] According to a preferred embodiment of the present invention, the non-metallic elements at least include sulfur. Preferably, the non-metallic elements are sulfur and phosphorus.

[0025] According to a preferred embodiment of the present invention, the mass ratio of sulfur to phosphorus is 0.5-2:1.

[0026] According to a preferred embodiment of the present invention, the specific surface area of ​​the carrier is 160-300 cm 2 / g.

[0027] In the present invention, there is no special requirement for the metal auxiliary element. The following is an exemplary description of the implementation mode of the present invention, but the present invention is not limited to this scope.

[0028] According to one embodiment of the present invention, the metal auxiliary element is selected from one or more of Cu, Zn, Ni, Fe, Mn, Cr, Co and La.

[0029] According to one embodiment of the present invention, the active component is selected from at least one of the noble metals, and preferably the active component is selected from one or more of gold, platinum, palladium and rhodium.

[0030] In the present invention, there is no special requirement for the type of the carrier. The following is an exemplary description of the implementation mode of the present invention, but the present invention is not limited to this scope.

[0031] According to one embodiment of the present invention, the carrier is selected from at least one of alumina and silica-alumina molecular sieve; preferably, the alumina contains a physical structure of at least one of γ-alumina, η-alumina and ρ-alumina.

[0032] In the present invention, the dehydrogenation catalysts having the above characteristics can achieve the purpose of the present invention. The present invention has no special requirements for the preparation method of the dehydrogenation catalyst. According to a preferred embodiment of the present invention, the second aspect of the present invention provides a preparation method of the dehydrogenation catalyst of the present invention, which comprises:

[0033] (1) impregnating a support with a solution containing a metal additive source, and performing a first drying and a first calcination to obtain a modified support;

[0034] (2) The modified carrier is impregnated with a solution containing an active metal source, and after a second drying and a second calcination, a catalyst matrix is ​​obtained.

[0035] (3) The catalyst matrix is ​​impregnated with a solution containing a non-metallic element source, and after drying, the catalyst is reduced in a reducing gas atmosphere to obtain a catalyst; the reducing gas contains 10-30V% of a carbon-containing gas.

[0036] In the present invention, there is no special requirement for the type of the metal additive source. The following exemplary embodiments of the present invention are described, but the present invention is not limited to this scope. According to a preferred embodiment of the present invention, in step (1), the metal additive source is selected from soluble salts of metal additives.

[0037] In the present invention, there is no special requirement for the type of the active metal source. The following exemplary embodiments of the present invention are described, but the present invention is not limited to this scope. According to a preferred embodiment of the present invention, in step (2), the active metal source is selected from a soluble salt of an active metal.

[0038] In the present invention, there is no special requirement for the type of the non-metallic element source. The following is an exemplary description of the implementation of the present invention, but the present invention is not limited to this scope.

[0039] According to one embodiment of the present invention, in step (3), the non-metallic element source is selected from one or more of ammonium salts, potassium salts and sodium salts containing the metal element.

[0040] According to a preferred embodiment of the present invention, in step (3), there is no particular limitation on the drying conditions, as long as the non-metallic element source can be loaded onto the catalyst matrix. For example, it can be air-dried in the reducing gas atmosphere, or dried at a temperature of 60-120° C., preferably for 3-24 hours.

[0041] In the present invention, the carbon-containing gas may be selected from a wide range of types. According to a preferred embodiment of the present invention, the carbon-containing gas is selected from at least one of methane, carbon monoxide, ethylene and propane.

[0042] According to a preferred embodiment of the present invention, in step (3), the reducing gas contains hydrogen and carbon-containing gas; preferably, the volume ratio of hydrogen to carbon-containing gas is 1-10.

[0043] The reducing gas atmosphere may further include inert gases, such as He, N2, etc. According to a preferred embodiment of the present invention, in step (3), the reducing gas atmosphere has a volume content of reducing gas of 60-90%; for example, according to an embodiment of the present invention, the reducing gas atmosphere is a mixture of methane, hydrogen and helium, containing 15% CH4, 45% H2 and 40% He by volume.

[0044] In the present invention, there is no special requirement for the reduction conditions. The following exemplary embodiments of the present invention are described, but the present invention is not limited to this scope. According to a preferred embodiment of the present invention, in step (3), the reduction conditions include: a temperature of 300-450°C, a time of 3-8h; and a preferred heating rate of 0.5-2°C / min.

[0045] According to a preferred embodiment of the present invention, in step (1), the specific surface area of ​​the carrier is 160-300 cm 2 / g.

[0046] In the present invention, there is no special requirement for drying conditions. The following exemplary embodiments of the present invention are described, but the present invention is not limited to this scope. According to a preferred embodiment of the present invention, the first drying and second drying conditions independently include: a temperature of 60-120°C and a time of 3-24h.

[0047] In the present invention, there is no special requirement for the calcination conditions. The following exemplary embodiments of the present invention are described, but the present invention is not limited to this scope. According to a preferred embodiment of the present invention, the first calcination and the second calcination conditions each independently include: a temperature of 400-600°C and a time of 3-8h; preferably, the heating rate is 0.5-10°C / min.

[0048] The third aspect of the present invention provides an application of the dehydrogenation catalyst of the present invention in the dehydrogenation of an organic liquid hydrogen storage compound. The dehydrogenation catalyst of the present invention is used for the dehydrogenation of hydrogen storage organic liquids, has good stability and target product selectivity, and does not require poisoning pretreatment, and can be directly used for the dehydrogenation of hydrogen storage organic liquids.

[0049] In the present invention, there is no special requirement for the dehydrogenation conditions. The following is an exemplary description of the embodiments of the present invention, but the present invention is not limited to this scope. According to a preferred embodiment of the present invention, the dehydrogenation conditions include: a reaction pressure of 0-1 MPa, a temperature of 300-350°C, a mass space velocity of 0.1-10 h -1 .

[0050] In the present invention, there is no special requirement for the type of organic liquid hydrogen storage compound. The following is an exemplary description of the implementation mode of the present invention, but the present invention is not limited to this scope.

[0051] According to a preferred embodiment of the present invention, the organic liquid hydrogen storage compound is selected from the product of at least partial hydrogenation of at least one compound selected from carbazole, N-alkyl substituted carbazole, benzene, toluene and naphthalene.

[0052] According to a preferred embodiment of the present invention, the N-alkyl substituted carbazole is selected from one or more of N-methyl substituted carbazole, N-ethyl substituted carbazole, N-propyl carbazole, N-n-propyl carbazole, N-isopropyl carbazole and N-n-butyl carbazole.

[0053] According to a preferred embodiment of the present invention, the organic liquid hydrogen storage compound is selected from at least one of methylcyclohexane, cyclohexane, tetralin, decalin, perhydroethylcarbazole and perhydrocarbazole.

[0054] The present invention will be described in detail below through examples.

[0055] Example 1

[0056] (1) 2.36 g of copper nitrate and 1.87 g of nickel nitrate were dissolved in 60 mL of deionized water and loaded onto 98.3 g of η-alumina (specific surface area 230 cm) by equal volume impregnation. 2 / g, with a diameter of 1 mm), dried at 80°C for 12 h, and then placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a modified carrier.

[0057] (2) 20.4 mL of chloroplatinic acid solution (concentration 14.7 mg Pt / mL) was added to 39.6 mL of deionized water, and platinum was loaded onto the modified support by equal volume impregnation. After drying at 80°C for 12 h, the support was placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a catalyst matrix.

[0058] (3) 0.138 g of ammonium persulfate was dissolved in 60 ml of deionized water, mixed with the catalyst matrix by equal volume impregnation, placed in an atmosphere furnace and introduced with 50 mL / min of a mixture of CH4, H2 and He (15% CH4, 45% H2, 40% He, volume content), and calcined and reduced at 400° C. for 6 h to obtain a catalyst. The content of each component was tested by ICP, and the results are shown in Table 1.

[0059] Example 2

[0060] (1) 2.36 g of copper nitrate and 1.87 g of nickel nitrate were dissolved in 60 mL of deionized water and loaded onto 98.3 g of η-alumina (specific surface area 166 cm) by equal volume impregnation. 2 / g, with a diameter of 1 mm), dried at 80°C for 12 h, and then placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a modified carrier.

[0061] (2) 20.4 mL of chloroplatinic acid solution (concentration 14.7 mg Pt / mL) was added to 39.6 mL of deionized water, and platinum was loaded onto the obtained modified support by equal volume impregnation. After drying at 80°C for 12 h, the support was placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a catalyst matrix.

[0062] (3) 0.12 g of ammonium persulfate was dissolved in 60 ml of deionized water, mixed with the catalyst matrix by equal volume impregnation, placed in an atmosphere furnace, and introduced with 50 mL / min of propane, H2 and He mixed gas (10% propane, 50% H2, 40% He, volume content), and calcined and reduced at 400° C. for 6 h to obtain a catalyst. The content of each component was tested by ICP, and the results are shown in Table 1.

[0063] Example 3

[0064] (1) 2.36 g of copper nitrate and 1.87 g of nickel nitrate were dissolved in 60 mL of deionized water and loaded onto 98.3 g of η-alumina (specific surface area 230 cm) by equal volume impregnation. 2 / g, with a diameter of 1 mm), dried at 80°C for 12 h, and then placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a modified carrier.

[0065] (2) 0.852 g of rhodium nitrate was added to 60 mL of deionized water, loaded onto the obtained modified support by equal volume impregnation, dried at 80° C. for 12 h, and then placed in a muffle furnace and calcined at a heating rate of 5° C. / min to 600° C. for 5 h to obtain a catalyst matrix.

[0066] (3) 0.138 g of ammonium persulfate was dissolved in 60 ml of deionized water, mixed with the catalyst matrix by equal volume impregnation, placed in an atmosphere furnace and introduced with 50 mL / min of a mixture of CH4, H2 and He (15% CH4, 45% H2, 40% He, volume content), and calcined and reduced at 400° C. for 6 h to obtain a catalyst. The content of each component was tested by ICP, and the results are shown in Table 1.

[0067] Example 4

[0068] (1) 2.36 g of copper nitrate and 1.87 g of nickel nitrate were dissolved in 60 mL of deionized water and loaded onto 98.3 g of η-alumina (specific surface area 230 cm) by equal volume impregnation. 2 / g, with a diameter of 1 mm), dried at 80°C for 12 h, and then placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a modified carrier.

[0069] (2) 20.4 mL of chloroplatinic acid solution (concentration 14.7 mg Pt / mL) was added to 39.6 mL of deionized water and loaded onto the obtained modified support by equal volume impregnation. After drying at 80°C for 12 h, the support was placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a catalyst matrix.

[0070] (3) 0.116 g of ammonium phosphate was dissolved in 60 ml of deionized water, mixed with the catalyst matrix by equal volume impregnation, placed in an atmosphere furnace and introduced with 50 mL / min of a mixture of CH4, H2 and He (15% CH4, 45% H2, 40% He, volume content), and calcined and reduced at 300° C. for 8 h to obtain a catalyst. The content of each component was tested by ICP, and the results are shown in Table 1.

[0071] Example 5

[0072] (1) 2.36 g of copper nitrate and 1.87 g of nickel nitrate were dissolved in 60 mL of deionized water and loaded onto 98.3 g of η-alumina (specific surface area 230 cm) by equal volume impregnation. 2 / g, with a diameter of 1 mm), dried at 80°C for 12 h, and then placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a modified carrier.

[0073] (2) 20.4 mL of chloroplatinic acid solution (concentration 14.7 mg Pt / mL) was added to 39.6 mL of deionized water, and platinum was loaded onto the modified support by equal volume impregnation. After drying at 80°C for 12 h, the support was placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a catalyst matrix.

[0074] (3) 0.078 g of ammonium persulfate and 0.083 g of ammonium phosphate were dissolved in 60 ml of deionized water, mixed with the catalyst matrix by equal volume impregnation, placed in an atmosphere furnace, and introduced with 50 mL / min of a mixture of CH4, H2 and He (15% CH4, 45% H2, 40% He, volume content), and calcined at 400° C. for 6 h to obtain a catalyst. The content of each component was tested by ICP, and the results are shown in Table 1.

[0075] Example 6

[0076] (1) 4.35 g of cobalt nitrate was dissolved in 60 mL of deionized water and copper was loaded onto 98.3 g of η-alumina (specific surface area 230 cm) by equal volume impregnation. 2 / g, with a diameter of 1 mm), dried at 80°C for 12 h, and then placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a modified carrier.

[0077] (2) 20.4 mL of chloroplatinic acid solution (concentration 14.7 mg Pt / mL) was added to 39.6 mL of deionized water, and platinum was loaded onto the obtained modified support by equal volume impregnation. After drying at 80°C for 12 h, the support was placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a catalyst matrix.

[0078] (3) 0.2 g of ammonium persulfate was dissolved in 60 ml of deionized water, mixed with the catalyst matrix by equal volume impregnation, placed in an atmosphere furnace, and introduced with 50 mL / min of ethylene, H2 and He mixed gas (30% ethylene, 30% H2, 40% He, volume content), and calcined at 400° C. for 6 h to obtain a catalyst. The content of each component was tested by ICP, and the results are shown in Table 1.

[0079] Comparative Example 1

[0080] (1) 2.36 g of copper nitrate and 1.87 g of nickel nitrate were dissolved in 60 mL of deionized water and copper was loaded onto 98.3 g of η-alumina (specific surface area 230 cm) by equal volume impregnation. 2 / g, with a diameter of 1 mm), dried at 80°C for 12 h, and then placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a modified carrier.

[0081] (2) 20.4 mL of chloroplatinic acid solution (concentration 14.7 mg Pt / mL) was added to 39.6 mL of deionized water, and platinum was loaded onto the obtained modified carrier by equal volume impregnation. After drying at 80°C for 12 h, the carrier was placed in a muffle furnace and heated to 600°C at a heating rate of 5°C / min for 5 h to obtain a catalyst.

[0082] (3) The catalyst obtained in step (2) was placed in an atmosphere furnace, and a mixture of CH4, H2 and He (15% CH4, 45% H2, 40% He, volume content) was introduced at 50 mL / min, and the catalyst was obtained after calcination at 400° C. for 6 h. The content of each component was tested by ICP, and the results are shown in Table 1.

[0083] Comparative Example 2

[0084] (1) 2.36 g of copper nitrate and 1.87 g of nickel nitrate were dissolved in 60 mL of deionized water and copper was loaded onto 98.3 g of η-alumina (specific surface area 230 cm) by equal volume impregnation.2 / g, with a diameter of 1 mm), dried at 80°C for 12 h, and then placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a modified carrier.

[0085] (2) 20.4 mL of chloroplatinic acid solution (concentration 14.7 mg Pt / mL) was added to 39.6 mL of deionized water, and platinum was loaded onto the obtained modified support by equal volume impregnation. After drying at 80°C for 12 h, the support was placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a catalyst matrix.

[0086] (3) 0.138 g of ammonium persulfate was dissolved in 60 ml of deionized water, mixed with the catalyst matrix by equal volume impregnation, placed in an atmosphere furnace, introduced with 50 mL / min of H2 and He mixed gas (60% H2, 40% He, volume content), and calcined and reduced at 400° C. for 6 h to obtain a catalyst. The content of each component was tested by ICP, and the results are shown in Table 1.

[0087] Comparative Example 3

[0088] (1) Take 0.138g of ammonium persulfate and dissolve it in 60ml of deionized water. Then, impregnate it with 98.3g of η-alumina (specific surface area 230cm) by equal volume. 2 / g, diameter 1mm) were mixed, placed in an atmosphere furnace and introduced with 50mL / min of CH4, H2 and He mixed gas (15% CH4, 45% H2, 40% He, volume content), and calcined at 400℃ for 6h to modify the carrier.

[0089] (2) 2.36 g of copper nitrate and 1.87 g of nickel nitrate were dissolved in 60 mL of deionized water, and copper was loaded onto the modified support obtained in step (1) by equal volume impregnation. After drying at 80° C. for 12 h, the support was placed in a muffle furnace and heated to 600° C. at a heating rate of 5° C. / min for 5 h to obtain an additive-modified support.

[0090] (3) 20.4 mL of chloroplatinic acid solution (concentration 14.7 mg Pt / mL) was added to 39.6 mL of deionized water, and platinum was loaded on the auxiliary agent modified support obtained in step (2) by equal volume impregnation. After drying at 80° C. for 12 h, the mixture was placed in a muffle furnace and heated to 600° C. at a heating rate of 5° C. / min for calcination for 5 h to obtain a catalyst;

[0091] The content of each component was tested by ICP, and the results are shown in Table 1.

[0092] Comparative Example 4

[0093] (1) 2.36 g of copper nitrate and 1.87 g of nickel nitrate were dissolved in 60 mL of deionized water and copper was loaded onto 98.3 g of η-alumina (specific surface area 230 cm) by equal volume impregnation.2 / g, with a diameter of 1 mm), dried at 80°C for 12 h, and then placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a modified carrier.

[0094] (2) 20.4 mL of chloroplatinic acid solution (concentration 14.7 mg Pt / mL) was added to 39.6 mL of deionized water, and platinum was loaded onto the obtained modified support by equal volume impregnation. After drying at 80°C for 12 h, the support was placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a catalyst matrix.

[0095] (3) 0.3 g of ammonium persulfate was dissolved in 60 ml of deionized water, mixed with the catalyst matrix by equal volume impregnation, placed in an atmosphere furnace, and introduced with 50 mL / min of a mixture of CH4, H2 and He (15% CH4, 45% H2, 40% He, volume content), and calcined at 400° C. for 6 h to obtain the catalytic material.

[0096] The content of each component was tested by ICP, and the results are shown in Table 1.

[0097] Comparative Example 5

[0098] (1) 2.36 g of copper nitrate and 1.87 g of nickel nitrate were dissolved in 60 mL of deionized water and loaded onto 98.3 g of η-alumina (specific surface area 230 cm) by equal volume impregnation. 2 / g, with a diameter of 1 mm), dried at 80°C for 12 h, and then placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a modified carrier.

[0099] (2) 20.4 mL of chloroplatinic acid solution (concentration 14.7 mg Pt / mL) was added to 39.6 mL of deionized water, and platinum was loaded onto the modified support by equal volume impregnation. After drying at 80°C for 12 h, the support was placed in a muffle furnace and calcined at a heating rate of 5°C / min to 600°C for 5 h to obtain a catalyst matrix.

[0100] (3) 0.138 g of ammonium persulfate was dissolved in 60 ml of deionized water, mixed with the catalyst matrix by equal volume impregnation, placed in an atmosphere furnace, and introduced with 50 mL / min of a mixture of CH4, H2 and He (45% CH4, 15% H2, 40% He, volume content), and calcined at 400° C. for 6 h to obtain a catalyst. The content of each component was tested by ICP, and the results are shown in Table 1.

[0101] Test Case

[0102] Methylcyclohexane was used as a representative raw material of hydrogen storage organic liquid. The catalysts obtained in the examples and comparative examples were loaded into a tubular reactor for evaluation. The evaluation conditions included: reaction pressure of 0.1 MPa, temperature of 320°C, mass space velocity of 6 h -1 The reaction product components were evaluated by gas chromatography results, the initial activity was used as the catalyst activity evaluation target, the methane peak area ratio was used to evaluate the amount of side reactions, i.e. selectivity, and the mass space velocity was 30h -1 After running for 24 hours, the airspeed is restored to 6 hours. -1 The stability was evaluated by the conversion rate. The evaluation results are shown in Table 2.

[0103] Table 1

[0104]

[0105]

[0106] Table 2

[0107]

[0108]

[0109] It can be seen from the results in Table 1 and Table 2 that the catalysts of Examples 1 to 6 of the present invention have the effects of high initial conversion rate and excellent stability in the dehydrogenation reaction.

[0110] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A dehydrogenation catalyst, characterized in that The dehydrogenation catalyst comprises a carrier and active component elements, metal auxiliary elements and non-metal elements loaded on the carrier; The non-metallic element is selected from one or more of sulfur, phosphorus and nitrogen; The molar ratio X of the non-metallic element to the active component element and the specific surface area S of the carrier have the following relationship: X=a*S n , where a is a natural number between 0.03 and 0.3, and n is a natural number between 0.01 and 0.

3.

2. The dehydrogenation catalyst according to claim 1, wherein The content of non-metallic elements is 0.01-0.3% based on the total weight of the catalyst; Preferably, based on the total weight of the catalyst, the content of the carrier is 96.7%-99.5%, the content of the active component element is 0.1%-1%, the content of the metal auxiliary element is 0.3%-2%, and the content of the non-metallic element is 0.01-0.3%.

3. The dehydrogenation catalyst according to claim 1 or 2, wherein The non-metallic element at least comprises sulfur, preferably, the non-metallic element is sulfur and phosphorus, more preferably, the mass ratio of sulfur to phosphorus is 0.5-2:1; and / or The specific surface area of ​​the carrier is 160-300cm 2 / g.

4. The dehydrogenation catalyst according to any one of claims 1 to 3, wherein The metal additive element is selected from one or more of Cu, Zn, Ni, Fe, Mn, Cr, Co and La, preferably Cu and / or Ni; and / or The active component is selected from at least one of the noble metals, preferably one or more of gold, platinum, palladium and rhodium; and / or The carrier is selected from at least one of alumina and silica-alumina molecular sieve; preferably, the alumina contains a phase structure of at least one of γ-alumina, η-alumina and ρ-alumina.

5. The method for preparing the dehydrogenation catalyst according to any one of claims 1 to 4, characterized in that: The method includes: (1) impregnating a support with a solution containing a metal additive source, and performing a first drying and a first calcination to obtain a modified support; (2) impregnating the modified support with a solution containing an active metal source, and performing a second drying and a second calcination to obtain a catalyst matrix; (3) impregnating the catalyst matrix with a solution containing a non-metallic element source, and reducing the solution in a reducing gas atmosphere after drying to obtain a catalyst; The reducing gas contains 10-30V% of carbon-containing gas.

6. The preparation method according to claim 5, wherein: In step (3), The non-metallic element source is selected from one or more of ammonium salts, potassium salts and sodium salts containing the metal element; and / or The carbon-containing gas is selected from at least one of methane, carbon monoxide, ethylene and propane; preferably, the reducing gas contains hydrogen and carbon-containing gas; preferably, the volume ratio of hydrogen to carbon-containing gas is 1-10; The reduction conditions include: temperature of 300-450°C and time of 3-8h.

7. The preparation method according to claim 5 or 6, wherein: In step (3), the reducing gas atmosphere has a volume content of 60-90% reducing gas.

8. The preparation method according to claim 5 or 6, wherein: The first drying and second drying conditions independently include: a temperature of 60-120° C. and a time of 3-24 hours; and / or The first calcination and the second calcination conditions independently include: a temperature of 400-600° C. and a time of 3-8 hours; preferably, a heating rate of 0.5-10° C. / min.

9. Use of the dehydrogenation catalyst according to any one of claims 1 to 4 in the dehydrogenation of organic liquid hydrogen storage compounds.

10. The use according to claim 9, wherein: Dehydrogenation conditions include: reaction pressure of 0-1MPa, temperature of 300-350℃, mass space velocity of 0.1-10h -1 ; and / or The organic liquid hydrogen storage compound is a product of at least partial hydrogenation of at least one compound selected from carbazole, N-alkyl substituted carbazole, benzene, toluene and naphthalene; Preferably, the N-alkyl substituted carbazole is selected from one or more of N-methyl substituted carbazole, N-ethyl substituted carbazole, N-propyl carbazole, N-n-propyl carbazole, N-isopropyl carbazole and N-n-butyl carbazole; Preferably, the organic liquid hydrogen storage compound is selected from at least one of methylcyclohexane, cyclohexane, tetralin, decalin, perhydroethylcarbazole and perhydrocarbazole.

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