Dehydrogenation catalyst, its preparation method and application

Abstract

The present invention provides a dehydrogenation catalyst, a preparation method thereof and an application thereof. The preparation method of the dehydrogenation catalyst includes: S1, adjusting the pH of a colloid containing noble metal single particles to 3-5 to obtain a first mixed solution; S2, dispersing the first mixed solution into a solution containing polyvinylpyrrolidone or polyvinyl alcohol to obtain a second mixed solution; S3, mixing an acidic-free metal oxide support with the second mixed solution, and calcining the obtained product after the reaction to obtain a solid powder; S4, heating and reducing the solid powder in a hydrogen atmosphere to obtain the dehydrogenation catalyst. The dehydrogenation catalyst prepared by using this preparation method has a low noble metal content, can effectively inhibit the occurrence of dehydrogenation side reactions, and improve the dehydrogenation activity of organic liquid hydrogen storage materials.

Description

Technical Field

[0001] The present invention relates to the field of chemical engineering technology, and in particular to a dehydrogenation catalyst, a preparation method thereof, and an application thereof. Background Art

[0002] Hydrogen has the highest calorific value among all chemical energy fuels, and the production and utilization of green hydrogen do not cause environmental pollution, so it is considered an ideal energy carrier in the future. With hydrogen energy gradually becoming a research and development hotspot in recent years, methods of hydrogen storage, transportation, and release have received extensive attention. Among them, the hydrogenation-dehydrogenation cycle hydrogen storage method of organic liquid hydrogen storage materials has the characteristics of safety, high efficiency, and suitability for large-scale long-distance transportation, and has great industrial application potential. However, at present, problems such as high reaction temperature and many by-products are faced during the hydrogen release process of organic liquid hydrogen storage materials, resulting in poor cyclic use performance and a large amount of energy waste.

[0003] In view of this, the present invention is specifically proposed. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems in the related art to some extent. For this reason, an object of the present invention is to provide a preparation method of a dehydrogenation catalyst. The dehydrogenation catalyst prepared by using this preparation method has a low noble metal content, can effectively inhibit the occurrence of dehydrogenation side reactions, and improve the dehydrogenation activity of organic liquid hydrogen storage materials.

[0005] In one aspect of the present invention, the present invention provides a preparation method of a dehydrogenation catalyst, and the preparation method includes:

[0006] S1. Adjust the pH of a colloid containing noble metal single-element particles to 3-5 to obtain a first mixed solution;

[0007] S2. Disperse the first mixed solution into a solution containing polyvinylpyrrolidone or polyvinyl alcohol to obtain a second mixed solution;

[0008] S3. Mix an acidic-free metal oxide carrier with the second mixed solution, and calcine the obtained product of the reaction to obtain a solid powder;

[0009] S4. Heat and reduce the solid powder in a hydrogen atmosphere to obtain the dehydrogenation catalyst.

[0010] Further, the noble metal single-element particles include at least one of Pt, Ru, and Pd;

[0011] And / or, the acidic-free metal oxide carrier includes MgO and / or ZrO2.

[0012] Further, in the second mixed solution, the mass ratio of polyvinylpyrrolidone to the noble metal single-element particles is 1 to 1.5:1.

[0013] Further, in step S3, the calcination temperature is 400 to 500 °C and the time is 3 to 5 h.

[0014] Further, in step S4, the heating reduction temperature is 300 to 500 °C and the reduction time is 3 to 5 h.

[0015] Further, the preparation method of the colloid containing noble metal single-element particles in step S1 includes:

[0016] Dissolving a noble metal salt and an alkali solution in an ethylene glycol solution to obtain a third mixed solution, and the pH of the third mixed solution is 9 to 12;

[0017] Heating the third mixed solution in an inert atmosphere to obtain a colloid containing noble metal single-element particles.

[0018] In another aspect of the present invention, the present invention provides a dehydrogenation catalyst prepared by using the foregoing preparation method, and the dehydrogenation catalyst includes:

[0019] Noble metal single-element particles;

[0020] A non-acidic metal oxide carrier, and the noble metal single-element particles are supported on at least part of the surface of the non-acidic metal oxide carrier;

[0021] Based on the total mass of the dehydrogenation catalyst, the content of the noble metal single-element particles is 0.1 to 0.5 wt%;

[0022] And / or, the particle size of the noble metal single-element particles is 1.5 to 1.8 nm.

[0023] In another aspect of the present invention, the present invention provides an application of a dehydrogenation catalyst, and the dehydrogenation catalyst is applied to the dehydrogenation of an organic liquid hydrogen storage material;

[0024] The dehydrogenation catalyst includes the dehydrogenation catalyst prepared by the foregoing preparation method or the foregoing dehydrogenation catalyst.

[0025] Further, the organic liquid hydrogen storage material includes perhydro-monobenzyltoluene and / or perhydro-dibenzyltoluene;

[0026] And / or, the reaction conditions for dehydrogenation are that the space velocity is 3 to 6 h -1 , the reaction pressure is 0.2 to 1.0 MPa, and the reaction temperature is 280 to 350 °C.

[0027] Further, the reaction device for dehydrogenation includes a fixed bed.

[0028] Compared with the prior art, the present invention can achieve at least the following beneficial effects:

[0029] In the colloid containing noble metal single - element particles, the sizes of the noble metal single - element particles are consistent and are relatively evenly dispersed, which is conducive to obtaining a dehydrogenation catalyst with evenly dispersed noble metal single - element particles and a low noble metal content; using a non - acidic metal oxide as a carrier, the noble metal single - element particles are evenly distributed on the surface of the carrier by electrostatic adsorption. The noble metal single - element transfers electrons to the carrier, reducing the electron cloud density of the noble metal single - element. On the one hand, it improves C - H activation and promotes the dehydrogenation rate. On the other hand, it reduces the adsorption intensity of intermediate species, promotes the desorption of the final dehydrogenation product, inhibits the occurrence of side reactions in the dehydrogenation of organic liquid hydrogen storage materials, and improves the dehydrogenation activity. Description of the Drawings

[0030] Figure 1 is the XPS result of the dehydrogenation catalyst in Example 1;

[0031] Figure 2 is the transmission electron microscopy image of the dehydrogenation catalyst in Example 1;

[0032] Figure 3 is the transmission electron microscopy image of the dehydrogenation catalyst in Example 11. Detailed Description of the Invention

[0033] The embodiments of the present invention are described in detail below. The described embodiments are exemplary and are only used to explain the present invention and should not be construed as limiting the present invention. For those technical or conditions not specified in the embodiments, they shall be carried out according to the technologies or conditions described in the literature in the field or according to the product specifications. For the reagents or instruments not indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0034] In one aspect of the present invention, the present invention provides a preparation method of a dehydrogenation catalyst, and the preparation method includes:

[0035] S1. Adjust the pH of the colloid containing noble metal single - element particles to 3 - 5 to obtain a first mixed solution;

[0036] S2. Disperse the first mixed solution into a solution containing polyvinylpyrrolidone or polyvinyl alcohol to obtain a second mixed solution;

[0037] S3. Mix the non - acidic metal oxide carrier with the second mixed solution, and calcine the product obtained from the reaction to obtain a solid powder;

[0038] S4. Heat and reduce the solid powder in a hydrogen atmosphere to obtain the dehydrogenation catalyst.

[0039] In the colloid containing noble metal single - element particles, the sizes of the noble metal single - element particles are consistent and they are relatively uniformly dispersed, which is conducive to obtaining a dehydrogenation catalyst with uniformly dispersed noble metal single - element particles and a relatively low noble metal content; using a non - acidic metal oxide as a carrier, the noble metal single - element particles are uniformly distributed on the surface of the carrier by electrostatic adsorption. The noble metal single - element transfers electrons to the carrier, reducing the electron cloud density of the noble metal single - element. On the one hand, it improves C - H activation and promotes the dehydrogenation rate. On the other hand, it reduces the adsorption strength of intermediate species, promotes the desorption of the final dehydrogenation product, inhibits the occurrence of side reactions in the dehydrogenation of organic liquid hydrogen storage materials, and improves the dehydrogenation activity.

[0040] It should be noted that the non - acidic metal oxides in this article refer to some inert or reducible carriers lacking or having a small amount of Bronsted acid.

[0041] In some embodiments of the present invention, hydrochloric acid is used to adjust the pH of the colloid containing noble metal single - element particles to 3 - 5.

[0042] In some embodiments of the present invention, the noble metal single - element particles include at least one of Pt (platinum), Ru (ruthenium), and Pd (palladium); the non - acidic metal oxide carrier includes MgO and / or ZrO2.

[0043] In some embodiments of the present invention, in the second mixed solution, the mass ratio of polyvinylpyrrolidone to the noble metal single - element particles is 1 - 1.5:1 (for example, it can be 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, or 1.5:1, etc.). Compared with the above - mentioned ratio range, when the mass ratio of polyvinylpyrrolidone to the noble metal single - element particles is less than 1:1, the Pt particles are not uniformly dispersed; when the mass ratio of polyvinylpyrrolidone to the noble metal single - element particles is greater than 1.5:1, the content of polyvinylpyrrolidone is excessive, and the residue on the catalyst surface affects the exposure of active sites.

[0044] In some embodiments of the present invention, in step S3, the temperature of the calcination is 400 - 500 °C (for example, it can be 400 °C, 500 °C, or 600 °C, etc.), and the time is 3 - 5 h (for example, it can be 3 h, 4 h, or 5 h, etc.). Compared with the above - mentioned calcination temperature, when the calcination temperature is lower than 400 °C, polyvinylpyrrolidone cannot be completely burned off, reducing the catalytic activity; when the calcination temperature is higher than 500 °C, the Pt particles aggregate and the dispersibility decreases, resulting in a decrease in dehydrogenation activity.

[0045] In some embodiments of the present invention, in step S4, the temperature of the heating reduction is 300 to 500 °C, and the reduction time is 3 to 5 h. Compared with the above temperature of the heating reduction, when the temperature of the heating reduction is lower than 300 °C, the reduction degree of Pt is low, resulting in a decrease in the catalyst activity; when the temperature of the heating reduction is higher than 500 °C, the Pt particles aggregate and the dispersibility decreases, resulting in a decrease in the dehydrogenation activity.

[0046] In some embodiments of the present invention, the method for preparing the colloid containing noble metal single - element particles in step S1 includes: dissolving a noble metal salt (when the noble metal is Pt, the corresponding noble metal salt can be chloroplatinic acid) and an alkali solution (for example, it can include but is not limited to sodium hydroxide solution) in an ethylene glycol solution to obtain a third mixed solution, and the pH of the third mixed solution is 9 to 12; heating the third mixed solution in an inert atmosphere (the inert atmosphere includes but is not limited to a nitrogen atmosphere, etc.) to obtain a colloid containing noble metal single - element particles. Thus, the particles of the noble metal single - element obtained by reducing the noble metal salt with ethylene glycol are smaller, making the activity of the dehydrogenation catalyst higher.

[0047] In some specific embodiments of the present invention, the method for preparing the dehydrogenation catalyst includes:

[0048] 1. Dissolve sodium hydroxide and chloroplatinic acid in ethylene glycol, stir at room temperature to form a transparent yellow solution, and the pH value is 9 to 12;

[0049] 2. Heat and stir the solution in a nitrogen atmosphere to finally form a dark - brown suspension colloid of Pt (platinum) particles;

[0050] 3. Add a quantitative Pt particle suspension to quantitative hydrochloric acid, adjust the pH to 3 to 5 to form a precipitate of Pt particles, then separate and recover them, and redisperse them into an ethanol or aqueous solution containing polyvinylpyrrolidone, and the ratio of polyvinylpyrrolidone to platinum nanoparticles is 1 to 1.3:1;

[0051] 4. Mix magnesium oxide (MgO) or zirconium dioxide (ZrO2) with the solution obtained in step 3, and after steps such as stirring, standing, separating, drying, and calcining, obtain a solid powder;

[0052] 5. Heat and reduce the solid powder obtained in step 4 in a hydrogen atmosphere, the temperature range can be: 300 to 500 °C, and the reduction time is 3 to 5 h, and finally obtain the dehydrogenation catalyst.

[0053] In another aspect of the present invention, the present invention provides a dehydrogenation catalyst prepared by the preparation method described above. The dehydrogenation catalyst includes: noble metal elemental particles; a non-acidic metal oxide support, and the noble metal elemental particles are loaded on at least a part of the surface of the non-acidic metal oxide support; based on the total mass of the dehydrogenation catalyst, the content of the noble metal elemental particles is 0.1 to 0.5 wt% (such as 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt% or 0.5 wt%, etc.). Thus, the noble metal content in the dehydrogenation catalyst is relatively low, and a non-acidic metal oxide is used as the support. The noble metal elemental particles are uniformly distributed on the surface of the support by electrostatic adsorption. The noble metal element transfers electrons to the support, reducing the electron cloud density of the noble metal elemental particles. On the one hand, it improves C-H activation and promotes the dehydrogenation rate. On the other hand, it reduces the adsorption strength of intermediate species, promotes the desorption of the final dehydrogenation product, inhibits the dehydrogenation side reaction of the organic liquid hydrogen storage material, and improves the dehydrogenation activity.

[0054] In some embodiments of the present invention, the noble metal elemental particles are deposited on the surface of the non-acidic metal oxide support by electrostatic adsorption.

[0055] In some embodiments of the present invention, the particle size of the noble metal elemental particles is 1.5 to 1.8 nm (for example, it can be 1.5 nm, 1.6 nm, 1.7 nm or 1.8 nm, etc.).

[0056] In some specific embodiments of the present invention, the dehydrogenation catalyst of the present invention is superior to commercial catalysts.

[0057] In another aspect of the present invention, the present invention provides an application of a dehydrogenation catalyst, applying the dehydrogenation catalyst to the dehydrogenation of an organic liquid hydrogen storage material; the dehydrogenation catalyst includes the dehydrogenation catalyst prepared by the preparation method described above or the dehydrogenation catalyst described above.

[0058] In some embodiments of the present invention, the organic liquid hydrogen storage material includes perhydro-monobenzyltoluene and / or perhydro-dibenzyltoluene. The principle of dehydrogenating perhydro-monobenzyltoluene and / or perhydro-dibenzyltoluene using the dehydrogenation catalyst of the present invention is as follows: The dehydrogenation catalyst of the present invention uses MgO or ZrO2 as the support, and the Pt elemental particles transfer more electrons to the support, reducing the electron cloud density, and Pt shows more positive valence states; compared with elements C and H in perhydro-monobenzyltoluene and perhydro-dibenzyltoluene, the electronegativity of C is greater, so C shows a slightly negative valence state. Since Pt in the dehydrogenation catalyst of the present invention can show more positive valence states, it is beneficial to the adsorption of reactants. At the same time, the bond between C and Pt is stable, which will weaken C-H, facilitate carbon-hydrogen activation, and thus promote the dehydrogenation reaction.

[0059] In some embodiments of the present invention, the reaction conditions for dehydrogenation are as follows: the space velocity is 3 to 6 h -1 (3 h -1 , 4 h -1 , 5 h -1 , or 6 h -1 etc.), the reaction pressure is 0.2 to 1.0 MPa (for example, it can be 0.2 MPa, 0.4 MPa, 0.6 MPa, 0.8 MPa, or 1 MPa, etc.), and the reaction temperature is 280 to 350 °C (for example, it can be 280 °C, 300 °C, 320 °C, 340 °C, or 350 °C, etc.). Thus, in the catalytic dehydrogenation of the dehydrogenation catalyst of the present invention, the reaction conditions are mild, the reaction dehydrogenation rate is high, and it has high industrial value.

[0060] In some embodiments of the present invention, the reaction device for dehydrogenation includes a fixed bed.

[0061] Examples

[0062] Example 1

[0063] The preparation method of the dehydrogenation catalyst includes the following steps:

[0064] 1. Dissolve 1 g of sodium hydroxide and 1 g of chloroplatinic acid hexahydrate in 100 mL of ethylene glycol. After stirring and dissolving, continuously introduce nitrogen for protection, heat to 170 °C, stir for 3 h, and then cool to form a dark brown colloid. Take out 10 mL of the brown colloid, add 2 mL of 2 mol / L hydrochloric acid, and adjust the pH to 3. Then disperse the platinum particles into a 400 mL ethanol solution containing 37.5 mg of polyvinylpyrrolidone. The mass ratio of Pt to polyvinylpyrrolidone is 1:1. Then add 6 g of MgO support, stir for 30 min, let it stand for 2 h, and then perform centrifugal separation, dry at 60 °C, and calcine at 450 °C for 4 h to obtain the catalyst precursor powder.

[0065] 2. Place the catalyst precursor powder obtained in step 1 in an H2 environment and reduce it at 350 °C for 1 h. After cooling, obtain the dehydrogenation catalyst, labeled as 0.5 wt% Pt / MgO. The X-ray photoelectron spectroscopy (XPS) results of the dehydrogenation catalyst in this example are as Figure 1 described, indicating that more electrons are transferred from Pt to MgO than to ZrO2. The transmission electron microscopy is as Figure 2 , 3 shown, indicating that the particle size distribution of Pt on the surfaces of Mg and ZrO2 is similar, and the particle size distribution is 1.7 nm.

[0066] Example 2

[0067] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1, except that the catalyst precursor powder obtained in Step 1 is placed in an H2 environment and reduced at 350 °C for 3 h, and the dehydrogenation catalyst is obtained after cooling.

[0068] Example 3

[0069] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1, except that the catalyst precursor powder obtained in Step 1 is placed in an H2 environment and reduced at 300 °C for 3 h, and the dehydrogenation catalyst is obtained after cooling.

[0070] Example 4

[0071] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1, except that the catalyst precursor powder obtained in Step 1 is placed in an H2 environment and reduced at 500 °C for 3 h, and the dehydrogenation catalyst is obtained after cooling.

[0072] Example 5

[0073] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1, except that in Step 1, 1 g of sodium hydroxide and 1 g of chloroplatinic acid hexahydrate are dissolved in 100 mL of ethylene glycol. After stirring and dissolving, nitrogen is continuously introduced for protection, heated to 100 °C, stirred for 3 h and then cooled to form a dark brown colloid. The obtained dehydrogenation catalyst has a particle size distribution of 1.9 nm.

[0074] Example 6

[0075] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1, except that in Step 1, the mass ratio of polyvinylpyrrolidone to platinum is 1.3:1, and other preparation conditions are the same as those of Example 1.

[0076] Example 7

[0077] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1, except that in Step 1, 2 mL of the brown liquid is taken out, 2 mL of 2 mol / L hydrochloric acid is added, and then the platinum particles are dispersed into a 400 mL ethanol solution containing 37.5 mg of polyvinylpyrrolidone, and then 6 g of MgO support is added. The obtained catalyst is denoted as 0.1 wt% Pt / MgO.

[0078] Example 8

[0079] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1, except that in Step 1, 4 mL of the brown colloid is taken out, 2 mL of 2 mol / L hydrochloric acid is added, and then the platinum particles are dispersed into a 400 mL ethanol solution containing 37.5 mg of polyvinylpyrrolidone, and then 6 g of MgO support is added. The obtained catalyst is denoted as 0.2 wt% Pt / MgO.

[0080] Example 9

[0081] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1. The difference lies in that in Step 1, 6 mL of brown colloid is taken out, 2 mL of 2 mol / L hydrochloric acid is added, and then the platinum particles are dispersed into a 400 mL ethanol solution containing 37.5 mg of polyvinylpyrrolidone, and then 6 g of MgO support is added. The obtained catalyst is denoted as 0.3 wt% Pt / MgO.

[0082] Example 10

[0083] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1. The difference lies in that in Step 1, 8 mL of brown colloid is taken out, 2 mL of 2 mol / L hydrochloric acid is added, and then the platinum particles are dispersed into a 400 mL ethanol solution containing 37.5 mg of polyvinylpyrrolidone, and then 6 g of MgO support is added. The obtained catalyst is denoted as 0.4 wt% Pt / MgO.

[0084] Example 11

[0085] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1. The difference is that the support is ZrO2, and the dehydrogenation catalyst is denoted as 0.5 wt% Pt / ZrO2.

[0086] Example 12

[0087] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1. The difference lies in that in Step 1, the mass ratio of polyvinylpyrrolidone to Pt is 1.5:1.

[0088] Example 13

[0089] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1. The difference lies in that in Step 1, the mass ratio of polyvinylpyrrolidone to Pt is 0.5:1.

[0090] Example 14

[0091] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1. The difference lies in that in Step 1, the mass ratio of polyvinylpyrrolidone to Pt is 2:1.

[0092] Example 15

[0093] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1. The difference lies in that in Step 2, the reduction temperature is 200 °C.

[0094] Example 16

[0095] The preparation method of the dehydrogenation catalyst is basically the same as that of Example 1. The difference lies in that in Step 2, the reduction temperature is 600 °C.

[0096] Comparative Example 1

[0097] Dissolve 1 g of sodium hydroxide and 1 g of chloroplatinic acid hexahydrate in 100 mL of ethylene glycol. After stirring until dissolved, introduce nitrogen, heat to 170 °C, stir for 3 h, and then cool. A dark brown colloid is formed. Take out 10 mL of the brown liquid, add 2 mL of 2 mol / L hydrochloric acid, and then disperse the platinum particles into a 400 mL ethanol solution containing 37.5 mg of polyvinylpyrrolidone. Subsequently, add 6 g of Al2O3 support, stir for 30 min, let stand for 2 h, then perform centrifugal separation, dry at 60 °C, and calcine at 450 °C for 4 h to obtain the catalyst precursor powder. Place the catalyst precursor in an H2 environment and reduce it at 350 °C for 1 h. After cooling, a dehydrogenation catalyst is obtained, labeled as 0.5 wt% Pt / Al2O3.

[0098] Comparative Example 2

[0099] The dehydrogenation catalyst is commercial 3 wt% Pt / Al2O3.

[0100] The specific operation steps for catalytic dehydrogenation are as follows:

[0101] Take 1 g of the dehydrogenation catalyst and load it into a stainless steel tube with an inner diameter of 8 mm. After reducing with hydrogen and purging with nitrogen to boost the pressure to 0.2 MPa, introduce the raw material (perhydro-monobenzyltoluene or perhydro-dibenzyltoluene) for reaction. Perform a flow rate test on the tail gas and simultaneously collect the liquid phase for chromatographic analysis.

[0102] The following Table 1 lists the catalytic dehydrogenation effects of different dehydrogenation catalysts on different raw materials (perhydro-monobenzyltoluene and perhydro-dibenzyltoluene), including the amount of dehydrogenation catalyst used, reaction space velocity, temperature, reaction pressure, and dehydrogenation rate.

[0103] Table 1

[0104]

[0105]

[0106]

[0107] For those not covered above, the prior art shall apply.

[0108] In the description of this specification, the description referring to terms such as "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0109] Although some specific embodiments of the present invention have been described in detail by way of examples, those skilled in the art should understand that the above examples are only for illustration and not for limiting the scope of the present invention. Those skilled in the technical field to which the present invention pertains can make various modifications or supplements to the described specific embodiments or use similar ways to replace them, but will not deviate from the direction of the present invention or exceed the scope defined by the appended claims. Those skilled in the art should understand that any modifications, equivalent replacements, improvements, etc. made to the above embodiments based on the technical essence of the present invention should be included in the protection scope of the present invention.

Claims

1. Application of a dehydrogenation catalyst, characterized in that, Applying a dehydrogenation catalyst to the dehydrogenation of organic liquid hydrogen storage materials; The organic liquid hydrogen storage materials include perhydro-monobenzyltoluene and / or perhydro-dibenzyltoluene; The dehydrogenation catalyst includes: Noble metal single-element particles; A non-acidic metal oxide support, and the noble metal single-element particles are loaded on at least a part of the surface of the non-acidic metal oxide support; Based on the total mass of the dehydrogenation catalyst, the content of the noble metal single-element particles is 0.1 to 0.5 wt%; And / or, the particle size of the noble metal single-element particles is 1.5 to 1.8 nm; The noble metal single-element particles are Pt; the non-acidic metal oxide support is MgO; The preparation method of the dehydrogenation catalyst includes: S1. Adjust the pH of the colloid containing noble metal single-element particles to 3 to 5 to obtain a first mixed solution; S2. Disperse the first mixed solution into a solution containing polyvinylpyrrolidone or polyvinyl alcohol to obtain a second mixed solution; S3. Mix and react the non-acidic metal oxide support with the second mixed solution, and calcine the product obtained by the reaction to obtain a solid powder; S4. Heat and reduce the solid powder in a hydrogen atmosphere to obtain the dehydrogenation catalyst.

2. The application according to claim 1, characterized in that In the second mixed solution, the mass ratio of polyvinylpyrrolidone to the noble metal single-element particles is 1 to 1.5:

1.

3. The application according to claim 1, wherein In step S3, the calcination temperature is 400 to 500 °C, and the time is 3 to 5 h.

4. The application according to claim 1, characterized in that, In step S4, the heating reduction temperature is 300 to 500 °C, and the reduction time is 3 to 5 h.

5. The application according to claim 1, wherein The preparation method of the colloid containing noble metal single-element particles in step S1 includes: Dissolve a noble metal salt and an alkali solution in an ethylene glycol solution to obtain a third mixed solution, and the pH of the third mixed solution is 9 to 12; Heat the third mixed solution in an inert atmosphere to obtain a colloid containing noble metal single-element particles.

6. The application according to claim 1, wherein The reaction conditions for dehydrogenation are as follows: the space velocity is 3 - 6 h -1 , the reaction pressure is 0.2 - 1.0 MPa, and the reaction temperature is 280 - 350 °C.

7. The application according to claim 1 or 6, characterized in that, The reaction device for the dehydrogenation includes a fixed bed.

Images