Preparation method and application of organic liquid dehydrogenation catalyst based on carrier modification

Abstract

The invention is suitable for the technical field of organic liquid dehydrogenation, and provides a preparation method and application of an organic liquid dehydrogenation catalyst based on carrier modification, and the method comprises the following steps: taking a certain mass of alumina carrier, adding an acid solution, and soaking at a certain temperature; roasting the soaked carrier; the preparation method comprises the following steps: preparing a carrier, roasting, soaking in an ammonium heptamolybdate solution with a certain concentration after roasting, draining, drying and roasting after soaking, heating under ammonia gas flow, preparing an impregnation liquid, adding the impregnation liquid into the carrier, stirring in the adding process, and standing for aging after stirring; drying the catalyst after aging; and roasting the catalyst after drying. According to the method, an acid pickling surface treatment means is adopted, active sites of an alumina carrier are adjusted through acid pickling, alkaline impurities are removed, the specific surface area is increased to optimize the surface structure of the carrier and enhance dispersion of active components on the carrier, and then molybdenum nitride is added as an auxiliary agent to improve the overall dehydrogenation activity of the catalyst.

Description

Technical Field

[0001] The invention belongs to the technical field of organic liquid dehydrogenation, and in particular relates to a preparation method and application of an organic liquid dehydrogenation catalyst based on carrier modification. Background Art

[0002] As energy demand has soared in recent decades, the use of fossil fuels has been increasing, and the greenhouse gases emitted during use have had a negative impact on the global environment. Hydrogen energy is considered to be a very promising energy source that can achieve the most ideal low-pollution emissions. Therefore, solving various problems in the fields of hydrogen production, storage, transportation, and utilization is a necessary condition for realizing the future hydrogen energy industry.

[0003] The essence of liquid organic hydrogen storage technology is to integrate hydrogen molecules into the molecular structure of unsaturated liquid organic substances such as olefins, alkynes, and aromatics through chemical reactions to achieve hydrogen storage, and then release hydrogen at the target location through chemical reactions. The dehydrogenation reaction is both an endothermic reaction and an organic reaction. To ensure the efficiency of the overall reaction and to minimize the purity of the produced hydrogen, it is necessary to develop new catalysts to meet such needs.

[0004] To achieve large-scale application of the dehydrogenation reaction of hydrogen storage organic liquid, it is necessary to ensure that the catalyst has high and stable hydrogen release activity. In the direction of the dehydrogenation reaction of perhydrodibenzyltoluene, the production technology of alumina carrier is mature and widely used, but the impurities left over from the preparation process of the carrier and the acidic sites of alumina itself will affect the actual dehydrogenation effect and stability of the catalyst in the dehydrogenation reaction of perhydrodibenzyltoluene; in addition, additives such as potassium are usually added to modify the carrier to a certain extent to improve the overall dehydrogenation performance. Summary of the invention

[0005] The purpose of the embodiments of the present invention is to provide a preparation method and application of a carrier-modified organic liquid dehydrogenation catalyst, aiming to solve the problems raised in the above background technology.

[0006] The embodiment of the present invention is implemented as follows: a method for preparing a carrier-modified organic liquid dehydrogenation catalyst comprises the following steps:

[0007] Step 1: Take a certain mass of alumina carrier, add acid solution and soak it at a certain temperature for a period of time;

[0008] Step 2, the carrier is calcined after soaking;

[0009] Step 3: After calcination, immerse the carrier in an ammonium heptamolybdate solution for a period of time;

[0010] Step 4, the carrier is calcined after soaking;

[0011] Step 5, after calcination, the carrier is placed under ammonia gas flow and heated for nitridation;

[0012] Step 6: After the nitridation is completed, the impregnation solution is prepared according to the mass of the alumina, and the impregnation solution is added to the carrier, and the carrier is stirred during the addition process. After the stirring is completed, the carrier is allowed to stand for aging for a period of time;

[0013] Step 7, drying the catalyst after aging;

[0014] Step 8: calcine the catalyst after drying.

[0015] According to a further technical solution, in step 1, the type of acid used for pickling and soaking is nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid.

[0016] According to a further technical solution, the concentration of the acid solution used in the pickling immersion is 0.1-1 mol / L; the solid-liquid ratio in the pickling immersion is 1 g: (5-25) mL; the immersion temperature of the pickling treatment is 10-80° C.; and the pickling immersion time is 0.5-100 h.

[0017] According to a further technical solution, in step 2, the calcination temperature is 350-550° C. and the calcination time is 3-6 hours.

[0018] According to a further technical solution, in step 3, the concentration of the ammonium heptamolybdate solution is 0.1-0.5 mol / L, and the soaking time is 1-10 h.

[0019] According to a further technical solution, in step 4, the calcination temperature is 500-800° C. and the calcination time is 3-8 hours.

[0020] According to a further technical solution, in step 5, the purity of ammonia is 80%-100%, the flow rate is 50-200 mL / min, the nitriding temperature is 400-600° C., and the nitriding time is 2-6 h.

[0021] According to a further technical solution, in step 6, the impregnation method is equal volume impregnation;

[0022] The precursor species for the impregnation operation are platinum nitrate, platinum chloride or chloroplatinic acid.

[0023] In a further technical solution, the impregnation liquid is added to the carrier and stirred for 0.5-2 hours; the aging time is 0.5-10 hours.

[0024] According to a further technical solution, in step 7, the drying temperature is 60-160°C.

[0025] According to a further technical solution, in step 8, the calcination temperature is 400-600° C. and the calcination time is 3-8 hours.

[0026] Another object of an embodiment of the present invention is to provide an application of a carrier-modified organic liquid dehydrogenation catalyst, wherein the catalyst prepared based on the above method is applied to the dehydrogenation reaction of perhydrodibenzyltoluene. Before the dehydrogenation reaction, the catalyst must be activated in situ. After the activation is completed, perhydrodibenzyltoluene is introduced and the temperature is increased to carry out the dehydrogenation reaction.

[0027] According to a further technical solution, in the in-situ activation operation, the hydrogen flow rate is 50-200 mL / min; the activation temperature is 300-500° C.; and the activation time is 2-24 h.

[0028] In a further technical solution, in the dehydrogenation reaction, the reaction temperature is 280-350°C, and the mass space velocity in the dehydrogenation reaction is 1-5h -1 .

[0029] The present invention provides a method for preparing a carrier-modified organic liquid dehydrogenation catalyst and its application. The method improves the catalytic activity of the catalyst dehydrogenation reaction by modifying the catalyst carrier by acid washing and adding molybdenum nitride, so that the hydrogen release efficiency of the modified catalyst in the dehydrogenation reaction is significantly improved. At the same time, the catalyst stability is improved by modification, the service life is extended, and the use cost is reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 Comparison of the stability of the catalyst before and after acid washing modification in Example 1 (reaction temperature 320°C mass space velocity 2g 全氢二苄基甲苯 / (g 催化剂 h));

[0031] Figure 2 Comparison of the stability of the catalyst before and after acid washing modification in Example 2 (reaction temperature 320°C mass space velocity 2g 全氢二苄基甲苯 / (g 催化剂 h));

[0032] Figure 3 Comparison of the stability of the catalyst before and after acid washing modification in Example 3 (reaction temperature 320°C mass space velocity 2g 全氢二苄基甲苯 / (g 催化剂 h));

[0033] Figure 4 Comparison of the stability of the catalyst before and after acid washing modification in Example 4 (reaction temperature 320°C mass space velocity 2g 全氢二苄基甲苯 / (g 催化剂 h)). DETAILED DESCRIPTION

[0034] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0035] The specific implementation of the present invention is described in detail below in conjunction with specific embodiments.

[0036] An embodiment of the present invention provides a method for preparing a carrier-modified organic liquid dehydrogenation catalyst, wherein the catalyst is a platinum-based catalyst in the form of aluminum oxide with a size between 5 mm and 25 mm; the method comprises the following steps:

[0037] Step 1: Take a certain mass of alumina carrier, add acid solution and soak it at a certain temperature for a period of time;

[0038] Step 2, the carrier is calcined after soaking;

[0039] Step 3: After calcination, immerse the carrier in an ammonium heptamolybdate solution for a period of time;

[0040] Step 4, the carrier is calcined after soaking;

[0041] Step 5, after calcination, the carrier is placed under ammonia gas flow and heated for nitridation;

[0042] Step 6: After the nitridation is completed, the impregnation solution is prepared according to the mass of the alumina, and the impregnation solution is added to the carrier, and the carrier is stirred during the addition process. After the stirring is completed, the carrier is allowed to stand for aging for a period of time;

[0043] Step 7, drying the catalyst after aging;

[0044] Step 8: calcine the catalyst after drying.

[0045] As a preferred embodiment of the present invention, in step 1, the type of acid used for pickling and soaking is nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid or citric acid, preferably nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid.

[0046] As a preferred embodiment of the present invention, the concentration of the acid solution used in the pickling immersion is 0.1-10 mol / L, preferably 0.1-5 mol / L, and more preferably 0.1-1 mol / L.

[0047] As a preferred embodiment of the present invention, the solid-liquid ratio in the pickling immersion is 1g:(1-100)mL, preferably 1g:(3-50)mL, and more preferably 1g:(5-25)mL.

[0048] As a preferred embodiment of the present invention, the soaking temperature of the pickling treatment is 0-95°C, preferably 5-90°C, and more preferably 10-80°C.

[0049] As a preferred embodiment of the present invention, the pickling soaking time is 0.5-200 hours, and the more preferred soaking time is 0.5-100 hours.

[0050] As a preferred embodiment of the present invention, in step 2, the calcination temperature of the calcination treatment is 250-800°C, preferably 300-600°C, and more preferably 350-550°C;

[0051] The calcination time is 0.5-10 h, preferably 0.5-10 h, and more preferably 3-6 h.

[0052] As a preferred embodiment of the present invention, in step 3, the concentration of the ammonium heptamolybdate solution is 0.01-0.5 mol / L, preferably 0.1-0.5 mol / L;

[0053] In the ammonium heptamolybdate soaking operation, the soaking time is 0.5-100 hours, preferably 0.5-20 hours, and more preferably 1-10 hours.

[0054] As a preferred embodiment of the present invention, in step 4, the calcination temperature of the calcination treatment is 400-800° C., preferably 500-800° C.;

[0055] In the roasting operation, the roasting time is 2-8 hours, preferably 3-8 hours.

[0056] As a preferred embodiment of the present invention, in step 5, the purity of the ammonia gas flow for nitridation treatment is 50%-100%, preferably 70%-100%;

[0057] During the nitriding operation, the gas flow rate is 20-400 mL / min, preferably 50-300 mL / min, and more preferably 50-200 mL / min;

[0058] In the nitriding operation, the nitriding temperature is 300-800°C, preferably 400-600°C;

[0059] In the nitriding operation, the nitriding temperature is 2-12h, preferably 2-6h.

[0060] As a preferred embodiment of the present invention, in step 6, the impregnation method is equal volume impregnation;

[0061] The types of precursors used in the impregnation operation are platinum nitrate, platinum chloride, and chloroplatinic acid;

[0062] In the impregnation operation, the concentration of the precursor solution is calculated and configured according to the loading amount, carrier mass, and water absorption rate;

[0063] In the impregnation operation, the impregnation liquid is added to the carrier and stirred for 0.1-10 hours, preferably for 0.5-2 hours;

[0064] In the impregnation operation, the aging time is 0.5-40 h, preferably 0.5-20 h, and more preferably 0.5-10 h.

[0065] As a preferred embodiment of the present invention, in step 7, the oven temperature is 40-200°C, preferably 50-190°C, and more preferably the drying temperature is 60-160°C.

[0066] As a preferred embodiment of the present invention, in step 8, the calcination temperature is 300-800° C., preferably 400-600° C.;

[0067] The calcination time is 0.5-15h, preferably 2-10h, and more preferably 3-8h.

[0068] Another embodiment of the present invention provides an application of a carrier-modified organic liquid dehydrogenation catalyst. The catalyst prepared based on the above method is applied to the dehydrogenation reaction of perhydrodibenzyltoluene. Before the dehydrogenation reaction, the catalyst needs to be activated in situ. After the activation is completed, perhydrodibenzyltoluene is introduced and the temperature is increased to carry out the dehydrogenation reaction.

[0069] As a preferred embodiment of the present invention, in the in-situ activation operation, the hydrogen flow rate is 10-400 mL / min, preferably, the hydrogen flow rate is 50-200 mL / min;

[0070] The activation temperature is 100-600°C, preferably 200-400°C, and more preferably 300-500°C;

[0071] The activation time is 2-24h, preferably 4-12h.

[0072] As a preferred embodiment of the present invention, the reaction temperature in the dehydrogenation reaction is 280-350°C, and the mass space velocity in the dehydrogenation reaction is 1-5h -1 .

[0073] Several specific examples are provided below to verify the effectiveness of this method:

[0074] Example 1: Weigh 10 g of the carrier, measure 25 mL of a hydrochloric acid solution with a molar concentration of 0.5 mol / L, take 5 g of the carrier and soak it in the solution, and heat it in a water bath for 4 h at a temperature of 20°C. After pickling, the carrier was placed in a muffle furnace and roasted at 450°C for 3 hours, taken out and cooled, and the cooled carrier was immersed in 0.1mol / L ammonium heptamolybdate solution for 2 hours. After soaking, it was roasted at 600°C for 8 hours. After roasting, the carrier was placed in a 70% purity, 100mL / min ammonia gas flow, and nitrided at 500°C for 3 hours. After nitriding, an equal volume of chloroplatinic acid solution was measured according to the water absorption rate of the carrier for impregnation, and placed in air for aging for 4 hours. After aging, it was placed in a 100°C oven for drying. The dried catalyst was placed in a muffle furnace again and roasted at 500°C for 4 hours. After roasting, it was loaded into a reaction device and pure hydrogen was passed at a flow rate of 50mL / min. The temperature was raised to 300°C at a heating rate of 3°C / min, and activated at this temperature for 12 hours to obtain a modified 1% catalyst. Take the remaining 5g of the carrier, and impregnate it with an equal volume of chloroplatinic acid solution according to the water absorption rate of the carrier, place it in air for aging for 4 hours, and place it in a 100°C oven for drying after aging. Take the dried catalyst and place it back in the muffle furnace and roast it at 500°C for 4 hours. After roasting, put it into the reaction device, introduce pure hydrogen at a flow rate of 50mL / min, and heat it to 300°C at a heating rate of 3°C / min. Activate it at this temperature for 12 hours to obtain an unmodified 1% catalyst.

[0075] The two catalysts obtained were used for organic liquid dehydrogenation experiments, and the dehydrogenation degrees of the two catalysts were recorded at the same time; the temperature and mass space velocity were then increased to allow the reaction to proceed at a high dehydrogenation degree, and the reaction was continued for 200 hours. A sample point was taken every 40 hours to record the dehydrogenation degree. The specific experimental results are recorded in Table 1. Figure 1 .

[0076] Example 2: Weigh 10 g of the carrier, measure 35 mL of sulfuric acid solution with a molar concentration of 0.1 mol / L, take 5 g of the carrier and soak it in the solution, and heat it in a water bath for 5 h at a temperature of 40°C. After pickling, the carrier was placed in a muffle furnace and roasted at 400°C for 4 hours, taken out and cooled, and the cooled carrier was immersed in a 0.4 mol / L ammonium heptamolybdate solution for 3 hours. After soaking, it was roasted at 500°C for 4 hours. After roasting, the carrier was placed in a 90% purity, 150 mL / min ammonia gas flow, and nitrided at 450°C for 6 hours. After nitriding, an equal volume of chloroplatinic acid solution was measured according to the water absorption rate of the carrier for impregnation, and placed in air for aging for 6 hours. After aging, it was placed in a 120°C oven for drying. The dried catalyst was placed in a muffle furnace again and roasted at 240°C for 3 hours. After roasting, it was loaded into a reaction device and pure hydrogen was passed at a flow rate of 120 mL / min. The temperature was raised to 450°C at a heating rate of 3°C / min, and activated at this temperature for 6 hours to obtain a modified 1.5% catalyst. Take the remaining 5g of the carrier, and impregnate it with an equal volume of chloroplatinic acid solution according to the water absorption rate of the carrier, place it in air for aging for 6 hours, and place it in a 120°C oven for drying after aging. Take the dried catalyst and place it back in the muffle furnace and roast it at 450°C for 3 hours. After roasting, load it into the reaction device, introduce pure hydrogen at a flow rate of 120mL / min, and heat it to 450°C at a heating rate of 3°C / min. Activate it at this temperature for 6 hours to obtain an unmodified 1.5% catalyst.

[0077] The two catalysts obtained were used for organic liquid dehydrogenation experiments, and the dehydrogenation degrees of the two catalysts were recorded at the same time; the temperature and mass space velocity were then increased to allow the reaction to proceed at a high dehydrogenation degree, and the reaction was continued for 200 hours. A sample point was taken every 40 hours to record the dehydrogenation degree. The specific experimental results are recorded in Table 1. Figure 2 .

[0078] Example 3: Weigh 10 g of the carrier, measure 30 mL of a phosphoric acid solution with a molar concentration of 0.8 mol / L, take 5 g of the carrier and soak it in the solution, and heat it in a water bath for 7 h at a temperature of 60°C. After pickling, the carrier was placed in a muffle furnace and roasted at 500°C for 5h, taken out and cooled, and the cooled carrier was immersed in a 0.2mol / L ammonium heptamolybdate solution for 6h. After soaking, it was roasted at 700°C for 5h. After roasting, the carrier was placed in an 80% purity, 50mL / min ammonia gas flow, and nitrided at 550°C for 2h. After nitriding, an equal volume of chloroplatinic acid solution was measured according to the water absorption rate of the carrier, and it was placed in the air for aging for 10h. After aging, it was placed in a 110°C oven for drying. The dried catalyst was placed in a muffle furnace again and roasted at 550°C for 5h. After roasting, it was loaded into a reaction device and pure hydrogen was passed at a flow rate of 200mL / min. The temperature was raised to 400°C at a heating rate of 3°C / min, and activated at this temperature for 10h to obtain a modified 0.8% catalyst. Take the remaining 5g of the carrier, and impregnate it with an equal volume of chloroplatinic acid solution according to the water absorption rate of the carrier, place it in air for aging for 10 hours, and place it in an oven at 110°C for drying after aging. Take the dried catalyst and place it back in the muffle furnace and roast it at 550°C for 5 hours. After roasting, put it into the reaction device, introduce pure hydrogen at a flow rate of 200mL / min, and heat it to 400°C at a heating rate of 3°C / min. Activate it at this temperature for 10 hours to obtain an unmodified 0.8% catalyst.

[0079] The two catalysts obtained were used for organic liquid dehydrogenation experiments, and the dehydrogenation degrees of the two catalysts were recorded at the same time; the temperature and mass space velocity were then increased to allow the reaction to proceed at a high dehydrogenation degree, and the reaction was continued for 200 hours. A sample point was taken every 40 hours to record the dehydrogenation degree. The specific experimental results are recorded in Table 1. Figure 3 .

[0080] Example 4: Weigh 10 g of the carrier, measure 25 mL of 0.3 mol / L nitric acid solution, soak 5 g of the carrier in the solution, and heat in a water bath for 4 h at 80°C. After pickling, the carrier was placed in a muffle furnace and calcined at 450°C for 6 hours, taken out and cooled, and the cooled carrier was immersed in a 0.5 mol / L ammonium heptamolybdate solution for 8 hours. After immersion, it was calcined at 800°C for 3 hours. After calcination, the carrier was placed in a 100% purity, 200 mL / min ammonia gas flow, and nitrided at 400°C for 4 hours. After nitridation, an equal volume of chloroplatinic acid solution was measured according to the water absorption rate of the carrier for immersion, and it was placed in the air for aging for 4 hours. After aging, it was placed in a 100°C oven for drying. The dried catalyst was placed in a muffle furnace again and calcined at 500°C for 4 hours. After calcination, it was loaded into a reaction device and pure hydrogen was introduced at a flow rate of 150 mL / min. The temperature was raised to 250°C at a heating rate of 3°C / min, and activated at this temperature for 7 hours to obtain a modified 2% catalyst. Take the remaining 5g of the carrier, measure an equal volume of chloroplatinic acid solution according to the water absorption rate of the carrier, and immerse it in the air for 4 hours. After aging, place it in an oven at 100°C for drying. After drying, place the catalyst back in a muffle furnace and roast it at 500°C for 4 hours. After roasting, put it into the reaction device, introduce pure hydrogen at a flow rate of 150mL / min, and heat it to 250°C at a heating rate of 3°C / min. Activate it at this temperature for 7 hours to obtain an unmodified 2% catalyst.

[0081] The two catalysts obtained were used for organic liquid dehydrogenation experiments, and the dehydrogenation degrees of the two catalysts were recorded at the same time; the temperature and mass space velocity were then increased to allow the reaction to proceed at a high dehydrogenation degree, and the reaction was continued for 200 hours. A sample point was taken every 40 hours to record the dehydrogenation degree. The specific experimental results are recorded in Table 1. Figure 4 .

[0082] Table 1 Comparison of dehydrogenation activity of catalysts in different embodiments before and after modification at different feed rates

[0083]

[0084]

[0085] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a carrier-modified organic liquid dehydrogenation catalyst, characterized in that: The following steps are involved: Step 1, take a certain mass of alumina carrier, add acid solution and soak it at a certain temperature for a certain time; Step 2, the carrier is calcined after soaking; Step 3: After calcination, immerse the carrier in an ammonium heptamolybdate solution for a certain period of time; Step 4, the carrier is calcined after soaking; Step 5, after calcination, the carrier is placed under ammonia gas flow and heated for nitridation; Step 6: After the nitridation is completed, an impregnation solution is prepared according to the mass of alumina, and the impregnation solution is added to the carrier, and the carrier is stirred during the addition process. After the stirring is completed, the carrier is allowed to stand for a certain period of aging; Step 7, drying the catalyst after aging; Step 8: calcine the catalyst after drying.

2. The method for preparing a carrier-modified organic liquid dehydrogenation catalyst according to claim 1, characterized in that: In step 1, the type of acid used for pickling and soaking is nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid; The acid concentration used in the pickling soaking is 0.1-1 mol / L; the solid-liquid ratio in the pickling soaking is 1g:(5-25)mL; the soaking temperature of the pickling treatment is 10-80°C; and the pickling soaking time is 0.5-100h.

3. The method for preparing a carrier-modified organic liquid dehydrogenation catalyst according to claim 2, characterized in that: In the step 2, the calcination temperature is 350-550° C. and the calcination time is 3-6 hours.

4. The method for preparing a carrier-modified organic liquid dehydrogenation catalyst according to claim 3, characterized in that: In step 3, the concentration of the ammonium heptamolybdate solution is 0.01-0.5 mol / L, and the soaking time is 0.5-100 h.

5. The method for preparing a carrier-modified organic liquid dehydrogenation catalyst according to claim 4, characterized in that: In step 4, the calcination temperature is 400-800° C. and the calcination time is 2-8 hours.

6. The method for preparing a carrier-modified organic liquid dehydrogenation catalyst according to claim 5, characterized in that: In step 5, the ammonia gas flow for nitridation treatment is a mixed gas of ammonia and hydrogen, the purity of ammonia is 50%-100%, the flow rate is 20-400 mL / min, the nitridation temperature is 300-800° C., and the nitridation time is 2-12 h.

7. The method for preparing a carrier-modified organic liquid dehydrogenation catalyst according to claim 6, characterized in that: In step 6, the impregnation method is equal volume impregnation; The precursor species for the impregnation operation is platinum nitrate, platinum chloride or chloroplatinic acid; The impregnation liquid is added to the carrier and stirred for 0.5-2 hours; the aging time is 0.5-10 hours.

8. The method for preparing a carrier-modified organic liquid dehydrogenation catalyst according to claim 7, characterized in that: In step 7, the drying temperature is 60-160°C.

9. The method for preparing a carrier-modified organic liquid dehydrogenation catalyst according to claim 8, characterized in that: In step 8, the calcination temperature is 400-600° C. and the calcination time is 3-8 hours.

10. An application of a carrier-modified organic liquid dehydrogenation catalyst, comprising a catalyst prepared by the method for preparing a carrier-modified organic liquid dehydrogenation catalyst according to any one of claims 1 to 9, wherein the catalyst is applied to the dehydrogenation reaction of perhydrodibenzyltoluene, and before the dehydrogenation reaction, the catalyst is activated in situ, and after the activation is completed, perhydrodibenzyltoluene is introduced and the temperature is raised to carry out the dehydrogenation reaction.

11. The use of the organic liquid dehydrogenation catalyst based on carrier modification according to claim 10, characterized in that: In the in-situ activation operation, the hydrogen flow rate is 50-200 mL / min; the activation temperature is 300-500°C; and the activation time is 2-24 h.

12. The use of the carrier-modified organic liquid dehydrogenation catalyst according to claim 10, characterized in that: In the dehydrogenation reaction, the reaction temperature is 280-350°C, and the mass space velocity in the dehydrogenation reaction is 1-5h -1 .

Images