Method for preparing Ni-N-coated SAPO-34 catalyst by recycling coal-based olefin waste SAPO-34 and application of Ni-N-coated SAPO-34 catalyst

Abstract

The invention discloses a method for preparing a Ni-N-coated SAPO-34 catalyst by recycling coal-based olefin waste SAPO-34, and relates to the technical field of industrial waste catalyst reutilization, alkali treatment is adopted to directionally depolymerize an ordered crystal structure of the waste SAPO-34 catalyst, and carbon substances and macromolecular tar organic matters in a pore structure are exposed, so that the Ni-N-coated SAPO-34 catalyst is prepared. Soluble macromolecular organic matters in the SAPO-34 carrier are removed through efficient extraction to obtain the amorphous SAPO-34 carrier, the amorphous Ni-N-coated SAPO-34 catalyst is prepared by loading Ni and doping N, a macromolecular substrate is enhanced, the active site density can be approached, and the catalytic reaction activity and efficiency are improved; the irregular structure can further reduce the strength of secondary side reaction by increasing the diffusion speed of the macromolecular substrate and the target product. The catalyst is applied to a multi-aromatic-ring organic liquid hydrogen storage system, the hydrogenation efficiency of organic liquid is improved, the production cost is reduced, and disordered discharge is reduced through resource utilization of waste; the preparation process is simple, low in cost and remarkable in resource and environment benefits.

Description

Technical Field

[0001] The present invention relates to the technical field of industrial waste catalyst recycling, and in particular to a method for preparing a Ni-N@SAPO-34 catalyst by recycling coal-based olefin waste SAPO-34, and a method and application of preparing a Ni-N@SAPO-34 catalyst by using coal-based olefin waste SAPO-34 catalyst. Background Art

[0002] With the high-quality development of the economy and society, human demand for energy is becoming increasingly diversified, and environmental requirements are becoming increasingly stringent. As an important component of the modern coal chemical industry, the output of industrial waste SAPO-34 catalysts formed by the circulating fluidized bed reaction unit of the coal-based olefin industry has been increasing year by year. Solving the resource, clean and high-value utilization of such waste catalysts is of great significance to the high-quality development of the coal-based olefin industry. However, the structure of the waste SAPO-34 catalyst has carbon deposits covering the active sites, and its special pore structure produces large molecular tar-like organic matter during the acid catalysis process. It is difficult to completely separate the above species from SAPO-34 through traditional roasting methods alone, which makes it difficult to further recycle the waste SAPO-34 catalyst, and its high-value utilization is hindered.

[0003] As a clean energy, hydrogen energy has a very broad prospect in the fields of future energy layout and development. However, due to the low density and flammability of hydrogen, storage and transportation face certain severe challenges. The traditional hydrogen storage process based on compression has problems such as high cost, low efficiency and high energy consumption. Therefore, finding an efficient, safe and low-carbon hydrogen storage technology is a key issue in the development of the hydrogen energy industry. Liquid organic hydrogen (LOHCs) technology is a new type of hydrogen storage technology with high hydrogen storage density, environmental protection and safety. It is considered to be an effective way to solve the problem of hydrogen storage and transportation. Conventional organic liquid hydrogen storage carriers include alkylbenzenes, alkylnaphthalenes, alkylanthracenes, etc. Alkyl aromatics and other macromolecules as organic liquid hydrogen storage carriers have the advantages of large hydrogen storage capacity, high stability, simple operation, easy recovery, good chemical inertness and integration with infrastructure. It is a hydrogen energy storage medium with great potential and provides new possibilities for the development of hydrogen energy economy. Summary of the invention

[0004] In order to solve the technical problem that waste SAPO-34 catalyst is difficult to recycle, the present invention discloses a method for preparing Ni-N@SAPO-34 catalyst from waste SAPO-34 of coal-based olefins. Firstly, the ordered crystal structure of the waste SAPO-34 catalyst is directionally depolymerized by alkali treatment to expose the carbon material and macromolecular tar organic matter in the pore structure, and then the soluble macromolecular organic matter is removed by efficient extraction to obtain an amorphous SAPO-34 carrier, and then non-precious metal Ni and doping N are loaded on N in sequence.2 and H 2 A highly active Ni-N@SAPO-34 catalyst was prepared under atmosphere; the catalyst was applied to a polyaromatic ring organic liquid hydrogen storage system, which improved the hydrogenation efficiency of the organic liquid, reduced production costs, and reduced disordered emissions through resource utilization of waste. The preparation process is simple, low-cost, and has significant resource and environmental benefits. The reaction conditions are mild, and it has broad application prospects in the field of organic liquid hydrogen storage.

[0005] To achieve the above object, the present invention adopts the following technical solutions:

[0006] The method for preparing Ni-N@SAPO-34 catalyst from coal-based olefin waste SAPO-34 includes the following specific steps:

[0007] a. Pretreatment of spent SAPO-34 catalyst

[0008] a1. The spent SAPO-34 catalyst is placed in an alkaline solution for directional depolymerization, sealed, heated, stirred, and then cooled to room temperature to obtain a mixture;

[0009] a2. Centrifuge the mixture obtained in step a1, collect the solid matter, wash it multiple times at room temperature, dry it to obtain solid powder, and grind it for later use;

[0010] a3. The solid powder obtained in step a2 is placed in an organic compound solvent, extracted under a closed environment at room temperature, and then subjected to ultrasonic washing, filtration, and heating to obtain an amorphous SAPO-34 carrier from which organic matter has been removed;

[0011] b. Preparation of Ni-N@SAPO-34 catalyst precursor

[0012] First, a certain amount of urea and Ni(NO 3 ) 2 6H 2 O is completely dissolved in deionized water, and then the amorphous SAPO-34 carrier obtained in step a3 is added, and a uniform mixed solution is obtained after sealing and ultrasonication, and the mixture is continued to be sealed and stirred at room temperature to ensure that the carrier is completely wetted; after drying, the Ni-N@SAPO-34 catalyst precursor is obtained, which is ground for standby use;

[0013] c. Preparation of Ni-N@SAPO-34 catalyst

[0014] c1. Place the Ni-N@SAPO-34 catalyst precursor obtained in step b2 in a tubular furnace and calcine it under a nitrogen atmosphere, raising the temperature to 500-600°C and maintaining it for 2-3h;

[0015] c2. After the temperature drops to 50℃ naturally, introduce H 2, heating to 450-550°C to reduce the Ni-N@SAPO-34 catalyst precursor, maintaining for 1-3 hours and then naturally cooling to room temperature to obtain the Ni-N@SAPO-34 catalyst.

[0016] Further, in step a1, the alkaline solution for directional depolymerization is aqueous ammonia, pH>11, and the solid-liquid ratio of the waste SAPO-34 catalyst to the alkaline solution is 1:20-30;

[0017] The sealing heating temperature is 80-90°C, the stirring time is 1-2h, and the rotation speed is 150-250rpm.

[0018] Furthermore, in step a2, washing is performed 3 times at room temperature, and the drying conditions are: temperature 80° C., time 2 h, and the solid powder is ground to less than 200 mesh.

[0019] Furthermore, in step a3, the solid-liquid ratio of the solid powder to the organic compound solvent is 1:5-15, and the organic compound solvent is prepared by acetone and carbon disulfide, and the volume ratio of the two is 1:1;

[0020] The extraction time is 20-40 minutes, the ultrasonic washing time is 30 minutes, and the temperature is raised to 60°C and maintained for 40 minutes.

[0021] Further, in step b, urea and Ni(NO 3 ) 2 6H 2 O, Ni loading is 8-15wt%;

[0022] The mass ratio of the added amorphous SAPO-34 carrier to urea is 1:1-5, the sealed ultrasonic time is 1-2h, and the sealed stirring time at room temperature is 2-3h;

[0023] Drying conditions of Ni-N@SAPO-34 catalyst precursor: temperature 60-80°C, time 8-12h;

[0024] The Ni-N@SAPO-34 catalyst precursor was ground to below 200 mesh.

[0025] Furthermore, in step c1, the roasting process controls N 2 Flow rate: 2-4 mL min -1 , heating rate is 1-5℃·min -1 , 600℃ holding time is 2h;

[0026] In step c2, H is controlled during the reduction process. 2 Flow rate: 5-8 mL min -1 , heating rate is 1-5℃·min -1 .

[0027] The invention discloses a Ni-N@SAPO-34 catalyst prepared by the method.

[0028] The invention discloses application of the Ni-N@SAPO-34 catalyst in a polycyclic aromatic ring organic liquid hydrogen storage system.

[0029] The beneficial effects of the present invention are:

[0030] 1. This method starts from the basic structural unit of the SAPO-34 catalyst. The substance is a trigonal crystal structure composed of silicon-oxygen tetrahedron, aluminum-oxygen tetrahedron and phosphorus-oxygen tetrahedron. The basic structural unit of its depolymerization is an excellent carrier for macromolecular catalytic hydrogenation reactions. The SAPO-34 amorphous carrier obtained by depolymerization has the characteristics of high density of accessible catalytic sites of polycyclic aromatic rings.

[0031] 2. In this method, the ratio of urea, Ni salt and SAPO-34 carrier must be strictly controlled to ensure that the multiphase system can not only micro-etch the SAPO-34 amorphous structure to achieve N element doping, but also enable the Ni salt to be deposited on the SAPO-34 amorphous carrier in a highly dispersed form.

[0032] 3. In this method, N is first used 2 The impurities in the amorphous structure of SAPO-34 were removed by calcination in H 2 Atmospheric reduction promotes the high dispersion of metal Ni particles, improves the activity of hydrogenation catalytic reaction by improving the utilization efficiency of loaded metal atoms, and optimizes the electron transfer efficiency of the catalyst by N doping to ensure the stability and activity of the catalyst.

[0033] 4. The highly active Ni-N@SAPO-34 catalyst prepared by this method can realize the efficient hydrogenation process of polycyclic aromatic ring organic liquids at low temperature, low hydrogen pressure and in a short time, thereby realizing hydrogen storage in organic liquids.

[0034] 5. The high-activity Ni-N@SAPO-34 catalyst prepared by this method has high activity and still maintains more than 98% of the catalytic reaction activity after being recycled 10 times. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is a SEM image of the 15Ni-N@SAPO-34 catalyst prepared in Example 1 of the present invention;

[0036] Figure 2 This is a TEM image of the 15Ni-N@SAPO-34 catalyst prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] Example 1

[0039] A method for preparing Ni-N@SAPO-34 catalyst by recycling coal-based olefin waste SAPO-34, the specific process is as follows:

[0040] 1. Take 10.0 g of coal-based olefin waste SAPO-34 catalyst, place it in 300 mL of ammonia solution with pH>11, seal and heat with stirring at 90°C for 2 h, with a stirring speed of 2000 rpm, and then cool to room temperature to obtain a mixture.

[0041] 2. Centrifuge the mixture to obtain a solid. Collect the solid and wash it three times at room temperature. Dry it at 80°C for 2 hours to obtain a solid powder. Grind it to a size of less than 200 mesh for later use.

[0042] 3. Take 10.0g of the ground solid powder and place it in 150mL of an organic compound solvent. Extract it in a closed environment at room temperature for 30min. Then filter it, heat it to 60°C, and maintain it for 40min to remove the compound solvent to obtain an amorphous SAPO-34 with organic matter removed as a carrier for standby use.

[0043] 4. Take 2.0g urea and 1.52g Ni(NO 3 ) 2 6H 2 O was dissolved in 20 mL of deionized water, and after being completely dissolved at room temperature, 2 g of amorphous SAPO-34 carrier from which organic matter had been removed was added. After all the dissolution was completed, the mixture was sealed and ultrasonicated for 1 h, and then the mixture was sealed and stirred for 3 h at room temperature to ensure that the carrier was completely wetted. The obtained mixed solution was placed in a forced air drying oven for drying at a temperature of 70° C. for a drying time of 10 h to obtain a 15Ni-N@SAPO-34 catalyst precursor with a Ni loading of 15 wt%, and the mixture was ground to 300 mesh for use.

[0044] 5. Take 2.0 g of the 15Ni-N@SAPO-34 catalyst precursor prepared in step 4 and place it in N 2 In the atmosphere tube furnace, control N 2 Flow rate: 2 mL min -1 , at 5℃·min -1The heating rate was raised to 600 °C for 3 h, then cooled to 50 °C and switched to H 2 Atmosphere, H 2 Flow rate: 8 mL min -1 After calcination and reduction for 2 hours, it is cooled to room temperature and the powder is ground into 300 mesh to obtain 15Ni-N@SAPO-34 catalyst.

[0045] Example 2

[0046] 1. Take 10.0 g of coal-based olefin waste SAPO-34 catalyst, place it in 300 mL of ammonia solution with pH>11, seal and heat with stirring at 90°C for 2 h, with a stirring speed of 2000 rpm, and then cool to room temperature to obtain a mixture.

[0047] 2. Centrifuge the mixture to obtain a solid. Collect the solid and wash it three times at room temperature. Dry it at 80°C for 2 hours to obtain a solid powder. Grind it to a size of less than 200 mesh for later use.

[0048] 3. Take 10.0 g of the ground solid powder and extract it in a closed environment at room temperature for 30 minutes. Then filter it, heat it to 60°C, and maintain it for 40 minutes to obtain SAPO-34 as a carrier for standby use.

[0049] 4. Take 2.0g urea and 1.52g Ni(NO 3 ) 2 6H 2 O was dissolved in 20 mL of deionized water, and after it was completely dissolved at room temperature, 2 g of SAPO-34 carrier was added. After it was completely dissolved, it was sealed and ultrasonicated for 1 hour, and then the sealed stirring was continued at room temperature for 3 hours to ensure that the carrier was completely wetted; the obtained mixed solution was placed in a forced air drying oven for drying at a temperature of 70° C. for 10 hours to obtain a 15Ni-N@SAPO-34-1 catalyst precursor with a mass ratio of Ni loading to SAPO-34 carrier of 15:100, and the catalyst precursor was ground to 300 mesh for use.

[0050] 5. Take 2.0 g of the 15Ni-N@SAPO-34-1 catalyst precursor prepared in step 4 and place it in N 2 In the atmosphere tube furnace, control N 2 Flow rate: 2 mL min -1 , at 5℃·min -1 The heating rate was raised to 600 °C for 3 h, then cooled to 50 °C and switched to H 2 Atmosphere, H 2 Flow rate: 8 mL min -1 After calcination and reduction for 2 hours, it is cooled to room temperature and the powder is ground into 300 mesh to obtain 15Ni-N@SAPO-34-1 catalyst.

[0051] Example 3

[0052] A method for preparing Ni-N@SAPO-34 catalyst by recycling coal-based olefin waste SAPO-34, the specific process is as follows:

[0053] 1. Take 10.0 g of coal-based olefin waste SAPO-34 catalyst, place it in 300 mL of ammonia solution with pH>11, seal and heat with stirring at 90°C for 2 h, with a stirring speed of 2000 rpm, and then cool to room temperature to obtain a mixture.

[0054] 2. Centrifuge the mixture to obtain a solid. Collect the solid and wash it three times at room temperature. Dry it at 80°C for 2 hours to obtain a solid powder. Grind it to a size of less than 200 mesh for later use.

[0055] 3. Take 10.0g of the ground solid powder and place it in 150mL of an organic compound solvent. Extract it in a closed environment at room temperature for 30min. Then filter it, heat it to 60°C, and maintain it for 40min to remove the compound solvent to obtain an amorphous SAPO-34 with organic matter removed as a carrier for standby use.

[0056] 4. Take 1.52g Ni(NO 3 ) 2 6H 2 O was dissolved in 20 mL of deionized water, and after being completely dissolved at room temperature, 2 g of amorphous SAPO-34 carrier from which organic matter had been removed was added. After all the dissolution, the mixture was sealed and ultrasonicated for 1 h, and then the mixture was sealed and stirred for 3 h at room temperature to ensure that the carrier was completely wetted. The obtained mixed solution was placed in a forced air drying oven for drying at a temperature of 70° C. for 10 h to obtain a 15Ni@SAPO-34 catalyst precursor with a Ni loading of 15:100 to the SAPO-34 carrier mass ratio, and the mixture was ground to 300 mesh for use.

[0057] 5. Take 2.0 g of the 15Ni@SAPO-34 catalyst precursor prepared in step 4 and place it in N 2 In the atmosphere tube furnace, control N 2 Flow rate: 2 mL min -1 , at 5℃·min -1 The heating rate was raised to 600 °C for 3 h, then cooled to 50 °C and switched to H 2 Atmosphere, H 2 Flow rate: 8 mL min -1 After calcination and reduction for 2 hours, it was cooled to room temperature and the powder was ground into 300 mesh to obtain 15Ni@SAPO-34 catalyst.

[0058] Example 4

[0059] A method for preparing Ni-N@SAPO-34 catalyst by recycling coal-based olefin waste SAPO-34, the specific process is as follows:

[0060] 1. Take 10.0 g of coal-based olefin waste SAPO-34 catalyst, place it in 300 mL of ammonia solution with pH>11, seal and heat with stirring at 90°C for 2 h, with a stirring speed of 2000 rpm, and then cool to room temperature to obtain a mixture.

[0061] 2. Centrifuge the mixture to obtain a solid. Collect the solid and wash it three times at room temperature. Dry it at 80°C for 2 hours to obtain a solid powder. Grind it to a size of less than 200 mesh for later use.

[0062] 3. Take 10.0g of the ground solid powder and place it in 150mL of an organic compound solvent. Extract it in a closed environment at room temperature for 30min. Then filter it, heat it to 60°C, and maintain it for 40min to remove the compound solvent to obtain an amorphous SAPO-34 with organic matter removed as a carrier for standby use.

[0063] 4. Take 2.0g urea and 0.31gg Ni(NO 3 ) 2 6H 2 O was dissolved in 20 mL of deionized water, and after being completely dissolved at room temperature, 2 g of amorphous SAPO-34 carrier from which organic matter had been removed was added. After all the dissolution, the mixture was sealed and ultrasonicated for 1 h, and then the mixture was sealed and stirred for 3 h at room temperature to ensure that the carrier was completely wetted. The obtained mixed solution was placed in a forced air drying oven for drying at 70 ° C for 10 h to obtain a 3Ni-N@SAPO-34 catalyst precursor with a Ni loading of 3:100 to the SAPO-34 carrier mass ratio, and the mixture was ground to 300 mesh for use.

[0064] 5. Take 2.0 g of the 3Ni-N@SAPO-34 catalyst precursor prepared in step 4 and place it in N 2 In the atmosphere tube furnace, control N 2 Flow rate: 2 mL min -1 , at 5℃·min -1 The heating rate was raised to 600 °C for 3 h, then cooled to 50 °C and switched to H 2 Atmosphere, H 2 Flow rate: 8 mL min -1 After calcination and reduction for 2 hours, it was cooled to room temperature and the powder was ground into 300 mesh to obtain 3Ni-N@SAPO-34 catalyst.

[0065] Example 5

[0066] A method for preparing Ni-N@SAPO-34 catalyst by recycling coal-based olefin waste SAPO-34, the specific process is as follows:

[0067] 1. Take 10.0 g of coal-based olefin waste SAPO-34 catalyst, place it in 300 mL of ammonia solution with pH>11, seal and heat with stirring at 90°C for 2 h, with a stirring speed of 2000 rpm, and then cool to room temperature to obtain a mixture.

[0068] 2. Centrifuge the mixture to obtain a solid. Collect the solid and wash it three times at room temperature. Dry it at 80°C for 2 hours to obtain a solid powder. Grind it to a size of less than 200 mesh for later use.

[0069] 3. Take 10.0g of the ground solid powder and place it in 150mL of an organic compound solvent. Extract it in a closed environment at room temperature for 30min. Then filter it, heat it to 60°C, and maintain it for 40min to remove the compound solvent to obtain an amorphous SAPO-34 with organic matter removed as a carrier for standby use.

[0070] 4. Take 2.0g urea and 0.52g Ni(NO 3 ) 2 6H 2 O was dissolved in 20 mL of deionized water, and after being completely dissolved at room temperature, 2 g of amorphous SAPO-34 carrier from which organic matter had been removed was added. After all the dissolution, the mixture was sealed and ultrasonicated for 1 h, and then the mixture was sealed and stirred for 3 h at room temperature to ensure that the carrier was completely wetted. The obtained mixed solution was placed in a forced air drying oven for drying at a temperature of 70° C. for 10 h to obtain a 5Ni-N@SAPO-34 catalyst precursor with a Ni loading of 5:100 to the SAPO-34 carrier mass ratio, and the mixture was ground to 300 mesh for use.

[0071] 5. Take 2.0 g of the 5Ni-N@SAPO-34 catalyst precursor prepared in step 4 and place it in N 2 In the atmosphere tube furnace, control N 2 Flow rate: 2 mL min -1 , at 5℃·min -1 The heating rate was raised to 600 °C for 3 h, then cooled to 50 °C and switched to H 2 Atmosphere, H 2 Flow rate: 8 mL min -1 After calcination and reduction for 2 hours, it was cooled to room temperature and the powder was ground into 300 mesh to obtain 5Ni-N@SAPO-34 catalyst.

[0072] Example 6

[0073] A method for preparing Ni-N@SAPO-34 catalyst by recycling coal-based olefin waste SAPO-34, the specific process is as follows:

[0074] 1. Take 10.0 g of coal-based olefin waste SAPO-34 catalyst, place it in 300 mL of ammonia solution with pH>11, seal and heat with stirring at 90°C for 2 h, with a stirring speed of 2000 rpm, and then cool to room temperature to obtain a mixture.

[0075] 2. Centrifuge the mixture to obtain a solid. Collect the solid and wash it three times at room temperature. Dry it at 80°C for 2 hours to obtain a solid powder. Grind it to a size of less than 200 mesh for later use.

[0076] 3. Take 10.0g of the ground solid powder and place it in 150mL of an organic compound solvent. Extract it in a closed environment at room temperature for 30min. Then filter it, heat it to 60°C, and maintain it for 40min to remove the compound solvent to obtain an amorphous SAPO-34 with organic matter removed as a carrier for standby use.

[0077] 4. Take 2.0g urea and 0.81g Ni(NO 3 ) 2 6H 2 O was dissolved in 20 mL of deionized water, and after being completely dissolved at room temperature, 2 g of amorphous SAPO-34 carrier from which organic matter had been removed was added. After all the dissolution, the mixture was sealed and ultrasonicated for 1 h, and then the mixture was sealed and stirred for 3 h at room temperature to ensure that the carrier was completely wetted. The obtained mixed solution was placed in a forced air drying oven for drying at 70 ° C for 10 h to obtain a 8Ni-N@SAPO-34 catalyst precursor with a Ni loading of 8:100 to the SAPO-34 carrier mass ratio, and the mixture was ground to 300 mesh for use.

[0078] 5. Take 2.0 g of 8Ni-N@SAPO-34 catalyst precursor prepared in step 4 and place it in N 2 In the atmosphere tube furnace, control N 2 Flow rate: 2 mL min -1 , at 5℃·min -1 The heating rate was raised to 600 °C for 3 h, then cooled to 50 °C and switched to H 2 Atmosphere, H 2 Flow rate: 8 mL min -1 After calcination and reduction for 2 hours, it was cooled to room temperature and the powder was ground into 300 mesh to obtain 8Ni-N@SAPO-34 catalyst.

[0079] Example 7

[0080] A method for preparing Ni-N@SAPO-34 catalyst by recycling coal-based olefin waste SAPO-34, the specific process is as follows:

[0081] 1. Take 10.0 g of coal-based olefin waste SAPO-34 catalyst, place it in 300 mL of ammonia solution with pH>11, seal and heat with stirring at 90°C for 2 h, with a stirring speed of 2000 rpm, and then cool to room temperature to obtain a mixture.

[0082] 2. Centrifuge the mixture to obtain a solid. Collect the solid and wash it three times at room temperature. Dry it at 80°C for 2 hours to obtain a solid powder. Grind it to a size of less than 200 mesh for later use.

[0083] 3. Take 10.0g of the ground solid powder and place it in 150mL of an organic compound solvent. Extract it in a closed environment at room temperature for 30min. Then filter it, heat it to 60°C, and maintain it for 40min to remove the compound solvent to obtain an amorphous SAPO-34 with organic matter removed as a carrier for standby use.

[0084] 4. Take 2.0g urea and 1.04g Ni(NO 3 ) 2 6H 2 O was dissolved in 20 mL of deionized water, and after being completely dissolved at room temperature, 2 g of amorphous SAPO-34 carrier from which organic matter had been removed was added. After all the dissolution, the mixture was sealed and ultrasonicated for 1 h, and then the mixture was sealed and stirred for 3 h at room temperature to ensure that the carrier was completely wetted. The obtained mixed solution was placed in a forced air drying oven for drying at 70 ° C for 10 h to obtain a 10Ni-N@SAPO-34 catalyst precursor with a Ni loading of 10:100 to the SAPO-34 carrier mass ratio, and the mixture was ground to 300 mesh for use.

[0085] 5. Take 2.0 g of the 10Ni-N@SAPO-34 catalyst precursor prepared in step 4 and place it in N 2 In the atmosphere tube furnace, control N 2 Flow rate: 2 mL min -1 , at 5℃·min -1 The heating rate was raised to 600 °C for 3 h, then cooled to 50 °C and switched to H 2 Atmosphere, H 2 Flow rate: 8 mL min -1 After calcination and reduction for 2 hours, it was cooled to room temperature and the powder was ground into 300 mesh to obtain 10Ni-N@SAPO-34 catalyst.

[0086] Application Example 1

[0087] The catalysts prepared in Examples 1 to 7 were respectively applied to the catalytic hydrogenation reaction of a polycyclic aromatic ring organic liquid model compound (toluene).

[0088] Reaction conditions: The catalysts were evaluated in a programmed temperature-controlled, high-pressure, mechanically stirred microreactor.

[0089] Taking toluene as a model compound, 0.05 g of catalyst, 0.1 g of toluene and 20.0 mL of n-hexane were added to a micro-autoclave in sequence, and the reaction conditions were: initial hydrogen pressure of 2.0 MPa, reaction temperature of 50°C, and reaction time of 20 min. This was used to evaluate the catalytic hydrogenation conversion capabilities of the catalysts of Examples 1 to 7.

[0090] Analysis method of hydrogenation products: Agilent 7890 / 5973 quadrupole gas chromatograph / mass spectrometer was used to analyze the composition of the catalytic hydrogenation conversion products in detail. The chromatographic column was a 60m×0.25mm×0.25μm HP-5MS capillary cross-linked column, and the data spectrum was the NIST20 spectrum library.

[0091] Under the same conditions, the catalytic hydrogenation conversion performance of toluene was evaluated, and the conversion rate of toluene and the molar yield of methylcyclohexane were obtained as shown in Table 1.

[0092] Table 1

[0093] Catalyst source Toluene conversion (mol%) Methylcyclohexane yield (mol%) Example 1 100 100 Example 2 32.1 32.1 Example 3 84.3 84.3 Example 4 76.9 76.9 Example 5 87.2 87.2 Example 6 95.6 95.6 Example 7 98.4 98.4

[0094] From the data shown in Table 1, it can be seen that in the evaluation of catalytic hydrogenation conversion of the model compound toluene, compared with 15Ni-N@SAPO-34-1, 15Ni-N@SAPO-34 loaded with the same amount of metal can effectively remove tar-like organic matter and improve the reaction efficiency by ultrasonic washing with a mixed solution of acetone and carbon disulfide. N doping loading can improve the electron transfer performance of metal Ni particles, improve the reaction activity and stability of the catalyst, and reduce side reactions. Comparing different loading amounts, 15Ni-N@SAPO-34 has more advantages. Under low temperature conditions, it can efficiently complete the efficient hydrogen storage of different polycyclic aromatic organic liquids. The reaction conditions are mild and the practical application prospects are broad.

[0095] Application Example 2

[0096] The catalysts prepared in Examples 1 to 7 were applied to the catalytic hydrogenation reaction of a polycyclic aromatic ring organic liquid model compound (1-methylnaphthalene).

[0097] Reaction conditions: The catalysts were evaluated in a programmed temperature-controlled, high-pressure, mechanically stirred microreactor.

[0098] Taking 1-methylnaphthalene as a model compound, 0.05 g of catalyst, 0.1 g of 1-methylnaphthalene and 20.0 mL of n-hexane were added to a micro-autoclave in sequence, and the reaction conditions were: initial hydrogen pressure of 3.0 MPa, reaction temperature of 80°C, and reaction time of 1.2 h. This was used to evaluate the catalytic hydrogenation conversion capabilities of the catalysts prepared in Examples 1 to 7.

[0099] Analysis method of hydrogenation products: Agilent 7890 / 5973 quadrupole gas chromatograph / mass spectrometer was used to analyze the composition of the catalytic hydrogenation conversion products in detail. The chromatographic column was a 60m×0.25mm×0.25μm HP-5MS capillary cross-linked column, and the data spectrum was the NIST20 spectrum library.

[0100] Under the same conditions, the catalytic hydrogenation conversion performance of 1-methylnaphthalene was evaluated, and the conversion rate of 1-methylnaphthalene and the molar yield of the product were obtained as shown in Table 2.

[0101] Table 2

[0102]

[0103] In Table 2 above, in the evaluation of catalytic hydrogenation conversion of the model compound 1-methylnaphthalene, 15Ni-N@SAPO-34 loaded with the same amount of metal was compared with 15Ni-N@SAPO-34-1. Ultrasonic washing with a mixed solution of acetone and carbon disulfide can effectively remove tar-like organic matter and improve reaction efficiency. N doping loading can improve the electron transfer performance of metal Ni particles, improve the reaction activity and stability of the catalyst, and reduce side reactions. In terms of different loading amounts, 15Ni-N@SAPO-34 has more advantages. Under low temperature conditions, it can efficiently complete the efficient hydrogen storage of different polycyclic aromatic organic liquids. The reaction conditions are mild and the practical application prospects are broad.

[0104] Application Example 3

[0105] The catalysts prepared in Examples 1 to 7 were applied to the catalytic hydrogenation reaction of a polycyclic aromatic ring organic liquid model compound (anthracene).

[0106] Reaction conditions: The catalysts were evaluated in a programmed temperature-controlled, high-pressure, mechanically stirred microreactor.

[0107] Taking 1-methylnaphthalene as a model compound, 0.05 g of catalyst, 0.1 g of anthracene and 20.0 mL of n-hexane were added to a micro-autoclave in sequence, and the reaction conditions were: initial hydrogen pressure of 5.0 MPa, reaction temperature of 100°C, and reaction time of 2 h. This was used to evaluate the catalytic hydrogenation conversion capabilities of the catalysts prepared in Examples 1 to 7.

[0108] Analysis method of hydrogenation products: Agilent 7890 / 5973 quadrupole gas chromatograph / mass spectrometer was used to analyze the composition of the catalytic hydrogenation conversion products in detail. The chromatographic column was a 60m×0.25mm×0.25μm HP-5MS capillary cross-linked column, and the data spectrum was the NIST20 spectrum library.

[0109] Under the same conditions, the catalytic hydrogenation conversion performance of anthracene was evaluated, and the conversion rate of anthracene and the molar yield of the product were obtained as shown in Table 3.

[0110] Table 3

[0111]

[0112] In Table 3 above, in the evaluation of the catalytic hydrogenation conversion of the model compound anthracene, 15Ni-N@SAPO-34 loaded with the same amount of metal was compared with 15Ni-N@SAPO-34-1. Ultrasonic washing with a mixed solution of acetone and carbon disulfide can effectively remove tar-like organic matter and improve the reaction efficiency. N doping loading can improve the electron transfer performance of metal Ni particles, improve the reaction activity and stability of the catalyst, and reduce side reactions. In terms of different loading amounts, 15Ni-N@SAPO-34 has more advantages. Under low temperature conditions, it can efficiently complete the efficient hydrogen storage of different polycyclic aromatic organic liquids. The reaction conditions are mild and the practical application prospects are broad.

[0113] The basic structural unit of the depolymerized SAPO-34 catalyst can be used in the organic liquid hydrogen storage system. By further loading non-precious metal Ni and doping N, a highly active Ni-N@SAPO-34 catalyst is developed, which can effectively improve the hydrogenation efficiency of organic liquids, reduce production costs, and reduce the disorderly emission of waste. This type of technology is in line with the concept of green environmental protection and sustainable anti-war, and has positive significance for promoting high-quality development in the energy field.

[0114] Of course, the above description is not a limitation of the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or substitutions made by technicians in this technical field within the essential scope of the present invention should also fall within the protection scope of the present invention.

Claims

1. A method for preparing Ni-N@SAPO-34 catalyst from coal-based olefin waste SAPO-34, characterized in that: The specific steps include: a. Pretreatment of spent SAPO-34 catalyst a1. The spent SAPO-34 catalyst is placed in an alkaline solution for directional depolymerization, sealed, heated, stirred, and then cooled to room temperature to obtain a mixture; a2. Centrifuge the mixture obtained in step a1, collect the solid matter, wash it multiple times at room temperature, dry it to obtain solid powder, and grind it for later use; a3. The solid powder obtained in step a2 is placed in an organic compound solvent, extracted under a closed environment at room temperature, and then subjected to ultrasonic washing, filtration, and heating to obtain an amorphous SAPO-34 carrier from which organic matter has been removed; b. Preparation of Ni-N@SAPO-34 catalyst precursor First, a certain amount of urea and Ni(NO3)2·6H2O are completely dissolved in deionized water, and then the amorphous SAPO-34 carrier obtained in step a3 is added, and a uniform mixed solution is obtained after sealing and ultrasonic treatment, and the mixture is continued to be stirred in a closed manner at room temperature to ensure that the carrier is completely wetted; after drying treatment, the Ni-N@SAPO-34 catalyst precursor is obtained, and the mixture is ground for standby use; c. Preparation of Ni-N@SAPO-34 catalyst c1. Place the Ni-N@SAPO-34 catalyst precursor obtained in step b2 in a tubular furnace and calcine it under a nitrogen atmosphere at 500-600°C for 2-3 hours; c2. After the temperature naturally drops to 50°C, H2 is introduced and the temperature is raised to 450-550°C to reduce the Ni-N@SAPO-34 catalyst precursor. After maintaining for 1-3 hours, the catalyst is naturally cooled to room temperature to obtain a Ni-N@SAPO-34 catalyst.

2. The method for preparing Ni-N@SAPO-34 catalyst from coal-based olefin waste SAPO-34 as claimed in claim 1, characterized in that: In step a1, the alkaline solution for directional depolymerization is aqueous ammonia or sodium hydroxide, pH>11, and the solid-liquid ratio of the waste SAPO-34 catalyst to the alkaline solution is 1:20-30; The sealing heating temperature is 80-90°C, the stirring time is 1-2h, and the rotation speed is 150-250rpm.

3. The method for preparing Ni-N@SAPO-34 catalyst from coal-based olefin waste SAPO-34 as claimed in claim 2, characterized in that: In step a2, washing is performed 3 times at room temperature, and the drying conditions are: temperature 80° C., time 2 h, and the solid powder is ground to less than 200 mesh.

4. The method for preparing Ni-N@SAPO-34 catalyst from coal-based olefin waste SAPO-34 as claimed in claim 3, characterized in that: In step a3, the solid-liquid ratio of the solid powder to the organic compound solvent is 1:5-15, and the organic compound solvent is prepared by acetone and carbon disulfide, and the volume ratio of the two is 1:1; The extraction time is 20-40 minutes, the ultrasonic washing time is 30 minutes, and the temperature is raised to 60°C and maintained for 40 minutes.

5. The method for preparing Ni-N@SAPO-34 catalyst from coal-based olefin waste SAPO-34 as claimed in claim 4, characterized in that: In step b, urea and Ni(NO3)2·6H2O, the mass ratio of the added amorphous SAPO-34 carrier to urea is 1:1, the Ni loading amount is 3-15wt%, the sealed ultrasonic time is 1-2h, and the sealed stirring time at room temperature is 2-3h; Drying conditions of Ni-N@SAPO-34 catalyst precursor: temperature 60-80°C, time 8-12h; The Ni-N@SAPO-34 catalyst precursor was ground to below 200 mesh.

6. The method for preparing Ni-N@SAPO-34 catalyst from coal-based olefin waste SAPO-34 as claimed in claim 5, characterized in that: In step c1, the N2 flow rate during the roasting process is controlled to be 2-4 mL min -1 , heating rate is 1-5℃·min -1 , 600oC maintenance time is 2h; In step c2, the H2 flow rate is controlled to be 5-8 mL min during the reduction process. -1 , heating rate is 1-5℃·min -1 .

7. Ni-N@SAPO-34 catalyst prepared by the method according to claim 6.

8. Use of the Ni-N@SAPO-34 catalyst as claimed in claim 7 in a polycyclic aromatic organic liquid hydrogen storage system.

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