Energy-saving catalyst carrier, energy-saving catalyst and preparation method thereof

Abstract

The present application discloses an energy-saving catalyst carrier, an energy-saving catalyst and a preparation method thereof, and relates to the field of catalyst materials. The energy-saving catalyst carrier comprises a boron nitride / silicon nitride composite porous material; the boron nitride / silicon nitride composite porous material is prepared by a template method; the energy-saving catalyst comprises an energy-saving catalyst carrier and an active ingredient; the active ingredient is loaded onto the energy-saving catalyst carrier by electrochemical reduction to prepare an energy-saving catalyst. The energy-saving catalyst can be used for industrial waste gas NO x It has high activity and obvious advantages of energy saving and environmental protection.

Description

Technical Field

[0001] The present application relates to the field of catalyst materials, specifically to an energy-saving catalyst carrier, an energy-saving catalyst and a preparation method thereof. Background Art

[0002] With the rapid advancement of industrialization and urbanization, energy consumption has increased dramatically. The combustion of traditional fossil fuels not only increases the risk of resource depletion, but also increases waste emissions, leading to serious environmental pollution. Therefore, the development of efficient, environmentally friendly, and energy-saving catalysts has become one of the key ways to address this problem.

[0003] Energy-saving catalysts can reduce energy consumption and waste emissions by lowering the activation energy of chemical reactions, increasing reaction rates and efficiency. These catalysts hold broad application prospects in a variety of fields, including but not limited to industrial catalysis, automobile exhaust treatment, and new energy development. For example, in automobile exhaust treatment, energy-saving catalysts can effectively reduce harmful gas emissions and alleviate air pollution. In new energy fields such as hydrogen energy and photocatalysis, energy-saving catalysts help improve energy conversion efficiency and promote the development of clean energy.

[0004] However, in current technical solutions, common energy-saving catalysts are mostly based on metal-based materials or silica, alumina, etc. as carriers, and rarely use non-metallic nitrides as carriers that have high hardness and wear resistance, high thermal stability and corrosion resistance and are very environmentally friendly.

[0005] Chinese patent publication number CN 112892547 A discloses a catalyst and preparation method for the simultaneous removal of nitrogen oxides and carbon monoxide. The catalyst is a supported catalyst, using γ-Al2O3 as a carrier and oxides of Mn, Cu, and Ce as active components. Metal salts of Mn, Cu, and Ce are prepared into a mixed salt solution in a specific ratio. The metal precursors are then uniformly loaded onto the surface of the γ-Al2O3 carrier under ultrasonic-assisted conditions. The supported catalyst is then dried and calcined to obtain the catalyst. The catalyst exhibits excellent NH3-SCR and CO oxidation performance under medium and low temperature conditions, enabling efficient removal of both nitrogen oxides and carbon monoxide. The catalyst preparation method is simple, low-cost, and highly applicable, making it widely applicable for flue gas treatment at the end of thermal power, steel, cement, ceramics, glass, and other industries.

[0006] However, the γ-alumina carrier used in the above scheme has weak performance in terms of stability and corrosion resistance. In addition, since the γ-alumina carrier does not have a porous structure, there are fewer sites where the catalyst can be loaded. Therefore, there is still much room for improvement in catalytic efficiency and energy-saving effects. Summary of the Invention

[0007] In response to the deficiencies in the prior art, the present application provides an energy-saving catalyst carrier, an energy-saving catalyst and a preparation method thereof with better catalytic efficiency, energy-saving effect, and stronger stability and corrosion resistance.

[0008] To achieve the above objectives, this application adopts the following technical solutions:

[0009] In a first aspect, the present application provides an energy-saving catalyst carrier, which includes a boron nitride / silicon nitride composite porous material; the boron nitride / silicon nitride composite porous material is prepared by a template method.

[0010] In a second aspect, the present application provides a method for preparing an energy-saving catalyst carrier, comprising the following steps:

[0011] Add the template, nitrogen source, boron source, silicon source and pure water into the reactor, start stirring, heat to 180-220°C, and keep the temperature to react for 48-72 hours;

[0012] After the reaction is completed, the temperature is naturally lowered to room temperature, the reaction product is filtered and washed with anhydrous ethanol, and then dried at 80-100°C for 1-2 hours to obtain product A;

[0013] Then, product A is placed in a tube furnace, heated from room temperature to 1200-1400°C at a heating rate of 5°C per minute under nitrogen, then kept at 1200-1400°C for 4-6 hours, and cooled to obtain product B.

[0014] Then, product B was soaked in hydrochloric acid with a concentration of 0.5-1.5 mol / L for 5-6 hours, ultrasonically stirred for 0.5-1 hour, and then filtered to obtain a solid substance, which was then washed three times with anhydrous ethanol;

[0015] Finally, the solid matter is dried at 100-120° C. for 6-8 hours, and cooled to obtain a boron nitride / silicon nitride composite porous material, namely the energy-saving catalyst carrier.

[0016] In a third aspect, the present application provides an energy-saving catalyst, which includes an active ingredient and the above-mentioned energy-saving catalyst carrier; the active ingredient includes copper and cobalt; the copper and cobalt are respectively derived from a copper-containing compound and a cobalt-containing compound; the copper and cobalt are loaded onto the boron nitride / silicon nitride composite porous material described in the first aspect by electrochemical reduction.

[0017] In a fourth aspect, the present application provides a method for preparing an energy-saving catalyst, comprising the following steps:

[0018] The energy-saving catalyst carrier is made into an electrode and connected to the negative electrode of a power supply; a copper-containing compound and a cobalt-containing compound are dissolved in pure water to obtain an electrolyte, and the pH range of the electrolyte is adjusted to 2 to 3; and the graphite electrode is connected to the positive electrode of the power supply;

[0019] Then, the power is turned on for 6 to 10 hours, and after the reaction is stopped, the energy-saving catalyst carrier is taken out and washed three times with pure water;

[0020] The cleaned energy-saving catalyst carrier is then dried at 140-160° C. for 1-3 hours under argon protection, calcined at 800-1000° C. for 6-8 hours under argon protection, and finally cooled naturally to room temperature to obtain the energy-saving catalyst.

[0021] Beneficial technical effects:

[0022] Unlike simply mixing boron nitride and silicon nitride in a physical manner, the present application uses a template method to disperse a template agent with a specific pore structure and a nitrogen source, a boron source, and a silicon source in a solution environment, so that the nitrogen source, the boron source, and the silicon source are filled into the pore structure of the template agent. Therefore, when the reaction occurs, the generated boron nitride and silicon nitride can be compounded together at a microscopic level and grown according to the morphology and size of the template agent pore structure, thereby producing a boron nitride / silicon nitride composite porous material. Boron nitride / silicon nitride composite porous materials have many pore structures and can therefore provide more sites for active ingredient loading. In this way, the active ingredient can be loaded more onto the boron nitride / silicon nitride composite porous material as a carrier, thereby greatly improving the catalytic efficiency of the catalyst and achieving energy-saving effects. Moreover, since boron nitride and silicon nitride are compounded together at the microscopic level, the resulting composite porous material has the advantages of high hardness and wear resistance, high thermal stability and corrosion resistance, which can enable the porous structure to exist for a long time without being destroyed, greatly extending the service life of the catalyst carrier and catalyst, and further improving the energy-saving effect.

[0023] In addition, unlike ordinary stirring and mixing, ultrasonic dispersion, solution impregnation and other methods, the active ingredients copper and cobalt used in this application are reduced to copper and cobalt in atomic form by electrochemical reduction, and then loaded onto electrodes made of boron nitride / silicon nitride composite porous material. When the electrochemical reduction reaction occurs, the current flows between the electrodes through the electrolyte solution. Since the distribution of current in the electrolyte is relatively uniform, the electron supply on the electrode made of boron nitride / silicon nitride composite porous material is also relatively uniform. This allows copper and cobalt to be more evenly and densely attached to the pore structure and surface of the boron nitride / silicon nitride composite porous material, and then through further high-temperature calcination under argon protection, the copper and cobalt remain in an atomic state and are more firmly bound to the pore structure and surface of the boron nitride / silicon nitride composite porous material. In this way, on the one hand, since the atomic form of copper and cobalt is directly exposed to the pore structure or surface of the carrier and participates in the reaction as catalytic active centers, the atomic utilization rate is very high, which can improve the catalytic efficiency of the catalyst; on the other hand, it can reduce the shedding of the loaded active components after a period of use, further increasing the service life of the catalyst, thereby achieving the purpose of further improving the energy-saving effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a schematic diagram of the structure of an energy-saving catalyst.

[0025] Figure 2 This is a flow chart for preparing energy-saving catalysts.

[0026] The meanings of the reference numerals are:

[0027] 1. Energy-saving catalyst carrier; 2. Active ingredient; 3. Porous structure. DETAILED DESCRIPTION

[0028] In order to make the technical problems, technical solutions and beneficial effects to be solved by this application more clearly understood, this application is further described in detail below with reference to the following embodiments. However, this should not be understood to limit the scope of this application to the following examples. Without departing from the above-mentioned method concept of this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0029] In this application, the terms used in this application are for the purpose of describing specific embodiments only and are not intended to be limiting of the application.

[0030] Figure 1In the structural schematic diagram of the energy-saving catalyst shown, the shapes and positions of the energy-saving catalyst, energy-saving catalyst carrier, porous structure and loaded active ingredients are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the energy-saving catalyst, energy-saving catalyst carrier, porous structure and loaded active ingredients must have specific shapes and positions, and therefore cannot be understood as a limitation on this application.

[0031] As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0032] In this application, the terms “first”, “second”, “third” and “fourth” are used for descriptive purposes only and should not be understood as indicating or implying relative importance.

[0033] In a first aspect, the present application provides an energy-saving catalyst carrier, which includes a boron nitride / silicon nitride composite porous material; the boron nitride / silicon nitride composite porous material is prepared by a template method.

[0034] In a second aspect, the present application provides a method for preparing an energy-saving catalyst carrier, comprising the following steps:

[0035] Add the template, nitrogen source, boron source, silicon source and pure water into the reactor, start stirring, heat to 180-220°C, and keep the temperature to react for 48-72 hours;

[0036] After the reaction is completed, the temperature is naturally lowered to room temperature, the reaction product is filtered and washed with anhydrous ethanol, and then dried at 80-100°C for 1-2 hours to obtain product A;

[0037] Then, product A is placed in a tube furnace, heated from room temperature to 1200-1400°C at a heating rate of 5°C per minute under nitrogen, then kept at 1200-1400°C for 4-6 hours, and cooled to obtain product B.

[0038] Then, product B was soaked in hydrochloric acid with a concentration of 0.5-1.5 mol / L for 5-6 hours, ultrasonically stirred for 0.5-1 hour, and then filtered to obtain a solid substance, which was then washed three times with anhydrous ethanol;

[0039] Finally, the solid matter is dried at 100-120° C. for 6-8 hours, and cooled to obtain a boron nitride / silicon nitride composite porous material, namely the energy-saving catalyst carrier.

[0040] A template with a specific pore structure and nitrogen, boron, and silicon sources are dispersed in a solution, allowing the nitrogen, boron, and silicon sources to fill the pores of the template. As a result, during the reaction, the boron nitride and silicon nitride formed can combine at a microscopic level and grow according to the morphology and size of the template's pore structure, thus producing a boron nitride / silicon nitride composite porous material.

[0041] Preferably, the template comprises a molecular sieve; the molecular sieve comprises one or more of MCM-41 molecular sieve, SBA-15 molecular sieve, SBA-16 molecular sieve and MSU-X molecular sieve.

[0042] Preferably, the nitrogen source comprises one or more of urea, melamine, biuret, ammonium chloride and ammonium nitrate.

[0043] Preferably, the boron source includes one or more of boric acid, boric anhydride and borax.

[0044] Preferably, the silicon source includes one or more of ethyl orthosilicate, butyl orthosilicate and silica sol.

[0045] Preferably, the mass ratio of the template, nitrogen source, boron source, silicon source and pure water is (5-10):(20-30):(10-20):(10-20):(40-50).

[0046] In the third aspect, the present application provides an energy-saving catalyst, which includes an active ingredient 2 and the above-mentioned energy-saving catalyst carrier 1; the surface of the energy-saving catalyst carrier 1 has a porous structure 3, and the active ingredient 2 includes copper and cobalt; the copper and cobalt are respectively derived from a copper-containing compound and a cobalt-containing compound; the copper and cobalt are loaded into the porous structure 3 on the surface of the energy-saving catalyst carrier 1 as described in the first aspect by electrochemical reduction. The structural diagram of the energy-saving catalyst is shown in FIG. Figure 1 shown.

[0047] Preferably, the copper-containing compound includes one or more of copper chloride, copper bromide, copper sulfate, copper acetate, and copper nitrate.

[0048] Preferably, the cobalt-containing compound includes one or more of cobalt chloride, cobalt sulfate, cobalt acetate, and cobalt nitrate.

[0049] In a fourth aspect, the present application provides a method for preparing an energy-saving catalyst, such as Figure 2 As shown, the following steps are included:

[0050] The energy-saving catalyst carrier is made into an electrode and connected to the negative electrode of a power supply; a copper-containing compound and a cobalt-containing compound are dissolved in pure water to obtain an electrolyte, and the pH range of the electrolyte is adjusted to 2 to 3; and the graphite electrode is connected to the positive electrode of the power supply;

[0051] Then, the power is turned on for 6 to 10 hours, and after the reaction is stopped, the energy-saving catalyst carrier is taken out and washed three times with pure water;

[0052] The cleaned energy-saving catalyst carrier is then dried at 140-160° C. for 1-3 hours under argon protection, calcined at 800-1000° C. for 6-8 hours under argon protection, and finally cooled naturally to room temperature to obtain the energy-saving catalyst.

[0053] Preferably, the mass ratio of the energy-saving catalyst carrier, the copper-containing compound, the cobalt-containing compound and pure water is (40-50): (5-10): (5-10): (40-50).

[0054] The experimental raw materials used in this application come from the following sources:

[0055] Pure water: homemade in the laboratory;

[0056] Anhydrous ethanol: Jiangsu Runfeng Synthetic Technology Co., Ltd.;

[0057] Copper-containing compounds: Shanghai MacLean Biochemical Technology Co., Ltd.;

[0058] Cobalt-containing compounds: Shanghai MacLean Biochemical Technology Co., Ltd.;

[0059] Template agent: Jiangsu Xianfeng Nanomaterial Technology Co., Ltd.

[0060] Nitrogen source: Jiangsu Runfeng Synthetic Technology Co., Ltd.;

[0061] Boron source: Jiangsu Runfeng Synthetic Technology Co., Ltd.;

[0062] Silicon source: Jiangsu Runfeng Synthetic Technology Co., Ltd.

[0063] γ-Alumina: Shanghai MacLean Biochemical Technology Co., Ltd.

[0064] The following will describe in detail an energy-saving catalyst carrier, energy-saving catalyst and preparation method thereof provided by the present application in combination with different examples.

[0065] Example 1:

[0066] like Figure 2 As shown, a method for preparing an energy-saving catalyst comprises:

[0067] First, prepare the energy-saving catalyst carrier, including the following steps:

[0068] 1. Add MCM-41 molecular sieve, urea, boric acid, ethyl orthosilicate and pure water into the reactor, start stirring, heat to 180°C, and keep the temperature for 72 hours;

[0069] 2. After the reaction is completed, the temperature is naturally lowered to room temperature, the reaction product is filtered and washed with anhydrous ethanol, and then dried at 80°C for 2 hours to obtain product A;

[0070] 3. Product A was then placed in a tube furnace and heated from room temperature to 1200°C at a heating rate of 5°C per minute under nitrogen, then kept at 1200°C for 6 hours, and cooled to obtain product B.

[0071] 4. Then, product B was soaked in 0.5 mol / L hydrochloric acid for 6 hours, ultrasonically stirred for 0.5 hours, and then filtered to obtain a solid substance, which was then washed three times with anhydrous ethanol;

[0072] 5. Finally, the solid matter was dried at 100° C. for 8 hours and cooled to obtain a boron nitride / silicon nitride composite porous material, namely the energy-saving catalyst carrier.

[0073] In the above steps 1 to 5, the mass ratio of the MCM-41 molecular sieve, urea, boric acid, ethyl orthosilicate and pure water is 10:25:10:10:45.

[0074] The energy-saving catalyst is then prepared, comprising the following steps:

[0075] 6. The prepared energy-saving catalyst carrier is made into an electrode and connected to the negative electrode of a power supply; a copper-containing compound and a cobalt-containing compound are dissolved in pure water to obtain an electrolyte, and the pH of the electrolyte is adjusted to 2; at the same time, the graphite electrode is connected to the positive electrode of the power supply;

[0076] 7. Then, the reaction was carried out for 10 hours. After the reaction was stopped, the energy-saving catalyst carrier was taken out and washed three times with pure water;

[0077] 8. The cleaned energy-saving catalyst carrier is then dried at 140° C. for 3 hours under argon protection, calcined at 1000° C. for 8 hours under argon protection, and finally cooled naturally to room temperature to obtain the energy-saving catalyst.

[0078] In the above steps 6 to 8, the mass ratio of the energy-saving catalyst carrier, copper sulfate, cobalt chloride and pure water is 40:5:5:50.

[0079] Example 2:

[0080] like Figure 2 As shown, a method for preparing an energy-saving catalyst comprises:

[0081] First, prepare the energy-saving catalyst carrier, including the following steps:

[0082] 1. Add SBA-15 molecular sieve, melamine, boric anhydride, butyl orthosilicate and pure water into the reactor, start stirring, heat to 220℃, and keep the temperature to react for 48 hours;

[0083] 2. After the reaction is completed, the temperature is naturally lowered to room temperature, the reaction product is filtered and washed with anhydrous ethanol, and then dried at 100°C for 1 hour to obtain product A;

[0084] 3. Product A was then placed in a tube furnace and heated from room temperature to 1400°C at a heating rate of 5°C per minute under nitrogen, then kept at 1400°C for 4 hours, and cooled to obtain product B.

[0085] 4. Then, product B was soaked in 1.5 mol / L hydrochloric acid for 5 hours, ultrasonically stirred for 1 hour, and then filtered to obtain a solid substance, which was then washed three times with anhydrous ethanol;

[0086] 5. Finally, the solid matter was dried at 120° C. for 6 hours and cooled to obtain a boron nitride / silicon nitride composite porous material, namely the energy-saving catalyst carrier.

[0087] In the above steps 1 to 5, the mass ratio of the SBA-15 molecular sieve, melamine, boric anhydride, butyl orthosilicate and pure water is 5:30:10:15:40.

[0088] The energy-saving catalyst is then prepared, comprising the following steps:

[0089] 6. The prepared energy-saving catalyst carrier is made into an electrode and connected to the negative electrode of a power supply; a copper-containing compound and a cobalt-containing compound are dissolved in pure water to obtain an electrolyte, and the pH of the electrolyte is adjusted to 3; and the graphite electrode is connected to the positive electrode of a power supply;

[0090] 7. Then, power on and react for 8 hours. After stopping the reaction, remove the energy-saving catalyst carrier and wash it three times with pure water;

[0091] 8. The cleaned energy-saving catalyst carrier is then dried at 160° C. for 1 hour under argon protection, calcined at 800° C. for 6 hours under argon protection, and finally cooled naturally to room temperature to obtain the energy-saving catalyst.

[0092] In the above steps 6 to 8, the mass ratio of the energy-saving catalyst carrier, copper chloride, cobalt sulfate and pure water is 45:10:5:40.

[0093] Example 3:

[0094] like Figure 2 As shown, a method for preparing an energy-saving catalyst comprises:

[0095] First, prepare the energy-saving catalyst carrier, including the following steps:

[0096] 1. Add SBA-16 molecular sieve, biuret, borax, silica sol and pure water into the reactor, start stirring, heat to 200℃, and keep the temperature to react for 60 hours;

[0097] 2. After the reaction is completed, the temperature is naturally lowered to room temperature, the reaction product is filtered and washed with anhydrous ethanol, and then dried at 90°C for 1.5 hours to obtain product A;

[0098] 3. Product A was then placed in a tube furnace and heated from room temperature to 1300°C at a heating rate of 5°C per minute under nitrogen, then kept at 1300°C for 5 hours, and cooled to obtain product B.

[0099] 4. Then, product B was soaked in 1 mol / L hydrochloric acid for 5.5 hours, ultrasonically stirred for 0.75 hours, and then filtered to obtain a solid substance, which was then washed three times with anhydrous ethanol;

[0100] 5. Finally, the solid matter was dried at 110° C. for 7 hours and cooled to obtain a boron nitride / silicon nitride composite porous material, namely the energy-saving catalyst carrier.

[0101] In the above steps 1 to 5, the mass ratio of the SBA-16 molecular sieve, biuret, borax, silica sol and pure water is 8:27:15:10:40.

[0102] The energy-saving catalyst is then prepared, comprising the following steps:

[0103] 6. The prepared energy-saving catalyst carrier is made into an electrode and connected to the negative electrode of a power supply; a copper-containing compound and a cobalt-containing compound are dissolved in pure water to obtain an electrolyte, and the pH of the electrolyte is adjusted to 2.5; and the graphite electrode is connected to the positive electrode of a power supply;

[0104] 7. Then, the power was turned on and the reaction was continued for 6 hours. After the reaction was stopped, the energy-saving catalyst carrier was taken out and washed three times with pure water;

[0105] 8. The cleaned energy-saving catalyst carrier is then dried at 150° C. for 2 hours under argon protection, calcined at 900° C. for 7 hours under argon protection, and finally cooled naturally to room temperature to obtain the energy-saving catalyst.

[0106] In steps 6 to 8 above, the mass ratio of the energy-saving catalyst carrier, copper acetate, cobalt acetate, and pure water is 40:8:8:44.

[0107] Example 4:

[0108] like Figure 2 As shown, a method for preparing an energy-saving catalyst comprises:

[0109] First, prepare the energy-saving catalyst carrier, including the following steps:

[0110] 1. Add MSU-X molecular sieve, ammonium chloride, boric anhydride, ethyl orthosilicate and pure water into the reactor, start stirring, heat to 190°C, and keep the temperature to react for 64 hours;

[0111] 2. After the reaction is completed, the temperature is naturally lowered to room temperature, the reaction product is filtered and washed with anhydrous ethanol, and then dried at 95°C for 1.5 hours to obtain product A;

[0112] 3. Product A was then placed in a tube furnace and heated from room temperature to 1250°C at a heating rate of 5°C per minute under nitrogen, then kept at 1250°C for 5.5 hours, and cooled to obtain product B.

[0113] 4. Then, product B was soaked in 0.75 mol / L hydrochloric acid for 5.5 hours, ultrasonically stirred for 1 hour, and then filtered to obtain a solid substance, which was then washed three times with anhydrous ethanol;

[0114] 5. Finally, the solid matter was dried at 110° C. for 7 hours and cooled to obtain a boron nitride / silicon nitride composite porous material, namely the energy-saving catalyst carrier.

[0115] In the above steps 1 to 5, the mass ratio of the MSU-X molecular sieve, ammonium chloride, boric anhydride, ethyl orthosilicate and pure water is 6:25:12:12:45.

[0116] The energy-saving catalyst is then prepared, comprising the following steps:

[0117] 6. The prepared energy-saving catalyst carrier is made into an electrode and connected to the negative electrode of a power supply; a copper-containing compound and a cobalt-containing compound are dissolved in pure water to obtain an electrolyte, and the pH of the electrolyte is adjusted to 2; at the same time, the graphite electrode is connected to the positive electrode of the power supply;

[0118] 7. Then, the power was turned on and the reaction was carried out for 9 hours. After the reaction was stopped, the energy-saving catalyst carrier was taken out and washed three times with pure water;

[0119] 8. The cleaned energy-saving catalyst carrier is then dried at 160° C. for 2 hours under argon protection, calcined at 950° C. for 6 hours under argon protection, and finally cooled naturally to room temperature to obtain the energy-saving catalyst.

[0120] In the above steps 6 to 8, the mass ratio of the energy-saving catalyst carrier, copper nitrate, cobalt sulfate and pure water is 42:6:6:46.

[0121] Example 5:

[0122] like Figure 2 As shown, a method for preparing an energy-saving catalyst comprises:

[0123] First, prepare the energy-saving catalyst carrier, including the following steps:

[0124] 1. Add SBA-15 molecular sieve, ammonium nitrate, borax, butyl orthosilicate and pure water into the reactor, start stirring, heat to 210℃, and keep the temperature to react for 68 hours;

[0125] 2. After the reaction is completed, the temperature is naturally lowered to room temperature, the reaction product is filtered and washed with anhydrous ethanol, and then dried at 85°C for 2 hours to obtain product A;

[0126] 3. Product A was then placed in a tube furnace and heated from room temperature to 1350°C at a heating rate of 5°C per minute under nitrogen, then kept at 1350°C for 5 hours, and cooled to obtain product B.

[0127] 4. Then, product B was soaked in 1.25 mol / L hydrochloric acid for 6 hours, ultrasonically stirred for 0.5 hours, and then filtered to obtain a solid substance, which was then washed three times with anhydrous ethanol;

[0128] 5. Finally, the solid matter was dried at 120° C. for 6 hours and cooled to obtain a boron nitride / silicon nitride composite porous material, namely the energy-saving catalyst carrier.

[0129] In the above steps 1 to 5, the mass ratio of the SBA-15 molecular sieve, ammonium nitrate, borax, butyl orthosilicate and pure water is 7:25:10:13:45.

[0130] The energy-saving catalyst is then prepared, comprising the following steps:

[0131] 6. The prepared energy-saving catalyst carrier is made into an electrode and connected to the negative electrode of a power supply; a copper-containing compound and a cobalt-containing compound are dissolved in pure water to obtain an electrolyte, and the pH of the electrolyte is adjusted to 3; and the graphite electrode is connected to the positive electrode of a power supply;

[0132] 7. Then, the power was turned on and the reaction was continued for 7 hours. After the reaction was stopped, the energy-saving catalyst carrier was taken out and washed three times with pure water;

[0133] 8. The cleaned energy-saving catalyst carrier is then dried at 140° C. for 3 hours under argon protection, calcined at 850° C. for 8 hours under argon protection, and finally cooled naturally to room temperature to obtain the energy-saving catalyst.

[0134] In the above steps 6 to 8, the mass ratio of the energy-saving catalyst carrier, copper bromide, cobalt chloride and pure water is 48:7:5:40.

[0135] Example 6:

[0136] like Figure 2As shown, a method for preparing an energy-saving catalyst comprises:

[0137] First, prepare the energy-saving catalyst carrier, including the following steps:

[0138] 1. Add MCM-41 molecular sieve, urea, boric acid, silica sol and pure water into the reactor, start stirring, heat to 220℃, and keep the temperature for 60 hours;

[0139] 2. After the reaction is completed, the temperature is naturally lowered to room temperature, the reaction product is filtered and washed with anhydrous ethanol, and then dried at 100°C for 1.5 hours to obtain product A;

[0140] 3. Product A was then placed in a tube furnace and heated from room temperature to 1400°C at a heating rate of 5°C per minute under nitrogen, then kept at 1400°C for 4 hours, and cooled to obtain product B.

[0141] 4. Then, product B was soaked in 1.5 mol / L hydrochloric acid for 5 hours, ultrasonically stirred for 1 hour, and then filtered to obtain a solid substance, which was then washed three times with anhydrous ethanol;

[0142] 5. Finally, the solid matter was dried at 100° C. for 8 hours and cooled to obtain a boron nitride / silicon nitride composite porous material, namely the energy-saving catalyst carrier.

[0143] In the above steps 1 to 5, the mass ratio of the MCM-41 molecular sieve, urea, boric acid, silica sol and pure water is 10:28:10:12:40.

[0144] The energy-saving catalyst is then prepared, comprising the following steps:

[0145] 6. The prepared energy-saving catalyst carrier is made into an electrode and connected to the negative electrode of a power supply; a copper-containing compound and a cobalt-containing compound are dissolved in pure water to obtain an electrolyte, and the pH of the electrolyte is adjusted to 2; at the same time, the graphite electrode is connected to the positive electrode of the power supply;

[0146] 7. Then, power on and react for 8 hours. After stopping the reaction, remove the energy-saving catalyst carrier and wash it three times with pure water;

[0147] 8. The cleaned energy-saving catalyst carrier is then dried at 150° C. for 3 hours under argon protection, calcined at 1000° C. for 7 hours under argon protection, and finally cooled naturally to room temperature to obtain the energy-saving catalyst.

[0148] In steps 6 to 8 above, the mass ratio of the energy-saving catalyst carrier, copper acetate, cobalt acetate, and pure water is 40:10:10:40.

[0149] Comparative Example 1:

[0150] A method for preparing an energy-saving catalyst, comprising:

[0151] 1. Make an electrode from γ-alumina and connect it to the negative electrode of the power supply; dissolve a copper-containing compound and a cobalt-containing compound in pure water to obtain an electrolyte, and adjust the pH of the electrolyte to 2; at the same time, connect the graphite electrode to the positive electrode of the power supply;

[0152] 2. Then, the reaction was continued for 10 hours. After the reaction was stopped, the γ-alumina was taken out and washed three times with pure water.

[0153] 3. The cleaned γ-alumina was then dried at 140° C. for 3 hours under argon protection, calcined at 1000° C. for 8 hours under argon protection, and finally cooled naturally to room temperature to obtain the energy-saving catalyst.

[0154] In the above steps 1 to 3, the mass ratio of the γ-alumina, the copper-containing compound, the cobalt-containing compound, and pure water is 40:5:5:50.

[0155] Comparative Example 2:

[0156] A method for preparing an energy-saving catalyst, comprising:

[0157] First, prepare the energy-saving catalyst carrier, including the following steps:

[0158] 1. Add SBA-16 molecular sieve, biuret, borax, silica sol and pure water into the reactor, start stirring, heat to 200℃, and keep the temperature to react for 60 hours;

[0159] 2. After the reaction is completed, the temperature is naturally lowered to room temperature, the reaction product is filtered and washed with anhydrous ethanol, and then dried at 90°C for 1.5 hours to obtain product A;

[0160] 3. Product A was then placed in a tube furnace and heated from room temperature to 1300°C at a heating rate of 5°C per minute under nitrogen, then kept at 1300°C for 5 hours, and cooled to obtain product B.

[0161] 4. Then, product B was soaked in 1 mol / L hydrochloric acid for 5.5 hours, ultrasonically stirred for 0.75 hours, and then filtered to obtain a solid substance, which was then washed three times with anhydrous ethanol;

[0162] 5. Finally, the solid matter was dried at 110° C. for 7 hours and cooled to obtain a boron nitride / silicon nitride composite porous material, namely the energy-saving catalyst carrier.

[0163] In the above steps 1 to 5, the mass ratio of the SBA-16 molecular sieve, biuret, borax, silica sol and pure water is 8:27:15:10:40.

[0164] The catalyst is then prepared, comprising the following steps:

[0165] 6. Mix the prepared energy-saving catalyst carrier, copper acetate, cobalt acetate and pure water together and stir under ultrasonication for 2 hours;

[0166] 7. Then stop stirring, filter to obtain the solid matter, and wash the solid matter three times with pure water;

[0167] 8. The cleaned solid material was then dried at 150° C. for 2 hours under argon protection, calcined at 900° C. for 7 hours under argon protection, and finally cooled naturally to room temperature to obtain the energy-saving catalyst.

[0168] In steps 6 to 8 above, the mass ratio of the energy-saving catalyst carrier, copper acetate, cobalt acetate, and pure water is 40:8:8:44.

[0169] Comparative Example 3:

[0170] A method for preparing an energy-saving catalyst, comprising:

[0171] 1. Mix γ-alumina, copper acetate, cobalt acetate and pure water together and stir under ultrasonication for 2 hours;

[0172] 2. Then stop stirring, filter to obtain the solid matter, and wash the solid matter three times with pure water;

[0173] 3. The cleaned solid material was then dried at 150° C. for 3 hours under argon protection, then calcined at 1000° C. for 7 hours under argon protection, and finally naturally cooled to room temperature to obtain the energy-saving catalyst.

[0174] In the above steps 1 to 3, the mass ratio of the γ-alumina, copper acetate, cobalt acetate and pure water is 40:10:10:40.

[0175] Referring to GB / T 38219-2019, the catalytic denitrification efficiency of the prepared energy-saving catalyst was tested; and the wear strength of the prepared energy-saving catalyst was tested using a rotary abrasion tester.

[0176] Table 1 Performance test results of energy-saving catalysts prepared in Examples 1 to 6 and Comparative Examples 1 to 3

[0177] Catalytic denitrification efficiency (%) Wear strength (mg / 100U) Example 1 95.3 37 Example 2 94.1 41 Example 3 96.4 42 Example 4 95.5 36 Example 5 94.7 35 Example 6 97.2 39 Comparative Example 1 56.7 143 Comparative Example 2 72.2 46 Comparative Example 3 43.1 152

[0178] As shown in Table 1, the catalytic denitrification efficiency and wear strength of Examples 1 to 6 are superior to those of Comparative Examples 1 to 3. This is because in Examples 1 to 6 of the present application, the active ingredients copper and cobalt are loaded onto the boron nitride / silicon nitride composite porous material prepared by the template method through electrochemical reduction.

[0179] In Examples 1 to 6, a template having a specific pore structure and a nitrogen source, a boron source, and a silicon source are dispersed in a solution environment, so that the nitrogen source, the boron source, and the silicon source are filled into the pore structure of the template. Therefore, when the reaction occurs, the generated boron nitride and silicon nitride can be compounded together at the microscopic level and grow according to the morphology and size of the pore structure of the template, thereby producing a boron nitride / silicon nitride composite porous material. Since the boron nitride / silicon nitride composite porous material has a large number of porous structures, it can provide more sites for active ingredient loading. In this way, the active ingredient can be loaded more onto the boron nitride / silicon nitride composite porous material as a carrier, thereby greatly improving the catalytic efficiency of the catalyst and achieving energy-saving effects. Moreover, since boron nitride and silicon nitride are compounded together at the microscopic level, the composite porous material obtained has the advantages of high hardness and wear resistance, high thermal stability and corrosion resistance, and can make the porous structure exist for a long time without being destroyed, greatly extending the service life of the catalyst carrier and the catalyst, and further improving the energy-saving effect.

[0180] In addition, in Examples 1 to 6, copper and cobalt in cationic form are reduced to atomic copper and cobalt by electrochemical reduction and then loaded onto electrodes made of boron nitride / silicon nitride composite porous material. When the electrochemical reduction reaction occurs, current flows between the electrodes through the electrolyte solution. Since the current is relatively evenly distributed in the electrolyte, the electron supply on the electrode made of the boron nitride / silicon nitride composite porous material is also relatively even, allowing copper and cobalt to be more evenly and densely attached to the pore structure and surface of the boron nitride / silicon nitride composite porous material. Further high-temperature calcination under argon protection allows copper and cobalt to remain in an atomic state and more firmly bound to the pore structure and surface of the boron nitride / silicon nitride composite porous material. In this way, on the one hand, since the atomic copper and cobalt are directly exposed to the pore structure or surface of the carrier and participate in the reaction as catalytic active centers, the atomic utilization rate is very high, thereby improving the catalytic efficiency of the catalyst; on the other hand, it can reduce the shedding of the loaded active components after a period of use, further improving the service life of the catalyst, thereby achieving the purpose of further improving the energy saving effect.

[0181] In Comparative Example 1, γ-alumina is used as a carrier, which does not have a porous structure, and has low hardness, wear resistance, etc., so the catalytic denitrification efficiency and wear strength are inferior to those of Examples 1 to 6; in Comparative Example 2, the active ingredients are not loaded onto the boron nitride / silicon nitride composite porous material by electrochemical reduction, but are simply stirred and mixed under ultrasound, so the catalytic denitrification efficiency is low compared to Examples 1 to 6, and the wear strength is equivalent to that of Examples 1 to 6; in Comparative Example 3, γ-alumina is used as a carrier and the active ingredients are not loaded onto the boron nitride / silicon nitride composite porous material by electrochemical reduction, so its catalytic denitrification efficiency and wear strength are the worst.

[0182] The above results show and describe the basic principles and main features of this application as well as the advantages of this application.

[0183] Those skilled in the art should understand that the present application is not limited to the above-described embodiments. The above-described embodiments and descriptions are merely illustrative of the principles of the present application. Various changes and improvements may be made to the present application without departing from the spirit and scope of the present application. Such changes and improvements are intended to fall within the scope of the present application. The scope of protection claimed in the present application is defined by the equivalents of the appended claims.

Claims

1. Application of an energy-saving catalyst in catalytic denitration, characterized in that: The energy-saving catalyst includes an active component and an energy-saving catalyst carrier; the active component includes copper and cobalt; the energy-saving catalyst carrier includes a boron nitride / silicon nitride composite porous material; the boron nitride / silicon nitride composite porous material is prepared by a template method; the preparation method of the energy-saving catalyst carrier includes the following steps: Add the template, nitrogen source, boron source, silicon source and pure water into the reactor, start stirring, heat to 180-220℃, and keep the temperature to react for 48-72 hours; After the reaction is completed, the temperature is naturally lowered to room temperature, the reaction product is filtered and washed with anhydrous ethanol, and then dried at 80-100°C for 1-2 hours to obtain product A; Then, product A is placed in a tube furnace and heated from room temperature to 1200-1400°C at a heating rate of 5°C per minute under nitrogen, then kept at 1200-1400°C for 4-6 hours, and cooled to obtain product B. Then, product B was soaked in 0.5-1.5 mol / L hydrochloric acid for 5-6 hours, ultrasonically stirred for 0.5-1 hour, and then filtered to obtain a solid substance, which was then washed three times with anhydrous ethanol; Finally, the solid matter is dried at 100-120° C. for 6-8 hours, and cooled to obtain a boron nitride / silicon nitride composite porous material, namely the energy-saving catalyst carrier; The template includes molecular sieves; the molecular sieves include one or more of MCM-41 molecular sieves, SBA-15 molecular sieves, SBA-16 molecular sieves and MSU-X molecular sieves.

2. Use of an energy-saving catalyst in catalytic denitration according to claim 1, characterized in that: The mass ratio of the template, nitrogen source, boron source, silicon source and pure water is (5-10): (20-30): (10-20): (10-20): (40-50); the nitrogen source includes one or more of urea, melamine, biuret, ammonium chloride and ammonium nitrate; the boron source includes one or more of boric acid, boric anhydride and borax; and the silicon source includes one or more of ethyl orthosilicate, butyl orthosilicate and silica sol.

3. The use of an energy-saving catalyst in catalytic denitration according to claim 1, characterized in that: The copper and cobalt are respectively derived from a copper-containing compound and a cobalt-containing compound; the copper and cobalt are loaded onto an energy-saving catalyst carrier by electrochemical reduction.

4. Use of an energy-saving catalyst in catalytic denitration according to claim 3, characterized in that: The copper-containing compound includes one or more of copper chloride, copper bromide, copper sulfate, copper acetate, and copper nitrate; the cobalt-containing compound includes one or more of cobalt chloride, cobalt sulfate, cobalt acetate, and cobalt nitrate.

5. Use of an energy-saving catalyst in catalytic denitration according to claim 4, characterized in that: The preparation method of the energy-saving catalyst comprises: The energy-saving catalyst carrier is made into an electrode and connected to the negative electrode of a power supply; a copper-containing compound and a cobalt-containing compound are dissolved in pure water to obtain an electrolyte, and the pH range of the electrolyte is adjusted to 2-3; and the graphite electrode is connected to the positive electrode of the power supply; Then, the reaction was continued for 6 to 10 hours. After the reaction was stopped, the energy-saving catalyst carrier was taken out and washed three times with pure water. The cleaned energy-saving catalyst carrier is then dried at 140-160° C. for 1-3 hours under argon protection, calcined at 800-1000° C. for 6-8 hours under argon protection, and finally cooled naturally to room temperature to obtain the energy-saving catalyst.

6. Use of an energy-saving catalyst in catalytic denitration according to claim 5, characterized in that: The mass ratio of the energy-saving catalyst carrier, the copper-containing compound, the cobalt-containing compound and pure water is (40-50): (5-10): (5-10): (40-50).

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