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

Abstract

The invention discloses an energy-saving catalyst carrier, an energy-saving catalyst and a preparation method thereof, and relates to the field of catalyst materials. Wherein 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 component; the active components are loaded on the energy-saving catalyst carrier in an electrochemical reduction manner to prepare the energy-saving catalyst. The energy-saving catalyst can be used for treating industrial waste gas NOx, has higher activity and has obvious energy-saving and environment-friendly advantages.

Description

Technical Field

[0001] This application relates to the field of catalyst materials, and 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 sharply. The combustion of traditional fossil fuels not only exacerbates the risk of resource depletion but also increases waste emissions, thereby causing serious environmental pollution problems. Therefore, developing efficient and environmentally friendly energy-saving catalysts has become one of the key ways to solve this problem.

[0003] Energy-saving catalysts can reduce the activation energy of chemical reactions, improve reaction rates and efficiencies, thereby reducing energy consumption and waste emissions. Such catalysts show broad application prospects in multiple fields, including but not limited to industrial catalysis, automotive exhaust treatment, new energy development, etc. For example, in automotive exhaust treatment, energy-saving catalysts can effectively reduce harmful gas emissions and reduce air pollution; in the new energy field, 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 mostly use metal-based materials or silica, alumina, etc. as carriers, and less use non-metallic nitrides with high hardness, wear resistance, high thermal stability, corrosion resistance, and being very environmentally friendly as carriers.

[0005] Chinese Patent with Publication No. CN 112892547 A discloses a catalyst for simultaneously removing nitrogen oxides and carbon monoxide and a preparation method thereof. The catalyst is a supported catalyst, using γ-Al 2 O 3 as the carrier and oxides of Mn, Cu, and Ce as the active components. The metal salts of Mn, Cu, and Ce are made into a mixed salt solution according to a certain ratio, and the metal precursors are uniformly loaded on the surface of the γ-Al 2 O 3 carrier under ultrasonic assistance. After drying and calcination, a supported catalyst is obtained. The catalyst has excellent NH 3 -SCR and CO oxidation performance under medium and low temperature conditions, and can simultaneously achieve efficient removal of nitrogen oxides and carbon monoxide. The preparation method of this catalyst is simple, with low cost and strong applicability, and can be widely used in flue gas treatment at the end of industries such as thermal power, steel, cement, ceramics, and glass.

[0006] However, in the above - mentioned solution, the performance of the γ - alumina support in terms of stability and corrosion resistance is weak. And since the γ - alumina support does not have a porous structure, there are fewer sites where the catalyst can be loaded. Therefore, there is still a large room for improvement in catalytic efficiency, energy - saving effect, etc. Summary of the Invention

[0007] In view of the deficiencies of the prior art, the present application provides an energy - saving catalyst support, an energy - saving catalyst and a preparation method thereof, which have better catalytic efficiency and energy - saving effect, and stronger stability and corrosion resistance, etc.

[0008] To achieve the above object, the present application adopts the following technical solutions:

[0009] In the first aspect, the present application provides an energy - saving catalyst support, and the energy - saving catalyst support 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 the second aspect, the present application provides a preparation method of an energy - saving catalyst support, including the following steps:

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

[0012] After the reaction ends, naturally cool to room temperature, filter the reaction product and wash it with absolute ethanol, and then dry it at 80 - 100 °C for 1 - 2 hours to obtain product A;

[0013] Then place product A in a tubular furnace, and heat from room temperature to 1200 - 1400 °C at a heating rate of 5 °C per minute under nitrogen, and then keep the temperature at 1200 - 1400 °C for 4 - 6 hours, and cool and discharge to obtain product B;

[0014] Then soak product B in hydrochloric acid with a concentration of 0.5 - 1.5 mol / L for 5 - 6 hours, stir ultrasonically for 0.5 - 1 hour, then filter to obtain a solid substance, and then wash the solid substance three times with absolute ethanol;

[0015] Finally, dry the solid substance at 100 - 120 °C for 6 - 8 hours, and after cooling, obtain a boron nitride / silicon nitride composite porous material, that is, the energy - saving catalyst support.

[0016] In the third aspect, the present application provides an energy - saving catalyst, and the energy - saving catalyst includes an active ingredient and the above - mentioned energy - saving catalyst support; the active ingredient includes copper and cobalt; the copper and cobalt respectively come 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 an electrochemical reduction method.

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

[0018] Fabricate the energy-saving catalyst support into an electrode and connect it to the negative electrode of a power supply; dissolve a copper-containing compound and a cobalt-containing compound in pure water to obtain an electrolyte solution, and adjust the pH range of the electrolyte solution to 2-3; simultaneously connect a graphite electrode to the positive electrode of the power supply;

[0019] Subsequently, conduct an electrolytic reaction for 6-10 hours. After stopping the reaction, take out the energy-saving catalyst support and wash it three times with pure water;

[0020] Then dry the washed energy-saving catalyst support at 140-160°C for 1-3 hours under argon protection, calcine it at 800-1000°C for 6-8 hours under argon protection, and finally cool it naturally to room temperature to obtain the energy-saving catalyst.

[0021] Advantageous technical effects:

[0022] Different from simply mixing boron nitride and silicon nitride physically, in the present application, by means of the template method, a templating agent with a specific pore structure, a nitrogen source, a boron source, and a silicon source are dispersed in a solution environment, such that the nitrogen source, the boron source, and the silicon source are filled into the pore structure of the templating agent. Therefore, during the reaction, 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 templating agent, thereby producing a boron nitride / silicon nitride composite porous material. Due to the presence of many pore structures in the boron nitride / silicon nitride composite porous material, more sites for loading active components can be provided. In this way, more active components can be loaded onto the boron nitride / silicon nitride composite porous material serving as a support, thereby greatly improving the catalytic efficiency of the catalyst and achieving an energy-saving effect. Moreover, since boron nitride and silicon nitride are compounded together at the microscopic level, the prepared composite porous material has advantages such as 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 damaged, greatly prolonging the service life of the catalyst support and the catalyst, and further enhancing the energy-saving effect.

[0023] In addition, different from ordinary methods such as stirring and mixing, ultrasonic dispersion, and solution impregnation, the active ingredients copper and cobalt used in this application are reduced from the cationic form of copper and cobalt to the atomic form of copper and cobalt by means of electrochemical reduction and then loaded onto the electrodes made of boron nitride / silicon nitride composite porous materials. When the electrochemical reduction reaction occurs, an electric current flows between the electrodes through the electrolyte solution. Since the distribution of the electric current in the electrolyte solution is relatively uniform, the electron supply on the electrodes made of boron nitride / silicon nitride composite porous materials is also relatively uniform. This enables copper and cobalt to adhere more uniformly and densely within the pore structure of the boron nitride / silicon nitride composite porous materials and on their surfaces. Through further high-temperature calcination under argon protection, copper and cobalt are maintained in the atomic state and more firmly bonded within the pore structure of the boron nitride / silicon nitride composite porous materials and on their surfaces. In this way, on the one hand, since the atomic forms of copper and cobalt are directly exposed in the pore structure or on the surface of the carrier and participate in the reaction as catalytic active centers, the atomic utilization rate is very high, thus improving the catalytic efficiency of the catalyst; on the other hand, it can reduce the shedding of the loaded active ingredients after being used for a period of time, further improving the service life of the catalyst, thereby achieving the purpose of further enhancing the energy-saving effect. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0025] Figure 2 is a flow chart for preparing an energy-saving catalyst.

[0026] The meanings of the reference numerals are as follows:

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

[0028] In order to make the technical problems, technical solutions, and beneficial effects to be solved by this application clearer and more understandable, the following further details this application in combination with embodiments. However, it should not be understood that the scope of this application is limited to the following examples. Without departing from the above method concept of this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of this application.

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

[0030] Figure 1In the schematic structural diagram of the energy-saving catalyst shown, the shapes and positions of the energy-saving catalyst, the energy-saving catalyst support, the porous structure, and the loaded active components are only for the convenience of describing the present application and simplifying the description, rather than indicating or implying that the energy-saving catalyst, the energy-saving catalyst support, the porous structure, and the loaded active components must have specific shapes and positions. Therefore, it should not be construed as a limitation to the present application.

[0031] As used in the present application and the appended claims, the singular forms "a" and "the" are intended to include the plural forms unless the context clearly dictates otherwise.

[0032] In the present application, when terms such as "first", "second", "third", and "fourth" appear, they are only for descriptive purposes and should not be construed as indicating or implying relative importance.

[0033] In a first aspect, the present application provides an energy-saving catalyst support, and the energy-saving catalyst support 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 support, including the following steps:

[0035] Add a templating agent, a nitrogen source, a boron source, a silicon source, and pure water into a reaction kettle, start stirring, heat to 180-220 °C, and keep the reaction at this temperature for 48-72 hours;

[0036] After the reaction is completed, naturally cool to room temperature, filter the reaction product and wash it with absolute ethanol, and then dry it at 80-100 °C for 1-2 hours to obtain product A;

[0037] Then place product A in a tube furnace, heat from room temperature to 1200-1400 °C at a heating rate of 5 °C per minute under nitrogen, then keep the temperature at 1200-1400 °C for 4-6 hours, and cool and discharge to obtain product B;

[0038] Then soak product B in hydrochloric acid with a concentration of 0.5-1.5 mol / L for 5-6 hours, stir ultrasonically for 0.5-1 hour, then filter to obtain a solid substance, and then wash the solid substance three times with absolute ethanol;

[0039] Finally, dry the solid substance at 100-120 °C for 6-8 hours, and after cooling, obtain the boron nitride / silicon nitride composite porous material, that is, the energy-saving catalyst support.

[0040] A templating agent with a specific pore structure, a nitrogen source, a boron source, and a silicon source are dispersed in a solution environment, such that the nitrogen source, the boron source, and the silicon source are filled into the pore structure of the templating agent. 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 templating agent, thereby producing a boron nitride / silicon nitride composite porous material.

[0041] Preferably, the templating agent includes a molecular sieve; the molecular sieve includes 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 includes 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 tetraethyl orthosilicate, tetrabutyl orthosilicate, and silica sol.

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

[0046] In a 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 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 means of electrochemical reduction. The structural schematic diagram of the energy-saving catalyst is as 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 preparation method of an energy-saving catalyst, as Figure 2 shown, which includes the following steps:

[0050] Making the energy-saving catalyst carrier into an electrode and connecting it to the negative electrode of the power supply; dissolving the copper-containing compound and the cobalt-containing compound in pure water to obtain an electrolyte solution, and adjusting the pH range of the electrolyte solution to 2-3; at the same time, connecting a graphite electrode to the positive electrode of the power supply;

[0051] Subsequently, power on the reaction for 6 - 10 hours. After stopping the reaction, take out the energy-saving catalyst support and wash it three times with pure water;

[0052] Then dry the washed energy-saving catalyst support at 140 - 160 °C for 1 - 3 hours under argon protection, calcine it at 800 - 1000 °C for 6 - 8 hours under argon protection, and finally cool it naturally to room temperature to obtain the energy-saving catalyst.

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

[0054] The sources of the experimental raw materials used in this application are as follows:

[0055] Pure water: Self-made in the laboratory;

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

[0057] Copper-containing compound: Shanghai Macklin Biochemical Co., Ltd.;

[0058] Cobalt-containing compound: Shanghai Macklin Biochemical Co., Ltd.;

[0059] Template agent: Jiangsu Xianfeng Nano Materials 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-aluminum oxide: Shanghai Macklin Biochemical Co., Ltd.

[0064] The following will specifically describe an energy-saving catalyst support, an energy-saving catalyst, and a preparation method thereof provided by this application in combination with different examples.

[0065] Example 1:

[0066] As Figure 2 shown, a preparation method of an energy-saving catalyst, the preparation method includes:

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

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

[0069] 2. After the reaction is completed, naturally cool to room temperature, filter the reaction product by suction and wash it with absolute ethanol, and then dry it at 80 °C for 2 hours to obtain product A;

[0070] 3. Then place product A in a tubular furnace, and under nitrogen, heat it from room temperature to 1200 °C at a heating rate of 5 °C per minute, then keep it at 1200 °C for 6 hours, and cool and discharge to obtain product B;

[0071] 4. Then soak product B in hydrochloric acid with a concentration of 0.5 mol / L for 6 hours, stir ultrasonically for 0.5 hours, then filter by suction to obtain a solid substance, and then wash the solid substance three times with absolute ethanol;

[0072] 5. Finally, dry the solid substance at 100 °C for 8 hours, and after cooling, obtain the boron nitride / silicon nitride composite porous material, that is, the energy-saving catalyst carrier.

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

[0074] Next, prepare the energy-saving catalyst, including the following steps:

[0075] 6. Make the prepared energy-saving catalyst carrier into an electrode and connect it to the negative electrode of the power supply; dissolve the copper-containing compound and the cobalt-containing compound in pure water to obtain an electrolyte solution, and adjust the pH of the electrolyte solution to 2; at the same time, connect the graphite electrode to the positive electrode of the power supply;

[0076] 7. Then, conduct an electric reaction for 10 hours. After stopping the reaction, take out the energy-saving catalyst carrier and wash it three times with pure water;

[0077] 8. Then dry the washed energy-saving catalyst carrier at 140 °C for 3 hours under argon protection, calcine it at 1000 °C for 8 hours under argon protection, and finally naturally cool to room temperature to obtain the energy-saving catalyst.

[0078] In the above steps 6-8, 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] As Figure 2 shown, a preparation method of an energy-saving catalyst, the preparation method includes:

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

[0082] 1. Add SBA-15 molecular sieve, melamine, boric anhydride, tetrabutyl orthosilicate and pure water into a reaction kettle, start stirring, heat to 220 °C, and keep the reaction for 48 hours;

[0083] 2. After the reaction is completed, naturally cool to room temperature, filter the reaction product and wash it with absolute ethanol, and then dry it at 100 °C for 1 hour to obtain product A;

[0084] 3. Then place product A in a tubular furnace, and heat from room temperature to 1400 °C at a heating rate of 5 °C per minute under nitrogen, then keep the temperature at 1400 °C for 4 hours, and cool and discharge to obtain product B;

[0085] 4. Then soak product B in hydrochloric acid with a concentration of 1.5 mol / L for 5 hours, stir ultrasonically for 1 hour, then filter to obtain a solid substance, and then wash the solid substance three times with absolute ethanol;

[0086] 5. Finally, dry the solid substance at 120 °C for 6 hours, and after cooling, obtain a boron nitride / silicon nitride composite porous material, that is, the energy-saving catalyst carrier.

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

[0088] Next, prepare an energy-saving catalyst, including the following steps:

[0089] 6. Make the prepared energy-saving catalyst carrier into an electrode and connect it to the negative electrode of the power supply; dissolve the copper-containing compound and cobalt-containing compound in pure water to obtain an electrolyte solution, and adjust the pH of the electrolyte solution to 3; at the same time, connect the graphite electrode to the positive electrode of the power supply;

[0090] 7. Then, conduct an electric reaction for 8 hours, take out the energy-saving catalyst carrier after the reaction stops, and wash it three times with pure water;

[0091] 8. Then dry the washed energy-saving catalyst carrier at 160 °C for 1 hour under argon protection, calcine it at 800 °C for 6 hours under argon protection, and finally naturally cool to room temperature to obtain the energy-saving catalyst.

[0092] In the above steps 6-8, 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] As Figure 2 shown, a preparation method of an energy-saving catalyst, the preparation method includes:

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

[0096] 1. Add SBA-16 molecular sieve, biuret, borax, silica sol and pure water into a reaction kettle, start stirring, heat to 200 °C, and keep the reaction for 60 hours;

[0097] 2. After the reaction is completed, naturally cool to room temperature, filter the reaction product and wash it with absolute ethanol, and then dry it at 90 °C for 1.5 hours to obtain product A;

[0098] 3. Then place product A in a tubular furnace, and heat from room temperature to 1300 °C at a heating rate of 5 °C per minute under nitrogen, then keep the temperature at 1300 °C for 5 hours, and cool and discharge to obtain product B;

[0099] 4. Then soak product B in hydrochloric acid with a concentration of 1 mol / L for 5.5 hours, stir ultrasonically for 0.75 hours, then filter to obtain solid matter, and then wash the solid matter three times with absolute ethanol;

[0100] 5. Finally, dry the solid matter at 110 °C for 7 hours, and after cooling, obtain the boron nitride / silicon nitride composite porous material, that is, the energy-saving catalyst carrier.

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

[0102] Next, prepare the energy-saving catalyst, including the following steps:

[0103] 6. Make the prepared energy-saving catalyst carrier into an electrode and connect it to the negative electrode of the power supply; dissolve the copper-containing compound and cobalt-containing compound in pure water to obtain an electrolyte solution, and adjust the pH of the electrolyte solution to 2.5; at the same time, connect the graphite electrode to the positive electrode of the power supply;

[0104] 7. Then conduct the reaction by power supply for 6 hours. After stopping the reaction, take out the energy-saving catalyst carrier and wash it three times with pure water;

[0105] 8. Then dry the washed energy-saving catalyst carrier at 150 °C for 2 hours under argon protection, calcine it at 900 °C for 7 hours under argon protection, and finally naturally cool to room temperature to obtain the energy-saving catalyst.

[0106] In the above steps 6-8, 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] As Figure 2 shown, a preparation method of an energy-saving catalyst, the preparation method includes:

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

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

[0111] 2. After the reaction, naturally cool to room temperature, filter the reaction product and wash it with absolute ethanol, and then dry it at 95 °C for 1.5 hours to obtain product A;

[0112] 3. Then place product A in a tubular furnace, and heat it from room temperature to 1250 °C at a heating rate of 5 °C per minute under nitrogen, and then keep it at 1250 °C for 5.5 hours, and cool and discharge to obtain product B;

[0113] 4. Then soak product B in hydrochloric acid with a concentration of 0.75 mol / L for 5.5 hours, stir ultrasonically for 1 hour, filter to obtain solid matter, and then wash the solid matter three times with absolute ethanol;

[0114] 5. Finally, dry the solid matter at 110 °C for 7 hours, and after cooling, obtain a boron nitride / silicon nitride composite porous material, that is, the energy-saving catalyst support.

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

[0116] Next, prepare an energy-saving catalyst, including the following steps:

[0117] 6. Make the prepared energy-saving catalyst support into an electrode and connect it to the negative electrode of the power supply; dissolve copper-containing compounds and cobalt-containing compounds in pure water to obtain an electrolyte solution, and adjust the pH of the electrolyte solution to 2; at the same time, connect a graphite electrode to the positive electrode of the power supply;

[0118] 7. Then conduct an electric reaction for 9 hours, stop the reaction, take out the energy-saving catalyst support, and wash it three times with pure water;

[0119] 8. Then dry the washed energy-saving catalyst support at 160 °C for 2 hours under argon protection, calcine it at 950 °C for 6 hours under argon protection, and finally naturally cool to room temperature to obtain the energy-saving catalyst.

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

[0121] Example 5:

[0122] As Figure 2 shown, a preparation method of an energy-saving catalyst, the preparation method includes:

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

[0124] 1. Add SBA-15 molecular sieve, ammonium nitrate, borax, tetrabutyl orthosilicate and pure water into a reaction kettle, start stirring, heat to 210 °C, and keep the reaction for 68 hours;

[0125] 2. After the reaction is completed, naturally cool to room temperature, filter the reaction product and wash it with absolute ethanol, and then dry it at 85 °C for 2 hours to obtain product A;

[0126] 3. Then place product A in a tubular furnace, heat from room temperature to 1350 °C at a heating rate of 5 °C per minute under nitrogen, then keep the temperature at 1350 °C for 5 hours, and cool and discharge to obtain product B;

[0127] 4. Then soak product B in hydrochloric acid with a concentration of 1.25 mol / L for 6 hours, stir ultrasonically for 0.5 hours, then filter to obtain solid matter, and then wash the solid matter three times with absolute ethanol;

[0128] 5. Finally, dry the solid matter at 120 °C for 6 hours, and after cooling, obtain a boron nitride / silicon nitride composite porous material, that is, the energy-saving catalyst support.

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

[0130] Next, prepare an energy-saving catalyst, including the following steps:

[0131] 6. Make the prepared energy-saving catalyst support into an electrode and connect it to the negative electrode of the power supply; dissolve the copper-containing compound and cobalt-containing compound in pure water to obtain an electrolyte solution, and adjust the pH of the electrolyte solution to 3; at the same time, connect the graphite electrode to the positive electrode of the power supply;

[0132] 7. Then, conduct an electric reaction for 7 hours. After stopping the reaction, take out the energy-saving catalyst support and wash it three times with pure water;

[0133] 8. Then dry the washed energy-saving catalyst support at 140 °C for 3 hours under argon protection, then calcine it at 850 °C for 8 hours under argon protection, and finally naturally cool to room temperature to obtain the energy-saving catalyst.

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

[0135] Example 6:

[0136] As Figure 2As shown, a preparation method of an energy-saving catalyst, the preparation method comprising:

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

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

[0139] 2. After the reaction is completed, naturally cool to room temperature, filter the reaction product and wash it with absolute ethanol, and then dry it at 100 °C for 1.5 hours to obtain product A;

[0140] 3. Then place product A in a tubular furnace, and under nitrogen, heat from room temperature to 1400 °C at a heating rate of 5 °C per minute, and then keep the temperature at 1400 °C for 4 hours, and cool and discharge to obtain product B;

[0141] 4. Then soak product B in hydrochloric acid with a concentration of 1.5 mol / L for 5 hours, stir ultrasonically for 1 hour and then filter to obtain a solid substance, and then wash the solid substance three times with absolute ethanol;

[0142] 5. Finally, dry the solid substance at 100 °C for 8 hours, and after cooling, obtain a boron nitride / silicon nitride composite porous material, that is, the energy-saving catalyst support.

[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] Next, prepare an energy-saving catalyst, including the following steps:

[0145] 6. Make the prepared energy-saving catalyst support into an electrode 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 solution, and adjust the pH of the electrolyte solution to 2; at the same time, connect a graphite electrode to the positive electrode of the power supply;

[0146] 7. Then, conduct an electric reaction for 8 hours, stop the reaction, take out the energy-saving catalyst support, and wash it three times with pure water;

[0147] 8. Then dry the washed energy-saving catalyst support at 150 °C for 3 hours under argon protection, then calcine it at 1000 °C for 7 hours under argon protection, and finally naturally cool to room temperature to obtain the energy-saving catalyst.

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

[0149] Comparative Example 1:

[0150] A preparation method of an energy-saving catalyst, the preparation method comprising:

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

[0152] 2. Subsequently, conduct an electrolytic reaction for 10 hours. After stopping the reaction, take out the γ-alumina and wash it three times with pure water;

[0153] 3. Then dry the washed γ-alumina at 140 °C for 3 hours under argon protection, then calcine it at 1000 °C for 8 hours under argon protection, and finally naturally cool it 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 the pure water is 40:5:5:50.

[0155] Comparative Example 2:

[0156] A preparation method of an energy-saving catalyst, the preparation method comprising:

[0157] First, prepare an energy-saving catalyst support, comprising the following steps:

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

[0159] 2. After the reaction is completed, naturally cool to room temperature, filter the reaction product by suction and wash it with absolute ethanol, and then dry it at 90 °C for 1.5 hours to obtain product A;

[0160] 3. Then place product A in a tubular furnace, and heat it from room temperature to 1300 °C at a heating rate of 5 °C per minute under nitrogen, and then keep the temperature at 1300 °C for 5 hours, and cool and discharge to obtain product B;

[0161] 4. Then soak product B in hydrochloric acid with a concentration of 1 mol / L for 5.5 hours, stir ultrasonically for 0.75 hours, then filter by suction to obtain a solid substance, and then wash the solid substance three times with absolute ethanol;

[0162] 5. Finally, dry the solid substance at 110 °C for 7 hours, and cool to obtain a boron nitride / silicon nitride composite porous material, which is the energy-saving catalyst support.

[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] Prepare the catalyst again, including the following steps:

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

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

[0167] 8. Then dry the washed solid substances at 150 °C for 2 hours under argon protection, calcine at 900 °C for 7 hours under argon protection, and finally cool naturally to room temperature to obtain the energy-saving catalyst.

[0168] In the above steps 6-8, 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 preparation method of an energy-saving catalyst, the preparation method includes:

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

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

[0173] 3. Then dry the washed solid substances at 150 °C for 3 hours under argon protection, calcine at 1000 °C for 7 hours under argon protection, and finally cool naturally to room temperature to obtain the energy-saving catalyst.

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

[0175] Refer to GB / T 38219-2019 to test the catalytic denitrification efficiency of the prepared energy-saving catalyst; and use a rotary abrasion tester to test the abrasion strength of the prepared energy-saving catalyst.

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

[0177] Catalytic denitrification efficiency (%) Wear intensity (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 can be seen from Table 1, the catalytic denitrification efficiency and abrasion strength of Examples 1-6 are better than those of Comparative Examples 1-3. This is because in Examples 1-6 of the present application, the active components 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 templating agent with a specific pore structure, a nitrogen source, a boron source, and a silicon source are dispersed in a solution environment, such that the nitrogen source, the boron source, and the silicon source are filled into the pore structure of the templating agent. 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 templating agent, thereby producing a boron nitride / silicon nitride composite porous material. Since the boron nitride / silicon nitride composite porous material has many pore structures, it can provide more sites for the loading of active ingredients. In this way, more active ingredients can be loaded onto the boron nitride / silicon nitride composite porous material as a carrier, thereby greatly improving the catalytic efficiency of the catalyst and achieving an energy-saving effect. Moreover, since boron nitride and silicon nitride are compounded together at the microscopic level, the prepared composite porous material has advantages such as 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 damaged, greatly prolonging the service life of the catalyst carrier and the catalyst, and further enhancing the energy-saving effect.

[0180] In addition, in Examples 1 to 6, by means of electrochemical reduction, copper and cobalt in cationic form are reduced to copper and cobalt in atomic form and then loaded onto an electrode made of a boron nitride / silicon nitride composite porous material. When the electrochemical reduction reaction occurs, an electric current flows between the electrodes through the electrolyte solution. Since the distribution of the electric current in the electrolyte solution is relatively uniform, the electron supply on the electrode made of the boron nitride / silicon nitride composite porous material is also relatively uniform, enabling copper and cobalt to adhere more uniformly and densely within and on the surface of the pore structure of the boron nitride / silicon nitride composite porous material. Through further high-temperature calcination under argon protection, copper and cobalt are maintained in an atomic state and more firmly bonded within and on the surface of the pore structure of the boron nitride / silicon nitride composite porous material. In this way, on the one hand, since copper and cobalt in atomic form are directly exposed in the pore structure or on the 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 ingredients after being used for a period of time, further improving the service life of the catalyst, and thus achieving the purpose of enhancing the energy-saving effect again.

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

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

[0183] Those skilled in the art should understand that this application is not limited by the above embodiments. What is described in the above embodiments and the specification only illustrates the principles of this application. Without departing from the spirit and scope of this application, this application will have various changes and improvements, and these changes and improvements all fall within the scope of this application claimed. The scope of protection claimed for this application is defined by the equivalents of the appended claims.

Claims

1. An energy-saving catalyst carrier, characterized in that: 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.

2. The method for preparing an energy-saving catalyst carrier according to claim 1, characterized in that: The following steps are involved: Add the template, nitrogen source, boron source, silicon source and pure water into the reaction kettle, start stirring, heat to 180-220°C, and keep the temperature 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, the product A is placed in a tube furnace, and the temperature is raised from room temperature to 1200-1400° C. at a heating rate of 5° C. per minute under nitrogen, and then kept at 1200-1400° C. for 4-6 hours, and the product is cooled and discharged to obtain the product B; Then, the product B is 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, and then the solid substance is washed three times with anhydrous ethanol; Finally, the solid matter is dried at 100-120° C. for 6-8 hours, and after cooling, a boron nitride / silicon nitride composite porous material, namely the energy-saving catalyst carrier, is obtained.

3. The method for preparing an energy-saving catalyst carrier according to claim 2, characterized in that: The template agent 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.

4. The method for preparing an energy-saving catalyst carrier according to claim 2, characterized in that: The nitrogen source includes one or more of urea, melamine, biuret, ammonium chloride and ammonium nitrate.

5. The method for preparing an energy-saving catalyst carrier according to claim 2, characterized in that: The boron source includes one or more of boric acid, boric anhydride and borax; the silicon source includes one or more of ethyl orthosilicate, butyl orthosilicate and silica sol.

6. The method for preparing an energy-saving catalyst carrier according to claim 2, 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).

7. An energy-saving catalyst, characterized in that: The energy-saving catalyst comprises an active ingredient and the energy-saving catalyst carrier as claimed in claim 1; the active ingredient comprises 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 energy-saving catalyst carrier as claimed in claim 1 by electrochemical reduction.

8. An energy-saving catalyst as claimed in claim 7, 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.

9. A method for preparing an energy-saving catalyst as claimed in claim 7 or 8, 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 the power supply; the copper-containing compound and the 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; Then, the reaction was continued for 6 to 10 hours, and 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.

10. The method for preparing an energy-saving catalyst according to claim 9, 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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