High-strength nano-zinc oxide composite desulfurizer and preparation method thereof

Abstract

The application belongs to the technical field of adsorptive desulfurizer, and particularly relates to a high-strength nanometer zinc oxide composite desulfurizer and a preparation method thereof. The composite desulfurizer contains the following raw materials in parts by weight: nanometer zinc oxide / activated carbon composite material 65-70 parts, filler 15-25 parts, and binder 40-50 parts. The desulfurizer prepared by the application has high mechanical strength, high sulfur capacity and high desulfurization efficiency.

Description

Technical Field

[0001] This invention belongs to the field of adsorption desulfurizing agent technology, specifically relating to a high-strength nano zinc oxide composite desulfurizing agent and its preparation method. Background Technology

[0002] In the process of industrial production and energy consumption, the emission of sulfur-containing compounds not only causes serious environmental pollution but also has various adverse effects on equipment, catalysts, and even human health. For example, sulfur dioxide (SO2) released during the combustion of fossil fuels such as coal and oil is a major factor in the formation of acid rain and disrupts the ecological balance; hydrogen sulfide (H2S) in industrial waste gas is highly toxic and easily corrodes metal equipment; and in industrial raw materials such as natural gas and syngas, sulfur can cause downstream catalysts to become poisoned and deactivated, greatly affecting production efficiency and product quality. Therefore, removing sulfur from various gas sources has become a crucial problem that must be solved in the industrial sector, and the research and development of desulfurization technology and the optimization of desulfurizing agent performance have always been the focus of industry attention.

[0003] Patent CN112691651B discloses a method for preparing a desulfurizing agent, the desulfurizing agent itself, and its application. The method includes the following steps: S1, mixing a silicon-containing compound with an aluminum-containing compound to obtain a silicon-aluminum slurry; S2, adding an alkaline solution to the obtained silicon-aluminum slurry, mixing evenly, and aging to obtain an aged slurry; S3, adding a metal solution to the obtained aged slurry, mixing evenly, and undergoing gelation and crystallization steps to obtain a solid crude product; S4: mixing the obtained solid crude product with a binder, molding, drying, and calcining to obtain the desulfurizing agent. This method, based on the formation of a Si-O-Al structure, adds metals for ion exchange, achieving one-step modification and low-cost desulfurizing agent preparation. After modification with metals from IB, IIB, and VIII, the desulfurization accuracy of the desulfurizing agent is improved under room temperature conditions, and it also has a large sulfur capacity. However, this invention does not consider desulfurization issues under high-temperature environments.

[0004] Patent CN115193391B discloses a nanorod-shaped zinc oxide desulfurizing agent, its preparation method, and its application. The desulfurizing agent comprises the following components by weight: 55-90 parts nanorod-shaped zinc oxide, 0.1-10 parts metal oxide, 0.1-8 parts binder, 0.1-5 parts pore-forming agent, and 0.1-5 parts solvent. At 200-500℃, the sulfur capacity of the desulfurizing agent is 23-36 wt%. The total specific surface area of ​​the nanorod-shaped zinc oxide is 100-225 m². 2 / g, with a particle size of 30-60nm and a compressive strength of 80-88N / cm; it has good desulfurization performance and good removal effect on organic sulfur and hydrogen sulfide. Although this invention solves the desulfurization problem under high temperature conditions, it does not focus on the regeneration of the desulfurizing agent.

[0005] Therefore, there is an urgent need to develop a desulfurizer that is not only suitable for high-temperature environments but also has excellent renewability. Summary of the Invention

[0006] To address the existing technical problems, the present invention aims to prepare a high-strength nano-zinc oxide composite desulfurizer with suitable bulk density, high mechanical strength, large specific surface area, high sulfur capacity, suitable for desulfurization under high temperature conditions, and excellent regeneration performance.

[0007] The present invention provides a high-strength nano zinc oxide composite desulfurizer, which, by weight, comprises the following raw materials: 65-70 parts of nano zinc oxide / activated carbon composite material, 15-25 parts of filler, and 40-50 parts of binder.

[0008] In some embodiments, the preparation method of the nano-zinc oxide / activated carbon composite material includes the following steps:

[0009] (1) Stir anhydrous ethanol solution of 0.05-0.06 mol / L zinc salt at 40-50℃ for 50-70 min, then add 0.08-0.09 mol / L alkali solution while stirring, and add hydroxyethyl methacrylate at the same time. After the addition is complete, stir at 40-50℃ for 1-2 h, let stand, filter, wash, and dry to obtain pretreated nano zinc oxide;

[0010] (2) Under the protection of an inert gas, the pretreated nano zinc oxide, acrylic acid and initiator obtained in step (1) are added to anhydrous ethanol and reacted at 55-65℃ for 5-6 hours to obtain modified nano zinc oxide.

[0011] (3) Add activated carbon to nitric acid solution and soak for 4-6 hours, then filter and wash to obtain pretreated activated carbon;

[0012] (4) Add 3-(phenylamino)propyltrimethoxysilane and the pretreated activated carbon obtained in step (3) to an ethanol solution, stir at 40-50℃ for 1-2 h, then add the modified nano zinc oxide obtained in step (2) and continue stirring for 2-3 h, filter, wash and dry to obtain nano zinc oxide / activated carbon composite material.

[0013] In some embodiments, the zinc salt is any one of zinc acetate, zinc sulfate, or zinc chloride.

[0014] Preferably, the zinc salt is zinc acetate.

[0015] In some embodiments, the alkaline solution is a sodium hydroxide solution, a sodium carbonate solution, or an ammonium bicarbonate solution.

[0016] Preferably, the alkaline solution is a sodium hydroxide solution.

[0017] Traditional methods produce zinc oxide with uneven particle size, small specific surface area, and a tendency to deactivate after high-temperature sintering. As a desulfurizing agent, it has few reactive sites and low sulfur capacity, affecting desulfurization efficiency. This invention modifies zinc oxide, increasing its porosity and improving desulfurization efficiency, sulfur capacity, and regeneration performance. This is likely because grafting double bonds onto the zinc oxide surface followed by polymerization with acrylic acid forms a coating structure that inhibits the aggregation of nano-zinc oxide particles, allowing for uniform dispersion and resulting in suitable bulk density and high crushing strength after sintering. Increased porosity maintains a high specific surface area, making it suitable for high-temperature environments. Furthermore, pretreatment of activated carbon enables it to react with 3-(phenylamino)propyltrimethoxysilane and increases the surface oxygen-containing functional groups, enhancing its adsorption capacity for sulfides. Simultaneously, modified nano-zinc oxide is chemically bonded to activated carbon; during sintering, the organic segments decompose, creating pores and resulting in a multi-level porous structure in the final desulfurizer. This enhances electron transport capacity, improving sulfur capacity and desulfurization efficiency through both chemical and physical adsorption.

[0018] In some embodiments, the mass ratio of the anhydrous ethanol solution of the zinc salt to hydroxyethyl methacrylate is 1:(0.2-0.5).

[0019] In some embodiments, the mass ratio of the pretreated nano-zinc oxide to acrylic acid in step (2) is 1:(0.1-0.2).

[0020] In some embodiments, the mass ratio of the pretreated activated carbon to the modified nano zinc oxide in step (4) is (0.1-0.3):1.

[0021] In some embodiments, the filler is any one or more of cobalt nitrate, zirconium nitrate, or copper oxide.

[0022] In some embodiments, the adhesive is a carboxymethyl cellulose solution.

[0023] Preferably, the adhesive is a 3-5 wt% aqueous solution of carboxymethyl cellulose.

[0024] A second aspect of this invention provides a method for preparing a high-strength nano-zinc oxide composite desulfurizer, comprising the following steps:

[0025] S1. Add the nano zinc oxide / activated carbon composite material and filler to the binder, stir evenly, and grind to obtain a mixture;

[0026] S2. The mixture obtained in step S1 is kneaded, extruded and shaped, then cured, and then microwave sintered to obtain a high-strength nano zinc oxide composite desulfurizer.

[0027] This invention utilizes microwave sintering technology to selectively heat at the molecular level, enabling rapid and uniform heating to form a dense and uniform microstructure. After sintering, the compressive strength of the desulfurizer is improved, making it suitable for high-pressure industrial desulfurization scenarios. At the same time, its tolerance is enhanced, and it can maintain a high sulfur capacity even after multiple regenerations. In addition, it can shorten the sintering time, retain the activity of nano zinc oxide, and further improve desulfurization efficiency.

[0028] In some embodiments, the mixing and grinding is carried out using a high-speed roller mill with a discharge flow rate of 0.5-1 t / h.

[0029] In some embodiments, the conditioning process involves standing at 70-80°C for 20-25 hours.

[0030] In some embodiments, the microwave sintering temperature is 500-700°C and the holding time is 10-20 minutes.

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0032] 1. This invention obtains a high-strength nano-zinc oxide composite desulfurizer by modifying zinc oxide, combining it with activated carbon, and then sintering it with fillers and binders. It has a large specific surface area, which significantly improves desulfurization efficiency, high compressive strength, and good renewability.

[0033] 2. This invention modifies zinc oxide to form a coating structure on the zinc oxide surface, which inhibits the aggregation of nano zinc oxide particles and enables them to be dispersed evenly. This solves the problems of traditional sulfurizing agents having few reactive sites, low sulfur capacity, and poor desulfurization effect. In addition, the combination with activated carbon makes the final desulfurizer form a multi-level porous structure, which enhances the electron transport capacity and improves sulfur capacity and desulfurization activity through chemical and physical adsorption.

[0034] 3. This invention utilizes microwave sintering technology to selectively heat at the molecular level, enabling rapid and uniform heating. This avoids the problems of particle coarsening or localized overheating caused by traditional high-temperature sintering, which leads to uneven desulfurizer structure and low compressive strength after sintering. At the same time, it improves tolerance, maintaining a high sulfur capacity even after multiple regenerations. Furthermore, it shortens the sintering time, preserves the activity of nano zinc oxide, and further improves desulfurization efficiency. Detailed Implementation

[0035] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0036] Each composite desulfurizer was prepared according to the proportions and preparation methods of the raw materials specified in the following examples and comparative examples.

[0037] To facilitate implementation of this invention by those skilled in the art, the manufacturers of some raw materials for the embodiments and comparative examples are described below:

[0038] The activated carbon was coconut shell activated carbon, purchased from Henan Yutai Environmental Protection Materials Co., Ltd., model number YT-19;

[0039] Unless otherwise specified, all other raw materials can be purchased from the market.

[0040] Preparation Example 1

[0041] The preparation method of nano zinc oxide / activated carbon composite material-1 includes the following steps:

[0042] (1) 100g of anhydrous ethanol solution of 0.058mol / L zinc acetate was stirred at 45℃ for 60min. Then, 34g of 0.085mol / L sodium hydroxide aqueous solution was added while stirring, along with 40g of hydroxyethyl methacrylate. After the addition was completed, the mixture was stirred at 45℃ for 1.5h, allowed to stand, filtered, washed, and dried to obtain pretreated nano zinc oxide.

[0043] (2) Under nitrogen protection, 10g of nano zinc oxide obtained in step (1), 1.5g of acrylic acid and 0.1g of azobisisobutyronitrile were added to 100ml of anhydrous ethanol and reacted at 60℃ for 5.5h to obtain modified nano zinc oxide.

[0044] (3) Add 20g of activated carbon to 200ml of 75wt% nitric acid solution and soak for 5h. Filter and wash to obtain pretreated activated carbon.

[0045] (4) Add 1g of 3-(phenylamino)propyltrimethoxysilane and 2g of the pretreated activated carbon obtained in step (3) to 100ml of 85wt% ethanol aqueous solution, stir at 45℃ for 1.5h, then add 10g of the modified nano zinc oxide obtained in step (2) and continue stirring for 2.5h. Filter, wash and dry to obtain nano zinc oxide / activated carbon composite material-1.

[0046] Preparation Example 2

[0047] The preparation method of nano zinc oxide / activated carbon composite material-2 is the same as that of preparation example 1, except that the amount of hydroxyethyl methacrylate added is 55g.

[0048] Preparation Example 3

[0049] The preparation method of nano zinc oxide / activated carbon composite material-3 is the same as that of preparation example 1, except that the amount of acrylic acid added is 2.5g.

[0050] Preparation Example 4

[0051] The preparation method of nano zinc oxide / activated carbon composite material-4 is the same as that of preparation example 1, except that the amount of pretreated activated carbon added in step (4) is 3.5g.

[0052] Preparation Example 5

[0053] The preparation method of nano zinc oxide / activated carbon composite material-5 is the same as that of preparation example 1, except that hydroxyethyl methacrylate is replaced with pentaerythritol triacrylate in equal amounts.

[0054] Preparation Example 6

[0055] The preparation method of nano zinc oxide / activated carbon composite material-6 is the same as that of preparation example 1, except that 3-(phenylamino)propyltrimethoxysilane is replaced by γ-aminopropyltriethoxysilane in equal amounts.

[0056] Preparation Example 7

[0057] The preparation method of nano zinc oxide / activated carbon composite material-7 includes the following steps:

[0058] (1) 100g of anhydrous ethanol solution of 0.058mol / L zinc acetate was stirred at 45℃ for 60min. Then, 34g of 0.085mol / L sodium hydroxide aqueous solution was added while stirring, along with 40g of hydroxyethyl methacrylate. After the addition was completed, the mixture was stirred at 45℃ for 1.5h, allowed to stand, filtered, washed, and dried to obtain pretreated nano zinc oxide.

[0059] (2) Under nitrogen protection, 10g of nano zinc oxide obtained in step (1), 1.5g of acrylic acid and 0.1g of azobisisobutyronitrile were added to 100ml of anhydrous ethanol and reacted at 60℃ for 5.5h to obtain modified nano zinc oxide.

[0060] (3) Add 20g of activated carbon to 200ml of 75wt% nitric acid solution and soak for 5h. Filter and wash to obtain pretreated activated carbon.

[0061] (4) Add 2g of the pretreated activated carbon obtained in step (3) to 100ml of 85wt% ethanol aqueous solution, stir at 45℃ for 1.5h, then add 10g of the modified nano zinc oxide obtained in step (2) and continue stirring for 2.5h. Filter, wash and dry to obtain nano zinc oxide / activated carbon composite material-7.

[0062] Preparation Example 8

[0063] The preparation method of modified nano zinc oxide includes the following steps:

[0064] (1) 100g of anhydrous ethanol solution of 0.058mol / L zinc acetate was stirred at 45℃ for 60min. Then, 34g of 0.085mol / L sodium hydroxide aqueous solution was added while stirring, along with 40g of hydroxyethyl methacrylate. After the addition was completed, the mixture was stirred at 45℃ for 1.5h, allowed to stand, filtered, washed, and dried to obtain pretreated nano zinc oxide.

[0065] (2) Under nitrogen protection, 10g of nano zinc oxide obtained in step (1), 1.5g of acrylic acid and 0.1g of azobisisobutyronitrile were added to 100ml of anhydrous ethanol and reacted at 60℃ for 5.5h to obtain modified nano zinc oxide.

[0066] Preparation Example 9

[0067] The preparation method of nano zinc oxide includes the following steps:

[0068] 100 g of anhydrous ethanol solution of 0.058 mol / L zinc acetate was stirred at 45 °C for 60 min. Then, 34 g of 0.085 mol / L sodium hydroxide aqueous solution was added while stirring, and the mixture was stirred at 45 °C for 1.5 h. After standing, the solution was filtered, washed, and dried to obtain nano-zinc oxide.

[0069] Example 1

[0070] A high-strength nano zinc oxide composite desulfurizer, by weight, comprises the following raw materials: 68 parts of nano zinc oxide / activated carbon composite material, 20 parts of zirconium nitrate, and 45 parts of 4 wt% carboxymethyl cellulose aqueous solution.

[0071] The preparation method of the high-strength nano-zinc oxide composite desulfurizer in this embodiment includes the following steps:

[0072] S1. Add nano zinc oxide / activated carbon composite material-1 and zirconium nitrate to a 4 wt% carboxymethyl cellulose aqueous solution, stir evenly, and then mix and grind using a high-speed roller mill with a discharge flow rate of 1 t / h to obtain a mixture;

[0073] S2. The mixture obtained in step S1 is kneaded for 2 hours and then extruded into a Φ5×15mm cylindrical shape under a pressure of 2000KN. After that, it is cured at 75℃ for 23 hours. Then, the cured material is microwave sintered at a temperature of 600℃ for 15 minutes to obtain a high-strength nano zinc oxide composite desulfurizer.

[0074] Example 2

[0075] A high-strength nano zinc oxide composite desulfurizer, by weight, comprises the following raw materials: 65 parts of nano zinc oxide / activated carbon composite material, 15 parts of zirconium nitrate, and 40 parts of 4 wt% carboxymethyl cellulose aqueous solution.

[0076] The preparation method of the high-strength nano-zinc oxide composite desulfurizer in this embodiment includes the following steps:

[0077] S1. Add nano zinc oxide / activated carbon composite material-1 and zirconium nitrate to a 4 wt% carboxymethyl cellulose aqueous solution, stir evenly, and then mix and grind using a high-speed roller mill with a discharge flow rate of 1 t / h to obtain a mixture;

[0078] S2. The mixture obtained in step S1 is kneaded for 2 hours and then extruded into a Φ5×15mm cylindrical shape under a pressure of 2000KN. After that, it is cured at 70℃ for 25 hours. Then, the cured material is microwave sintered at a temperature of 500℃ for 20 minutes to obtain a high-strength nano zinc oxide composite desulfurizer.

[0079] Example 3

[0080] A high-strength nano zinc oxide composite desulfurizer, by weight, comprises the following raw materials: 70 parts of nano zinc oxide / activated carbon composite material-1, 25 parts of zirconium nitrate, and 50 parts of 4 wt% carboxymethyl cellulose aqueous solution.

[0081] The preparation method of the high-strength nano-zinc oxide composite desulfurizer in this embodiment includes the following steps:

[0082] S1. Add nano zinc oxide / activated carbon composite material-1 and zirconium nitrate to a 4 wt% carboxymethyl cellulose aqueous solution, stir evenly, and then mix and grind using a high-speed roller mill with a discharge flow rate of 1 t / h to obtain a mixture;

[0083] S2. The mixture obtained in step S1 is kneaded for 2 hours and then extruded into a Φ5×15mm cylindrical shape under a pressure of 2000KN. After that, it is cured at 80℃ for 20 hours. Then, the cured material is microwave sintered at a temperature of 700℃ for 10 minutes to obtain a high-strength nano zinc oxide composite desulfurizer.

[0084] Example 4

[0085] A high-strength nano zinc oxide composite desulfurizer and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that nano zinc oxide / activated carbon composite material-1 is replaced by an equal amount of nano zinc oxide / activated carbon composite material-2.

[0086] Example 5

[0087] A high-strength nano zinc oxide composite desulfurizer and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that nano zinc oxide / activated carbon composite material-1 is replaced with an equal amount of nano zinc oxide / activated carbon composite material-3.

[0088] Example 6

[0089] A high-strength nano zinc oxide composite desulfurizer and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that nano zinc oxide / activated carbon composite material-1 is replaced with an equal amount of nano zinc oxide / activated carbon composite material-4.

[0090] Example 7

[0091] A high-strength nano zinc oxide composite desulfurizer and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that nano zinc oxide / activated carbon composite material-1 is replaced with an equal amount of nano zinc oxide / activated carbon composite material-5.

[0092] Example 8

[0093] A high-strength nano zinc oxide composite desulfurizer and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that the nano zinc oxide / activated carbon composite material-1 is replaced by an equal amount of nano zinc oxide / activated carbon composite material-6.

[0094] Example 9

[0095] A high-strength nano zinc oxide composite desulfurizer and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that the nano zinc oxide / activated carbon composite material-1 is replaced with an equal amount of nano zinc oxide / activated carbon composite material-7.

[0096] Comparative Example 1

[0097] A high-strength nano-zinc oxide composite desulfurizer and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that the nano-zinc oxide / activated carbon composite material-1 is replaced with an equal amount of modified nano-zinc oxide.

[0098] Comparative Example 2

[0099] A high-strength nano zinc oxide composite desulfurizer and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that the nano zinc oxide / activated carbon composite material-1 is replaced with an equal amount of nano zinc oxide.

[0100] Performance testing

[0101] The composite desulfurizing agents prepared in the above examples and comparative examples were subjected to the following tests:

[0102] 1. Crushing resistance: Measured using a particle strength tester.

[0103] 2. Bulk density: Determined in accordance with GB / T 6286-2021.

[0104] 3. Specific surface area and sulfur capacity

[0105] The composite desulfurizing agents prepared in the above embodiments and comparative examples were ground into 40-60 mesh particles, and their specific surface area was tested by the BET method.

[0106] Sulfur capacity was tested using a hydrogen sulfide penetration test. The experimental conditions were: sample tube inner diameter 6 mm, sample loading height 2 cm, gas flow rate 100 ml / min, experimental temperature 350℃, experimental pressure atmospheric pressure, inlet hydrogen sulfide concentration 100 ppm, and the experiment was stopped when the outlet hydrogen sulfide concentration was less than 0.02 ppm. The hydrogen sulfide content in the gas was determined by gas chromatography. Sulfur capacity was calculated using chemical analysis: sulfur capacity = weight of hydrogen sulfide / weight of desulfurizing agent × 100%.

[0107] The test results are shown in Table 1.

[0108] Table 1

[0109]

[0110] The experimental data in Table 1 show that the composite desulfurizers prepared in Examples 1-3 have suitable bulk density, high mechanical strength, large specific surface area, and large sulfur capacity. A comparison of the data from Examples 1 with Examples 4, 5, and 7 shows that the ratio of anhydrous ethanol solution of zinc salt to hydroxyethyl methacrylate, the ratio of pretreated nano-zinc oxide to acrylic acid, and replacing hydroxyethyl methacrylate with an equal amount of pentaerythritol triacrylate may all alter the crosslinking degree of the nano-zinc oxide surface coating, leading to a reduction in the active sites and sulfur capacity of the desulfurizer. A comparison of the data from Examples 1 and 6 shows that the ratio of pretreated activated carbon to modified nano-zinc oxide... Changes in the zinc oxide ratio may cause some modified nano zinc oxide to enter the pore structure of activated carbon, causing pore blockage and affecting the specific surface area and sulfur capacity of the desulfurizer. A comparison of data from Examples 1 and 8 shows that changes in the type of silane may reduce the steric hindrance between activated carbon and modified nano zinc oxide, easily causing agglomeration and pore blockage, thus reducing the specific surface area and sulfur capacity of the desulfurizer. A comparison of data from Examples 1 and 9 shows that directly combining activated carbon with modified nano zinc oxide results in a decrease in all performance characteristics. A comparison of data from Example 1 and Comparative Examples 1 and 2 shows that directly using modified nano zinc oxide or nano zinc oxide results in a decrease in all performance characteristics.

[0111] (2) The composite desulfurizing agent was placed in a fixed-bed U-shaped reactor, and the U-shaped tube was placed in the reactor. The composite desulfurizing agent was heated at a rate of 10℃ / min under N2, with a gas flow rate of 80mL / min. When the temperature reached 600℃, O2 was introduced and kept constant. The regeneration was completed when no SO2 was discharged from the outlet. The regeneration performance of the composite desulfurizing agent was evaluated. The regeneration cycle was 3 times, and the test results are shown in Table 2.

[0112] Table 2

[0113]

[0114] As shown in Table 2, the composite desulfurizers prepared in Examples 1-3 have excellent renewability and still have high bulk density and mechanical strength, as well as large specific surface area and sulfur capacity.

[0115] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present application in any way. Although the present application discloses the preferred embodiment as described above, it is not intended to limit the present application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of the present application using the disclosed technical content are equivalent to equivalent implementation cases. Any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the technical solution of the present invention are still within the scope of the technical solution.

Claims

1. A high-strength nano-zinc oxide composite desulfurizer, characterized in that, The material comprises, by weight, 65-70 parts of nano-zinc oxide / activated carbon composite material, 15-25 parts of filler, and 40-50 parts of binder; the preparation method of the nano-zinc oxide / activated carbon composite material includes the following steps: (1) Stir anhydrous ethanol solution of 0.05-0.06 mol / L zinc salt at 40-50℃ for 50-70 min, then add 0.08-0.09 mol / L alkali solution while stirring, and add hydroxyethyl methacrylate at the same time. After the addition is completed, stir at 40-50℃ for 1-2 h, let stand, filter, wash and dry to obtain pretreated nano zinc oxide; (2) Under the protection of inert gas, the pretreated nano zinc oxide, acrylic acid and initiator obtained in step (1) are added to anhydrous ethanol and reacted at 55-65℃ for 5-6h to obtain modified nano zinc oxide. (3) Soak activated carbon in nitric acid solution for 4-6 hours, filter and wash to obtain pretreated activated carbon; (4) Add 3-(phenylamino)propyltrimethoxysilane and the pretreated activated carbon obtained in step (3) to an ethanol solution, stir at 40-50℃ for 1-2 h, then add the modified nano zinc oxide obtained in step (2) and continue stirring for 2-3 h, filter, wash and dry to obtain nano zinc oxide / activated carbon composite material. The mass ratio of the anhydrous ethanol solution of the zinc salt to hydroxyethyl methacrylate is 1:(0.2-0.5). The mass ratio of pretreated nano-zinc oxide to acrylic acid in step (2) is 1:(0.1-0.2). The mass ratio of pretreated activated carbon to modified nano zinc oxide in step (4) is (0.1-0.3):

1.

2. The high-strength nano-zinc oxide composite desulfurizer according to claim 1, characterized in that, The filler is any one or more of cobalt nitrate, zirconium nitrate, or copper oxide.

3. The high-strength nano-zinc oxide composite desulfurizer according to claim 1, characterized in that, The adhesive is a carboxymethyl cellulose solution.

4. A method for preparing the high-strength nano-zinc oxide composite desulfurizer according to any one of claims 1-3, characterized in that, Includes the following steps: S1. Add the nano zinc oxide / activated carbon composite material and filler to the binder, stir evenly, and grind to obtain a mixture; S2. The mixture obtained in step S1 is kneaded, extruded and shaped, then cured, and then microwave sintered to obtain a high-strength nano zinc oxide composite desulfurizer.

5. The preparation method of the high-strength nano-zinc oxide composite desulfurizer according to claim 4, characterized in that, The aforementioned conditioning process involves letting the food stand at 70-80℃ for 20-25 hours.

6. The preparation method of the high-strength nano-zinc oxide composite desulfurizer according to claim 4, characterized in that, The microwave sintering temperature is 500-700℃, and the holding time is 10-20 minutes.

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