High-sulfur-capacity iron oxyhydroxide desulfurization catalyst and preparation method thereof
By adding specific additives and carbonized fine pellets to the iron hydroxyoxide desulfurization catalyst, a high specific surface area and high porosity structure is formed, which solves the problem of insufficient catalyst active sites and significantly improves its sulfur capacity and reaction activity.
Patent Information
- Application Number
- CN202510464971.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-15
- Publication Date
- 2025-06-27
AI Technical Summary
The catalyst active sites of existing iron hydroxyoxide desulfurization catalysts are insufficient, resulting in weak sulfur adsorption ability, which easily hinders the diffusion of hydrogen sulfide and reduces its sulfur capacity performance.
By adding components such as graphene oxide, modified iron tetraoxide and ethylenediamine, a desulfurization catalyst with a high specific surface area and three-dimensional network structure is formed, and a high porosity carbon framework is generated by carbonizing coconut shell powder and walnut shell powder to enhance the sulfur capacity and reaction activity of the catalyst.
The penetration and specific surface area performance of the iron hydroxyoxide desulfurization catalyst is significantly improved, and its use performance and upper sulfur capacity limit are improved.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of desulfurization catalysts, and specifically provides a high sulfur capacity iron oxyhydroxide desulfurization catalyst and a preparation method thereof. Background Art
[0002] The iron oxyhydroxide desulfurization catalyst is a desulfurizer with excellent performance. With iron oxyhydroxide as the main active ingredient, it has the advantages of high sulfur capacity, high desulfurization efficiency, fast reaction speed, good stability, etc., and can effectively remove sulfur-containing impurities such as hydrogen sulfide in various gases.
[0003] In the prior art, the active sites of the iron oxyhydroxide desulfurization catalyst are insufficient, resulting in weak sulfur adsorption ability, which easily hinders the diffusion of hydrogen sulfide and reduces its sulfur capacity performance. Based on this, the present invention provides a high sulfur capacity iron oxyhydroxide desulfurization catalyst and a preparation method thereof. Summary of the Invention
[0004] The purpose of the present invention is to provide a high sulfur capacity iron oxyhydroxide desulfurization catalyst and a preparation method thereof. The high sulfur capacity iron oxyhydroxide desulfurization catalyst prepared by the present invention not only has good breakthrough sulfur capacity performance, but also has excellent specific surface area performance, effectively improving the use performance of the iron oxyhydroxide desulfurization catalyst.
[0005] To achieve the above purpose, the present invention provides the following technical solutions: In the first aspect, the present invention provides a high sulfur capacity iron oxyhydroxide desulfurization catalyst, which comprises the following raw materials in weight percentage: 30-40% iron oxyhydroxide, 20-30% sodium hydroxide, 10-20% additive, 4-6% powder, and the balance is auxiliary agent; The raw materials of the additive are composed of graphene oxide, modified magnetite, and ethylenediamine; The raw materials of the modified magnetite are composed of magnetite, methyl isobutyl ketone solution, and treatment agent.
[0006] Further, the additive is prepared by the following method: Graphene oxide and modified magnetite are added into a beaker, and the mass ratio of graphene oxide to modified magnetite is 1:(0.4 - 0.6). Deionized water is added into the beaker, and a magnetic stirrer is used to stir at 160 - 200 r / min for 16 - 20 min. After the stirring is completed, the obtained product is subjected to ultrasonic treatment. The ultrasonic treatment is set at 200 - 300 W, and the treatment time is 12 - 16 min. The product obtained by ultrasonic treatment is transferred into a beaker, and a magnetic stirrer is used to stir at 300 - 500 r / min. During the stirring process, ethylenediamine is slowly added dropwise. After the addition of ethylenediamine is completed, the magnetic stirrer is set at 500 - 600 r / min and stirred for 1 - 3 h. The product obtained by stirring is added into a reaction kettle, and the reaction kettle is set to heat up to 60 - 80 °C, and the stirring speed is 160 - 200 r / min. It is set to keep warm and stir for 20 - 30 min.
[0007] Further, the product obtained by keeping warm and stirring in the reaction kettle is cooled to room temperature, immersed in deionized water and soaked and washed 4 - 6 times, and the soaking time for each time is 40 - 60 min to obtain the additive.
[0008] Further, the mass of the deionized water is 60 - 80% of the mass of graphene oxide, and the mass of ethylenediamine is 6 - 8% of the mass of graphene oxide.
[0009] Further, the modified magnetite is prepared by the following method: Magnetite and methyl isobutyl ketone solution are added into a reaction kettle, a treating agent is added into the reaction kettle, the reaction kettle is set to heat up to 80 - 120 °C, the stirring speed is 200 - 300 r / min, and it is set to keep warm and stir for 20 - 30 min. The obtained product is subjected to centrifugation and washing treatment, and then sent into an oven. The oven is set to dry at 60 - 70 °C for 2 - 4 h to obtain the modified magnetite. Among them, the mass ratio of magnetite to methyl isobutyl ketone solution is 1:(10 - 20), and the mass concentration of the methyl isobutyl ketone solution is 10 - 20%.
[0010] Further, the magnetite selected is a powder with a particle size of 20 - 40 nm.
[0011] Further, the treating agent is prepared by mixing 1,2-epoxydodecane, sodium hydroxide and deionized water, and the mass ratio of 1,2-epoxydodecane, sodium hydroxide and deionized water is 1:(0.1 - 0.3):(10 - 12).
[0012] Further, the auxiliary agent selected is an equal amount mixture of hydroxymethyl cellulose, guar gum and sodium alginate.
[0013] Further, the powder material is prepared by the following method: The powder material selects coconut shell powder, walnut shell powder, and iron oxyhydroxide as raw materials. The mass ratio of the coconut shell powder, walnut shell powder, and iron oxyhydroxide is 1:(1.2 - 1.4):(0.4 - 0.6). The coconut shell powder, walnut shell powder, and iron oxyhydroxide are all selected as powder materials with a particle size of 4 - 10 μm. After the coconut shell powder, walnut shell powder, and iron oxyhydroxide are mixed evenly, they are added to a carbonization furnace. The carbonization furnace is set with a heating rate of 6 - 8 °C / min and heated to 600 - 800 °C, and kept warm for 1 - 3 h. Nitrogen is introduced during the carbonization process to obtain the powder material.
[0014] In a second aspect, the present invention also provides a preparation method of a high sulfur capacity iron oxyhydroxide desulfurization catalyst, including the following steps: Weigh iron oxyhydroxide and sodium hydroxide as needed for kneading treatment. Weigh additives, powder materials, and auxiliaries as needed and add them to continue kneading treatment to obtain a mud material. The mud material is added to a reaction kettle, and deionized water is added to the reaction kettle. The mass of the deionized water is 20 - 30% of the mass of the mud material. The reaction kettle is set to be heated to 100 - 160 °C and kept warm for reaction for 20 - 30 h. After the heat preservation reaction ends and cools to room temperature, the obtained product is washed, filtered, dried, and crushed to obtain a high sulfur capacity iron oxyhydroxide desulfurization catalyst.
[0015] Compared with the prior art, the beneficial effects of the present invention are: 1. In the present invention, during the preparation process of the high sulfur capacity iron oxyhydroxide desulfurization catalyst, by adding additives, among which, using methyl isobutyl ketone solution as a dispersant and combining 1,2-epoxydodecane in the treatment agent can reduce the surface energy of the magnetite particles, inhibit the agglomeration of the magnetite particles, increase the exposure of their active sites, improve the specific surface area and reaction activity. The addition of ethylenediamine can act as a bridging agent, and through the coordination of amino groups with graphene oxide and magnetite, a three-dimensional network structure is formed, further improving the specific surface area performance of the material, and thus improving its sulfur capacity performance.
[0016] 2. In the present invention, by adding various fine particle materials in the powder material, the coconut shell powder and walnut shell powder can generate a high-porosity carbon skeleton after carbonization, providing a large specific surface area and hierarchical pores, promoting the diffusion and adsorption of sulfides. Through the preloading treatment of iron oxyhydroxide, iron oxyhydroxide is evenly embedded in the carbon matrix during the carbonization process, forming a composite support with enriched active sites, further improving the upper limit of the sulfur capacity of the material. Detailed implementation manners
[0017] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
[0018] Among them, it should be noted that the raw materials used in the following embodiments are all commercially available raw materials. Embodiment
[0019] A high-sulfur-capacity iron oxyhydroxide desulfurization catalyst comprises the following raw materials by weight percentage: 30% iron oxyhydroxide, 20% sodium hydroxide, 10% additive, 4% powder, and the balance is auxiliary agent; The raw materials of the additive are composed of graphene oxide, modified magnetite, and ethylenediamine; The raw materials of the modified magnetite are composed of magnetite, methyl isobutyl ketone solution, and treating agent.
[0020] The additive is prepared by the following method: Graphene oxide and modified magnetite are added into a beaker, and the mass ratio of graphene oxide to modified magnetite is 1:(0.4). Deionized water is added into the beaker, and a magnetic stirrer is used to set the stirring speed at 160 r / min for 16 min. After the stirring is completed, the obtained product is subjected to ultrasonic treatment. The ultrasonic treatment is set at 200 W, and the treatment time is 12 min. The product obtained by ultrasonic treatment is transferred to a beaker, and a magnetic stirrer is used to set the stirring speed at 300 r / min. During the stirring process, ethylenediamine is slowly added dropwise. After the dropwise addition of ethylenediamine is completed, the magnetic stirrer is set at 500 r / min for 1 h of stirring treatment. The product obtained by stirring is added into a reaction kettle, and the reaction kettle is set to heat up to 60 °C, the stirring speed is 160 r / min, and the holding and stirring treatment is set for 20 min.
[0021] The product obtained by holding and stirring in the reaction kettle is cooled to room temperature and immersed in deionized water for soaking and washing 4 times, and the soaking time for each time is 40 min to obtain the additive.
[0022] The mass of deionized water is 60% of the mass of graphene oxide, and the mass of ethylenediamine is 6% of the mass of graphene oxide.
[0023] The modified iron tetroxide is prepared by the following method: Iron tetroxide and methyl isobutyl ketone solution are added into a reaction kettle, a treating agent is added into the reaction kettle, the reaction kettle is set to be heated to 80 °C, the stirring speed is 200 r / min, the heat preservation and stirring treatment is set for 20 min, the obtained product is centrifuged and washed, and then sent into an oven, and the oven is set for drying treatment at 60 °C for 2 h to obtain the modified iron tetroxide. Among them, the mass ratio of iron tetroxide to methyl isobutyl ketone solution is 1:(10), and the mass concentration of the methyl isobutyl ketone solution is 10%.
[0024] The iron tetroxide selected is a powder with a particle size of 20 nm.
[0025] The treating agent is prepared by mixing 1,2-epoxydodecane, sodium hydroxide and deionized water. The mass ratio of 1,2-epoxydodecane, sodium hydroxide and deionized water is 1:(0.1):(10).
[0026] The auxiliary agent selected is an equal-mass mixture of hydroxymethyl cellulose, guar gum and sodium alginate.
[0027] The powder is prepared by the following method: The powder selected is coconut shell powder, walnut shell powder and iron oxyhydroxide as raw materials. The mass ratio of coconut shell powder, walnut shell powder and iron oxyhydroxide is 1:(1.2):(0.4). The coconut shell powder, walnut shell powder and iron oxyhydroxide are all selected as powders with a particle size of 4 μm. After the coconut shell powder, walnut shell powder and iron oxyhydroxide are mixed evenly, they are added into a carbonization furnace. The carbonization furnace is set to have a heating rate of 6 °C / min and is heated to 600 °C and kept warm for 1 h. Nitrogen is introduced during the carbonization process to obtain the powder.
[0028] A preparation method of a high-sulfur-capacity iron oxyhydroxide desulfurization catalyst includes the following steps: Weigh iron oxyhydroxide and sodium hydroxide as required for kneading treatment. Weigh additives, powder and auxiliary agent as required and add them to continue kneading treatment to obtain a mud. The mud is added into a reaction kettle, and deionized water is added into the reaction kettle. The mass of the deionized water is 20% of the mass of the mud. The reaction kettle is set to be heated to 100 °C and kept warm for reaction for 20 h. After the heat preservation reaction is completed and cooled to room temperature, the obtained product is washed, filtered, dried and crushed to obtain the high-sulfur-capacity iron oxyhydroxide desulfurization catalyst. Example
[0029] A high-sulfur-capacity iron oxyhydroxide desulfurization catalyst includes the following raw material components by weight percentage: 35% iron oxyhydroxide, 25% sodium hydroxide, 15% additive, 5% powder, and the balance is auxiliary agent; The raw materials of the additive are composed of graphene oxide, modified iron tetroxide and ethylenediamine; The raw materials of the modified iron tetroxide are composed of iron tetroxide, methyl isobutyl ketone solution and treating agent.
[0030] The additive is prepared by the following method: Graphene oxide and modified magnetite are added into a beaker. The mass ratio of graphene oxide to modified magnetite is 1:(0.5). Deionized water is added into the beaker. A magnetic stirrer is used to stir at 180 r / min for 18 min. After the stirring is completed, the obtained product is subjected to ultrasonic treatment. The ultrasonic treatment is set at 250 W and the treatment time is 14 min. The product obtained by ultrasonic treatment is transferred into a beaker. A magnetic stirrer is used to stir at 400 r / min. Ethylenediamine is slowly added dropwise during the stirring. After the addition of ethylenediamine is completed, the magnetic stirrer is set at 550 r / min and stirred for 2 h. The product obtained by stirring is added into a reaction kettle. The reaction kettle is set to heat up to 70 °C, the stirring speed is 180 r / min, and it is set to keep warm and stir for 25 min.
[0031] The product obtained by keeping warm and stirring in the reaction kettle is cooled to room temperature and immersed in deionized water for soaking and washing 5 times, with each soaking time being 50 min, to obtain the additive.
[0032] The mass of deionized water is 70% of the mass of graphene oxide, and the mass of ethylenediamine is 7% of the mass of graphene oxide.
[0033] The modified magnetite is prepared by the following method: Magnetite and methyl isobutyl ketone solution are added into a reaction kettle. A treating agent is added into the reaction kettle. The reaction kettle is set to heat up to 100 °C, the stirring speed is 250 r / min, and it is set to keep warm and stir for 25 min. The obtained product is subjected to centrifugation and washing treatments, and then sent into an oven. The oven is set to dry at 65 °C for 3 h to obtain the modified magnetite. Among them, the mass ratio of magnetite to methyl isobutyl ketone solution is 1:(15), and the mass concentration of the methyl isobutyl ketone solution is 15%.
[0034] The magnetite selected is powder with a particle size of 30 nm.
[0035] The treating agent is prepared by mixing 1,2-epoxydodecane, sodium hydroxide and deionized water. The mass ratio of 1,2-epoxydodecane, sodium hydroxide and deionized water is 1:(0.2):(11).
[0036] The auxiliary agent selected is an equal-mass mixture of hydroxymethyl cellulose, guar gum and sodium alginate.
[0037] The powder is prepared by the following method: The powder selected uses coconut shell powder, walnut shell powder and iron hydroxyoxide as raw materials. The mass ratio of coconut shell powder, walnut shell powder and iron hydroxyoxide is 1:(1.3):(0.5). The coconut shell powder, walnut shell powder and iron hydroxyoxide are all selected as powders with a particle size of 6 μm. After the coconut shell powder, walnut shell powder and iron hydroxyoxide are mixed evenly, they are added into a carbonization furnace. The carbonization furnace is set to have a heating rate of 7 °C / min and heated to 700 °C, and kept warm for 2 h. Nitrogen is introduced during the carbonization process to obtain the powder.
[0038] A preparation method of a high sulfur capacity iron oxyhydroxide desulfurization catalyst, comprising the following steps: Weigh iron oxyhydroxide and sodium hydroxide as needed for kneading treatment, weigh additives, powder materials and auxiliaries as needed and add them to continue kneading treatment to obtain a mud material. The mud material is added to a reaction kettle, and deionized water is added to the reaction kettle. The mass of the deionized water is 25% of the mass of the mud material. The reaction kettle is set to heat up to 130 °C and keep the temperature for reaction for 25 h. After the heat preservation reaction is completed, wait until it cools to room temperature. The obtained product is washed, filtered, dried and crushed to obtain a high sulfur capacity iron oxyhydroxide desulfurization catalyst. Example
[0039] A high sulfur capacity iron oxyhydroxide desulfurization catalyst, comprising the following raw materials by weight percentage: 40% iron oxyhydroxide, 30% sodium hydroxide, 20% additives, 6% powder materials, and the balance is auxiliaries; The raw materials of the additive are composed of graphene oxide, modified magnetite, and ethylenediamine; The raw materials of the modified magnetite are composed of magnetite, methyl isobutyl ketone solution, and treatment agent.
[0040] The additive is prepared by the following method: Graphene oxide and modified magnetite are added to a beaker. The mass ratio of graphene oxide to modified magnetite is 1:(0.6). Deionized water is added to the beaker. Use a magnetic stirrer to set the stirring speed at 200 r / min and stir for 20 min. After the stirring is completed, the obtained product is subjected to ultrasonic treatment. The ultrasonic treatment is set at 300 W and the treatment time is 16 min. The product obtained by ultrasonic treatment is transferred to a beaker. Use a magnetic stirrer to set the stirring speed at 500 r / min. During the stirring process, ethylenediamine is slowly added dropwise. After the addition of ethylenediamine is completed, the magnetic stirrer is set at 600 r / min and stirred for 3 h. The product obtained by stirring is added to a reaction kettle. The reaction kettle is set to heat up to 80 °C, the stirring speed is 200 r / min, and the heat preservation stirring treatment is set for 30 min.
[0041] The product obtained by heat preservation stirring in the reaction kettle is cooled to room temperature and immersed in deionized water for soaking and washing 6 times, and the soaking time for each time is 60 min to obtain the additive.
[0042] The mass of the deionized water is 80% of the mass of the graphene oxide, and the mass of the ethylenediamine is 8% of the mass of the graphene oxide.
[0043] The modified iron tetroxide is prepared by the following method: Iron tetroxide and methyl isobutyl ketone solution are added into a reaction kettle, a treating agent is added into the reaction kettle, the reaction kettle is set to be heated to 120 °C, the stirring speed is 300 r / min, the heat preservation and stirring treatment is set for 30 min, the obtained product is centrifuged and washed, and then sent into an oven. The oven is set to be dried at 70 °C for 4 h to obtain the modified iron tetroxide. Among them, the mass ratio of iron tetroxide to methyl isobutyl ketone solution is 1:(20), and the mass concentration of the methyl isobutyl ketone solution is 20%.
[0044] The iron tetroxide selected is a powder with a particle size of 40 nm.
[0045] The treating agent is prepared by mixing 1,2-epoxydodecane, sodium hydroxide and deionized water. The mass ratio of 1,2-epoxydodecane, sodium hydroxide and deionized water is 1:(0.3):(12).
[0046] The auxiliary agent selected is an equal amount mixture of hydroxymethyl cellulose, guar gum and sodium alginate.
[0047] The powder is prepared by the following method: The powder selected is coconut shell powder, walnut shell powder and iron oxyhydroxide as raw materials. The mass ratio of coconut shell powder, walnut shell powder and iron oxyhydroxide is 1:(1.4):(0.6). The coconut shell powder, walnut shell powder and iron oxyhydroxide are all selected as powders with a particle size of 10 μm. After the coconut shell powder, walnut shell powder and iron oxyhydroxide are mixed evenly, they are added into a carbonization furnace. The carbonization furnace is set to have a heating rate of 8 °C / min and heated to 800 °C, and kept warm for 1 - 3 h. Nitrogen is introduced during the carbonization process to obtain the powder.
[0048] A preparation method of a high sulfur capacity iron oxyhydroxide desulfurization catalyst includes the following steps: Weigh iron oxyhydroxide and sodium hydroxide as required for kneading treatment, weigh additives, powder and auxiliary agent as required and add them to continue kneading treatment to obtain a mud. The mud is added into a reaction kettle, and deionized water is added into the reaction kettle. The mass of the deionized water is 30% of the mass of the mud. The reaction kettle is set to be heated to 160 °C and kept warm for reaction for 30 h. After the heat preservation reaction is completed, wait until it cools to room temperature. The obtained product is washed, filtered, dried and crushed to obtain the high sulfur capacity iron oxyhydroxide desulfurization catalyst.
[0049] Comparative Example 1. The difference between this comparative example and Example 1 is that: In this comparative example, an equal amount of coconut shell powder is selected to replace the powder.
[0050] Comparative Example 2. The difference between this comparative example and Example 1 is that: In this comparative example, an equal amount of iron tetroxide is selected to replace the additive.
[0051] Comparative Example 3. The difference between this comparative example and Example 1 is that: This comparative example does not contain an additive.
[0052] Comparative Example 4: The difference between this comparative example and Example 1 is that this comparative example does not contain powder materials.
[0053] Performance test: Performance tests were carried out on the high sulfur capacity iron oxyhydroxide desulfurization catalysts prepared in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4. The obtained test data are recorded in the following table: It can be seen that the breakthrough sulfur capacity performance and specific surface area performance of the high sulfur capacity iron oxyhydroxide desulfurization catalysts prepared in Comparative Examples 1, 2, 3, and 4 are lower than those in Examples 1, 2, and 3. This shows that: during the preparation process of the high sulfur capacity iron oxyhydroxide desulfurization catalyst, by adding additives, using methyl isobutyl ketone solution as a dispersant and combining 1,2-epoxydodecane in the treatment agent, the surface energy of the magnetite particles can be reduced, the agglomeration phenomenon of the magnetite particles can be inhibited, the exposure of their active sites can be increased, the specific surface area and reaction activity can be improved. The addition of ethylenediamine can act as a bridging agent, and through the coordination of amino groups with graphene oxide and magnetite, a three-dimensional network structure is formed, further improving the specific surface area performance of the material, and thus improving its sulfur capacity performance. By adding various fine particle materials in the powder, coconut shell powder and walnut shell powder can generate a high-porosity carbon skeleton after carbonization, providing a large specific surface area and hierarchical pores, promoting the diffusion and adsorption of sulfides. Through the preloading treatment of iron oxyhydroxide, iron oxyhydroxide is uniformly embedded in the carbon matrix during the carbonization process, forming a composite support with enriched active sites, further improving the sulfur capacity upper limit of the material.
[0054] By comparing and analyzing the relevant data in the table, it can be known that the high sulfur capacity iron oxyhydroxide desulfurization catalyst prepared by the present invention not only has good breakthrough sulfur capacity performance but also has excellent specific surface area performance. This shows that the high sulfur capacity iron oxyhydroxide desulfurization catalyst provided by the present invention has a broader market prospect and is more suitable for promotion.
[0055] In the description of this specification, the descriptions referring to terms such as "one embodiment", "example", "specific example", etc. mean that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.
[0056] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific embodiments described. Obviously, many modifications and variations can be made according to the content of this specification. These embodiments are selected and specifically described in this specification in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.
Claims
1. A high sulfur capacity iron oxyhydroxide desulfurization catalyst, characterized in that: The method comprises the following raw materials in percentage by weight: 30-40% ferric oxyhydroxide, 20-30% sodium hydroxide, 10-20% additives, 4-6% powder, and the remainder is auxiliary agent; The raw materials of the additive are composed of graphene oxide, modified ferrosoferric oxide and ethylenediamine; The raw materials of the modified ferroferric oxide are composed of ferroferric oxide, methyl isobutyl ketone solution and a treating agent.
2. The high sulfur capacity iron oxyhydroxide desulfurization catalyst according to claim 1, characterized in that: The additive is prepared by the following method: graphene oxide and modified ferroferric oxide are added to a beaker, wherein the mass ratio of the graphene oxide to the modified ferroferric oxide is 1:(0.4-0.6), deionized water is added to the beaker, a magnetic stirrer is set at 160-200 r / min for stirring for 16-20 min, an ultrasonic treatment is performed on the obtained product after the stirring is completed, the ultrasonic treatment is set at 200-300 W, and the treatment time is 12-16 min, the product obtained by the ultrasonic treatment is transferred to a beaker, a magnetic stirrer is set at 300-500 r / min, ethylenediamine is slowly added dropwise during the stirring process, and after the addition of ethylenediamine is completed, the magnetic stirrer is set at 500-600 r / min for stirring for 1-3 h, the product obtained by stirring is added to a reactor, the reactor is set to be heated to 60-80° C., the stirring speed is 160-200 r / min, and the heat preservation stirring treatment is set for 20-30 min.
3. The high sulfur capacity iron oxyhydroxide desulfurization catalyst according to claim 2, characterized in that: The product obtained by stirring and heat preservation in the reaction kettle is cooled to room temperature, and then immersed in deionized water for immersion and washing for 4 to 6 times, with each immersion time being 40 to 60 minutes, to obtain the additive.
4. The high sulfur capacity iron oxyhydroxide desulfurization catalyst according to claim 3, characterized in that: The mass of the deionized water is 60-80% of the mass of the graphene oxide, and the mass of the ethylenediamine is 6-8% of the mass of the graphene oxide.
5. The high sulfur capacity iron oxyhydroxide desulfurization catalyst according to claim 1, characterized in that: The modified ferrosoferric oxide is prepared by the following method: ferrosoferric oxide and methyl isobutyl ketone solution are added into a reaction kettle, a treatment agent is added into the reaction kettle, the temperature of the reaction kettle is set to rise to 80-120° C., the stirring speed is 200-300 r / min, and the heat preservation stirring treatment is set for 20-30 min. The obtained product is centrifuged and washed, and then sent into an oven, and the oven is set at 60-70° C. for drying for 2-4 h to obtain the modified ferrosoferric oxide, wherein the mass ratio of ferrosoferric oxide to methyl isobutyl ketone solution is 1:(10-20), and the mass concentration of methyl isobutyl ketone solution is 10-20%.
6. The high sulfur capacity iron oxyhydroxide desulfurization catalyst according to claim 5, characterized in that: The ferroferric oxide is powdered material with a particle size of 20 to 40 nm.
7. The high sulfur capacity iron oxyhydroxide desulfurization catalyst according to claim 5, characterized in that: The treating agent is prepared by mixing 1,2-epoxydodecane, sodium hydroxide and deionized water, wherein the mass ratio of the 1,2-epoxydodecane, sodium hydroxide and deionized water is 1:(0.1-0.3):(10-12).
8. The high sulfur capacity iron oxyhydroxide desulfurization catalyst according to claim 1, characterized in that: The auxiliary agent is a mixture of equal amounts of hydroxymethyl cellulose, guar gum and sodium alginate.
9. The high sulfur capacity iron oxyhydroxide desulfurization catalyst according to claim 1, characterized in that: The powder is prepared by the following method: coconut shell powder, walnut shell powder and hydroxyl iron are selected as raw materials, the mass ratio of the coconut shell powder, walnut shell powder and hydroxyl iron is 1: (1.2-1.4): (0.4-0.6), the coconut shell powder, walnut shell powder and hydroxyl iron are all selected as powders with a particle size of 4-10 μm, the coconut shell powder, walnut shell powder and hydroxyl iron are mixed and then added to a carbonization furnace, the carbonization furnace is set to a heating rate of 6-8°C / min, the temperature is raised to 600-800°C, and the temperature is kept for 1-3 hours, and nitrogen is introduced during the carbonization process to obtain the powder.
10. A method for preparing a high sulfur capacity iron oxyhydroxide desulfurization catalyst according to any one of claims 1 to 9, characterized in that: The following steps are involved: Weigh ferric hydroxide and sodium hydroxide as needed and knead them, weigh additives, powders and auxiliaries as needed and add them to continue kneading to obtain mud, add the mud into a reactor, add deionized water into the reactor, the mass of the deionized water is 20-30% of the mass of the mud, set the reactor to heat up to 100-160°C, keep the reaction warm for 20-30h, after the reaction is finished, wait for cooling to room temperature, wash, filter, dry and crush the product to obtain a high sulfur capacity ferric hydroxide desulfurization catalyst.