A modified carbon-based catalyst for the synergistic catalytic hydrolysis of COS and CS2, its preparation method and application

Abstract

This invention relates to a modified carbon-based catalyst for the synergistic catalytic hydrolysis of COS and CS2, its preparation method, and its application. The catalyst is composed of activated carbon and titanium dioxide, wherein the titanium dioxide content is 40-70% by mass. The preparation method is as follows: first, the activated carbon is pretreated to remove impurities; then, nano-titanium dioxide is prepared by the sol-gel method; finally, the pretreated activated carbon and nano-titanium dioxide are mixed, ground, filtered, extruded, dried, and calcined to obtain the hydrolysis catalyst. Compared with the prior art, the preparation method of this invention is simple, and the obtained catalyst can simultaneously catalyze the hydrolysis of COS and CS2. The titanium dioxide is uniformly dispersed on the activated carbon support, exhibiting high resistance to toxicity. The hierarchical porous structure of the activated carbon facilitates the adsorption and mass transfer of reactant gases, maintaining stable hydrolysis activity even at high throughput. It can be used for the removal of COS and CS2 from blast furnace gas and coke oven gas in industrial applications.

Description

Technical Field

[0001] This invention relates to the field of desulfurization technology, specifically to a modified carbon-based catalyst for synergistic catalytic hydrolysis of COS and CS2, its preparation method, and its application. Background Technology

[0002] Carbonyl sulfide (COS) and carbon disulfide (CS2) are two types of highly toxic, corrosive, and relatively stable organic sulfur gases, widely present in feedstock gases from chemical production using coal, petroleum, and natural gas. These organic sulfides cause equipment corrosion and catalyst poisoning during industrial processes, and if released into the atmosphere without treatment, they can further oxidize and produce acid rain, posing significant threats to human health and the environment. Therefore, research on the fine removal processes of carbonyl sulfide and carbon disulfide is of great importance. Currently, hydrolysis is widely used for the removal of COS and CS2 from industrial feedstock gases and industrial waste gases due to its advantages such as high catalytic efficiency, low energy consumption, and few byproducts. Hydrolysis involves reacting COS and CS2 with H2O to produce H2S and CO2, followed by the removal of H2S.

[0003] Because COS and CS2 have low reactivity, they require a catalyst for effective hydrolysis. Currently, industrially, catalysts such as alumina, titanium dioxide, and other metal oxides supported on active components, or activated carbon-based catalysts, are commonly used to catalyze the hydrolysis of COS and CS2. Industrial gases such as coke oven gas have complex compositions, containing not only organic sulfur gases such as COS, CS2, thiophene, and methanethiol, but also gases like oxygen and carbon dioxide that can cause competitive adsorption. Due to the presence of O2 during the reaction, the H2S generated during hydrolysis, if not promptly removed, is easily oxidized into elemental sulfur and sulfate deposits. Elemental sulfur easily covers the active components and blocks mass transfer channels, while sulfates, being acidic, can destroy the base active sites, thus reducing catalyst activity.

[0004] CN102600850A discloses a method for preparing an activated carbon-based catalyst that simultaneously removes carbonyl sulfide and carbon disulfide. This method uses microwave-activated carbon as a support and alkaline substances and metal oxides as active components to prepare an activated carbon-based catalyst capable of simultaneously removing carbonyl sulfide and carbon disulfide. This catalyst can simultaneously remove COS and CS2 from gases at relatively low temperatures (30–90°C), along with their byproducts. The method is simple, easy to operate, and has low operating costs. It achieves high COS and CS2 removal efficiencies, with conversion rates exceeding 90% for both. However, this catalyst has two drawbacks: firstly, the inorganic sulfates formed by the catalytic oxidation of H2S may deposit on the catalyst surface and consume the active components; secondly, the presence of a carbon support can easily lead to carbon buildup, clogging the catalyst pores. Both of these factors contribute to a decrease in catalyst activity. Summary of the Invention

[0005] The purpose of this invention is to provide a modified carbon-based catalyst for the synergistic catalytic hydrolysis of COS and CS2, its preparation method and application, which effectively improves the hydrolysis catalytic activity of COS and CS2.

[0006] The objective of this invention can be achieved through the following technical solution: a modified carbon-based catalyst for the synergistic catalytic hydrolysis of COS and CS2, wherein the catalyst is composed of activated carbon and titanium dioxide, wherein titanium dioxide accounts for 40-70% of the mass percentage of the catalyst.

[0007] Alumina-based catalysts are prone to sulfate deposition, while titanium dioxide exhibits better sulfate resistance but poor sulfur resistance. The small specific surface area and pore size of titanium dioxide limit its catalytic activity. Activated carbon, as a porous material, possesses not only a large specific surface area and abundant porosity but also a wide range of tunable surface properties. The catalyst of this invention consists of activated carbon and titanium dioxide. On one hand, the titanium dioxide loading enhances the catalyst's anti-poisoning performance; on the other hand, the activated carbon disperses the titanium dioxide particles, mitigating the problems of small specific surface area and small pore volume of titanium dioxide, thus improving hydrolysis performance.

[0008] A method for preparing the modified carbon-based catalyst that synergistically catalyzes the hydrolysis of COS and CS2 involves adding nano-titanium dioxide and pretreated activated carbon to a mixed solvent of ethanol, deionized water, and nitric acid, stirring vigorously at room temperature, grinding, and drying overnight to obtain a powder. The powder is then mixed with additives, extruded into shape, dried, and calcined to obtain the catalyst.

[0009] Preferably, the stirring speed is 500-1000 rpm, and the stirring time is 2-4 hours.

[0010] Preferably, the specific surface area of ​​the pretreated activated carbon is >200 m². 2 / g, pore volume 0.1~1cm 3 / g.

[0011] More preferably, the specific surface area of ​​the pretreated activated carbon is >1000 m². 2 / g, pore volume 0.4~1cm 3 / g.

[0012] Preferably, the average pore size of the pretreated activated carbon is 2-10 nm.

[0013] Preferably, the pretreatment process includes calcination at 300–400°C in a nitrogen atmosphere for 2–3 hours.

[0014] More preferably, the activated carbon is first rinsed 2-3 times with deionized water and ethanol, dried in an oven at 70-90°C, and then calcined at 300-400°C under a nitrogen atmosphere for 2-3 hours.

[0015] Preferably, the nano-titanium dioxide is prepared by the sol-gel method.

[0016] More preferably, the preparation method of the nano-titanium dioxide is as follows: dissolving titanium alkoxide in the corresponding alcohol to prepare a precursor solution, then adding the precursor solution to distilled water and mixing, stirring vigorously, adjusting the pH to 2-4 with an acid solution, aging, filtering the precipitate and washing it with ethanol, and vacuum drying at 90-110℃ for 2-3 hours to obtain powder, and finally annealing the prepared powder for 2-3 hours to obtain nano-titanium dioxide.

[0017] More preferably, the stirring speed is 500-1000 rpm, and the stirring time is 2-4 hours.

[0018] More preferably, the titanium alkoxide is one of titanium isopropoxide, titanium butoxide, and titanium ethoxide.

[0019] More preferably, the alcohol is one of isopropanol, butanol, or ethanol.

[0020] More preferably, the volume ratio of the alcohol to the titanium alkoxide is 2 to 4:1.

[0021] More preferably, the volume ratio of distilled water to precursor solution is 5 to 8:1.

[0022] More preferably, the acid solution is either nitric acid or acetic acid.

[0023] More preferably, the aging temperature is 60-80℃ and the aging time is 15-20h, and more preferably the aging temperature is 60-70℃ and the aging time is 18-20h.

[0024] More preferably, the annealing temperature is 200–800°C.

[0025] Preferably, the mixed solvent contains 75-80% ethanol by volume, 15-20% deionized water by volume, 2-5% nitric acid by volume, and the concentration of nitric acid is 0.5-1.5 mol / L.

[0026] Preferably, the catalyst is obtained by mixing and extruding the powder with the additives, drying at 70-90°C, and calcining at 300-400°C for 2-4 hours (preferably 2-3 hours).

[0027] Preferably, the additive is an aqueous solution of sawdust and binder.

[0028] More preferably, the binder is one or more of sodium carboxymethyl cellulose, chlorocalcium, bentonite, clay, phenolic resin, and coal tar.

[0029] More preferably, the sawdust accounts for 2% to 15% of the total mass of the additives, the adhesive aqueous solution accounts for 10% to 40% of the total mass of the additives, and the adhesive accounts for 10% to 50% of the mass of the adhesive aqueous solution.

[0030] More preferably, the extrusion molding is carried out at room temperature using a small single-screw extruder with an extrusion rate of 0.1 to 0.3 m / min and a pipe diameter of 2 to 6 mm.

[0031] This invention first pretreats activated carbon to remove impurities; then prepares nano-titanium dioxide using the sol-gel method; finally, mixes the pretreated activated carbon with nano-titanium dioxide, grinds, filters, extrudes, dries, and calcines to obtain a hydrolysis catalyst.

[0032] The application of a modified carbon-based catalyst that synergistically catalyzes the hydrolysis of COS and CS2, wherein the catalyst is used for the removal of carbonyl sulfur and carbon disulfide from blast furnace gas and coke oven gas.

[0033] The preparation method of this invention is simple, and the resulting catalyst can simultaneously catalyze the hydrolysis of COS and CS2. Titanium dioxide is uniformly dispersed on the activated carbon support and has high resistance to poisoning. The hierarchical porous structure of the activated carbon helps the adsorption and mass transfer of reactant gases and can maintain stable hydrolysis activity even at high throughput. It can be used for the removal of COS and CS2 from blast furnace gas and coke oven gas in industry.

[0034] Compared with the prior art, the present invention has the following advantages:

[0035] 1. The catalyst preparation method of the present invention is relatively simple and can effectively improve the hydrolysis catalytic activity of COS and CS2; it can solve the problems of low hydrolysis activity of COS and CS2, short catalyst life, and difficulty in removing CS2 when impurities are present.

[0036] 2. The specific surface area and pore volume of the catalyst after molding of the present invention decrease simultaneously, but the average pore size does not change significantly; the oxygen-containing functional groups on the surface of the pretreated activated carbon and the amorphous carbon in the catalyst after molding have a promoting effect on the catalytic hydrolysis of COS and CS2.

[0037] 3. The preparation method of this invention is simple. Activated carbon and titanium dioxide have a certain synergistic effect. On the one hand, the loading of titanium dioxide enhances the catalyst's anti-poisoning performance. On the other hand, activated carbon disperses titanium dioxide particles, improving the problems of small specific surface area and small pore volume of titanium dioxide, thereby improving the hydrolysis performance.

[0038] 4. The activated carbon selected in this invention has a hierarchical pore structure of macropores, mesopores and micropores, which increases the probability of contact between active sites and reactants, facilitates the adsorption of reactants and the diffusion of product gases in the pores, makes the pores less prone to clogging, slows down sulfate deposition, and extends the catalyst life. Attached Figure Description

[0039] Figure 1 The image shows the isothermal adsorption-desorption curves of activated carbon after pretreatment in Example 1 of this invention.

[0040] Figure 2 This is a DFT pore size distribution diagram of the activated carbon after pretreatment in Example 1 of the present invention.

[0041] Figure 3 The isothermal adsorption-desorption curves of the catalyst in Example 1 of this invention are shown.

[0042] Figure 4 This is a DFT pore size distribution diagram of the catalyst in Example 1 of the present invention. Detailed Implementation

[0043] The embodiments of the present invention will be described in detail below. The following embodiments are implemented based on the technical solution of the present invention, and detailed implementation methods and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0044] In the following examples, the activated carbon was purchased from Shanghai Tongzhu Chemical Technology Co., Ltd., and was 100-200 mesh wood powder with high adsorption regenerated carbon.

[0045] Example 1

[0046] The activated carbon was first rinsed three times with deionized water and ethanol, dried in an oven at 80°C, and then dried at 5°C for 5 minutes. -1 The temperature was increased to 350℃ at a heating rate, and calcined for 2 hours. The isothermal adsorption-desorption curves of the pretreated activated carbon are shown below. Figure 1 As shown, the DFT aperture distribution is as follows: Figure 2 As shown, the specific surface area of ​​the pretreated activated carbon is 1105 m². 2 / g, pore volume 0.78m 3 / g, average pore size 2.7nm.

[0047] A titanium precursor solution was prepared by dissolving 10 ml of titanium isopropoxide in 30 ml of isopropanol. This precursor solution was then added to 250 ml of distilled water for hydrolysis. HNO3 was added to adjust the pH to 3, and the solution was stirred vigorously and heated to 60°C for aging for approximately 18 hours. The precipitate was filtered, washed with ethanol, and dried under vacuum at 100°C for 2 hours to obtain a powder. Finally, the prepared powder was annealed at 400°C under a nitrogen atmosphere for 2 hours.

[0048] 2g of pretreated activated carbon and 2g of titanium dioxide were mixed in a mixed solvent of 15mL ethanol, 4mL deionized water and 1mL 1mol / L HNO3, stirred vigorously at room temperature, and ground. The mixture was then dried overnight in an oven at 80℃ to obtain a powder. The powder was extruded with additives, dried, and then dried at 5℃ for 1 minute. -1 The temperature was increased to 350℃ at a heating rate, and then calcined at 350℃ in a nitrogen atmosphere for 2 hours. The isothermal adsorption-desorption curve of the obtained catalyst is shown below. Figure 3 As shown, the DFT aperture distribution is as follows: Figure 4 As shown, the catalyst has a specific surface area of ​​653 m². 2 / g, pore volume 0.34m 3 / g, average pore size 4.5nm.

[0049] Catalyst activity test:

[0050] The obtained catalyst was used to simultaneously catalyze the hydrolysis of COS and CS2. An appropriate amount of catalyst was loaded into a fixed-bed reactor, and the reaction conditions were: COS concentration 210 mg / m³. 3 CS2 concentration 110 mg / m³ 3 The reaction temperature was 100℃ and the space velocity was 5000 h⁻¹. -1 With an oxygen content of 0.8% and a reaction time of 720 min, the average COS conversion rate was 99%, and the average CS2 conversion rate was 49%.

[0051] Example 2

[0052] The activated carbon was first rinsed three times with deionized water and ethanol, dried in an oven at 80°C, and then dried at 5°C for 5 minutes. -1 The temperature was increased to 350℃ at a heating rate, and calcined for 2 hours. The specific surface area was 1042 m². 2 / g, pore volume 0.68m 3 / g.

[0053] A titanium precursor solution was prepared by dissolving 10 ml of titanium butoxide in 30 ml of butanol. This precursor solution was then added to 250 ml of distilled water for hydrolysis. HNO3 was added to adjust the pH of the solution to 2, and the mixture was stirred vigorously and heated to 70°C for aging for approximately 20 hours. The precipitate was filtered, washed with ethanol, and dried under vacuum at 100°C for 2 hours to obtain a powder. Finally, the prepared powder was annealed at 500°C under a nitrogen atmosphere for 3 hours.

[0054] 2g of pretreated activated carbon and 2g of titanium dioxide were mixed in a mixed solvent of 20mL ethanol, 5mL deionized water and 1mL 1mol / L HNO3, stirred vigorously at room temperature, and ground. The mixture was then dried overnight in an oven at 80℃ to obtain a powder. The powder was extruded with additives, dried, and then dried at 5℃ for 1 minute. -1The temperature was increased to 400℃ at a heating rate, and then calcined at 400℃ in a nitrogen atmosphere for 3 hours. The catalyst has a specific surface area of ​​526 m². 2 / g, pore volume is 0.29m 3 / g.

[0055] Catalyst activity test:

[0056] The obtained catalyst was used to simultaneously catalyze the hydrolysis of COS and CS2. An appropriate amount of catalyst was loaded into a fixed-bed reactor, and the reaction conditions were: COS concentration 210 mg / m³. 3 CS2 concentration 110 mg / m³ 3 The reaction temperature was 90℃ and the space velocity was 5000 h⁻¹. -1 The oxygen content was 0.8%, the reaction time was 720 min, the average COS conversion rate was 99%, and the average CS2 conversion rate was 45%.

[0057] Example 3

[0058] The activated carbon was first rinsed three times with deionized water and ethanol, dried in an oven at 80°C, and then dried at 5°C for 5 minutes. -1 The temperature was increased to 350℃ at a heating rate, and calcined for 2 hours. The specific surface area was 1034 m². 2 / g, pore volume is 0.69m 3 / g.

[0059] A titanium precursor solution was prepared by dissolving 10 ml of titanium butoxide in 30 ml of butanol. This precursor solution was then added to 250 ml of distilled water for hydrolysis. HNO3 was added to adjust the pH of the solution to 2, and the mixture was stirred vigorously and heated to 70°C for aging for approximately 20 hours. The precipitate was filtered, washed with ethanol, and dried under vacuum at 100°C for 2 hours to obtain a powder. Finally, the prepared powder was annealed at 500°C under a nitrogen atmosphere for 3 hours.

[0060] 2g of pretreated activated carbon and 3g of titanium dioxide were mixed in a mixed solvent of 20mL ethanol, 5mL deionized water and 1mL 1mol / L HNO3, stirred vigorously at room temperature, and ground. The mixture was then dried overnight in an oven at 80℃ to obtain a powder. The powder was extruded with additives, dried, and then dried at 5℃ for 1 minute. -1 The temperature was increased to 500℃ at a heating rate, and then calcined at 500℃ in a nitrogen atmosphere for 3 hours. The catalyst has a specific surface area of ​​426 m². 2 / g, pore volume 0.24m 3 / g.

[0061] Catalyst activity test:

[0062] The obtained catalyst was used to simultaneously catalyze the hydrolysis of COS and CS2. An appropriate amount of catalyst was loaded into a fixed-bed reactor, and the reaction conditions were: COS concentration 210 mg / m³.3 CS2 concentration 110 mg / m³ 3 The reaction temperature was 90℃ and the space velocity was 5000 h⁻¹. -1 With an oxygen content of 0.8% and a reaction time of 720 min, the average COS conversion rate was 98%, and the average CS2 conversion rate was 40%.

[0063] Comparative Example 1

[0064] A titanium precursor solution was prepared by dissolving 10 ml of titanium isopropoxide in 30 ml of isopropanol. This precursor solution was then added to 250 ml of distilled water for hydrolysis. HNO3 was added to adjust the pH to 3, and the solution was stirred vigorously and heated to 60°C for aging for approximately 18 hours. The precipitate was filtered, washed with ethanol, and dried under vacuum at 100°C for 2 hours to obtain a powder. Finally, the prepared powder was annealed at 400°C under a nitrogen atmosphere for 2 hours.

[0065] 2g of activated carbon and 2g of titanium dioxide were mixed in a mixed solvent of 15mL ethanol, 4mL deionized water and 1mL 1mol / L HNO3. The mixture was stirred vigorously at room temperature and ground. The mixture was then dried overnight in an oven at 80℃ to obtain a powder. The powder was extruded with additives, dried, and then dried at 5℃ for 1 minute. -1 The temperature was increased to 450℃ at a heating rate, and then calcined at 450℃ in a nitrogen atmosphere for 2 hours. The catalyst has a specific surface area of ​​314 m². 2 / g, pore volume is 0.19m 3 / g

[0066] Catalyst activity test:

[0067] The obtained catalyst was used to simultaneously catalyze the hydrolysis of COS and CS2. An appropriate amount of catalyst was loaded into a fixed-bed reactor, and the reaction conditions were: COS concentration 210 mg / m³. 3 CS2 concentration 110 mg / m³ 3 The reaction temperature was 100℃ and the space velocity was 5000 h⁻¹. -1 The oxygen content was 0.8%, the reaction time was 720 min, the average COS conversion rate was 63%, and the average CS2 conversion rate was 25%.

[0068] Compared to Example 1, the difference lies in that the activated carbon is not pretreated. Pretreatment removes impurities adsorbed by the activated carbon, which may affect the final desulfurization effect, leading to side reactions and catalyst deactivation. Pretreatment also activates the activated carbon, expanding its pores, increasing specific surface area and pore volume, and improving its microstructure.

[0069] Comparative Example 2

[0070] A titanium precursor solution was prepared by dissolving 10 ml of titanium isopropoxide in 30 ml of isopropanol. This precursor solution was then added to 250 ml of distilled water for hydrolysis. HNO3 was added to adjust the pH to 3, and the solution was stirred vigorously and heated to 60°C for aging for approximately 18 hours. The precipitate was filtered, washed with ethanol, and dried under vacuum at 100°C for 2 hours to obtain a powder. Finally, the prepared powder was annealed at 400°C under a nitrogen atmosphere for 2 hours to obtain a titanium dioxide catalyst. The catalyst had a specific surface area of ​​35.2 m². 2 / g, pore volume 0.02m 3 / g.

[0071] Catalyst activity test:

[0072] The obtained catalyst was used to simultaneously catalyze the hydrolysis of COS and CS2. An appropriate amount of catalyst was loaded into a fixed-bed reactor, and the reaction conditions were: COS concentration 210 mg / m³. 3 CS2 concentration 110 mg / m³ 3 The reaction temperature was 100℃ and the space velocity was 5000 h⁻¹. -1 The oxygen content was 0.8%, the reaction time was 600 min, the average COS conversion rate was 11%, and the average CS2 conversion rate was 2%.

[0073] Although pure titanium dioxide can act as a catalyst, it is limited by its small specific surface area, insufficient pore volume, poor catalytic effect, short catalyst life, and high compressive strength, making it difficult to form and thus hindering industrial applications.

[0074] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. The application of a modified carbon-based catalyst for the synergistic catalytic hydrolysis of COS and CS2, characterized in that, Modified carbon-based catalysts are used for the removal of carbonyl sulfur and carbon disulfide from blast furnace gas and coke oven gas. The catalyst is composed of activated carbon and titanium dioxide, wherein the titanium dioxide accounts for 40-70% by mass. The catalyst is prepared by adding nano-titanium dioxide and pretreated activated carbon into a mixed solvent of ethanol, deionized water and nitric acid, stirring, grinding and drying at room temperature to obtain powder, mixing and extruding the powder with additives, drying at 70~90℃ and calcining at 300~400℃ to obtain the catalyst. The specific surface area of ​​the pretreated activated carbon is >200m². 2 / g, pore volume 0.1~1cm 3 / g; The pretreatment process includes calcination at 300~400℃ in a nitrogen atmosphere for 2~3 hours; The nano-titanium dioxide was prepared by the sol-gel method. The preparation method is as follows: titanium alkoxide was dissolved in the corresponding alcohol to prepare a precursor solution. Then, the precursor solution was added to distilled water and mixed. The mixture was stirred vigorously, and the pH was adjusted to 2-4 with an acid solution. The mixture was aged, and the precipitate was filtered, washed with ethanol, and vacuum dried at 90-110℃ for 2-3 h to obtain powder. Finally, the prepared powder was annealed for 2-3 h to obtain nano-titanium dioxide. The mixed solvent contains 75-80% ethanol by volume, 15-20% deionized water by volume, 2-5% nitric acid by volume, and the concentration of nitric acid is 0.5-1.5 mol / L. The additive is a mixture of wood chips and an aqueous solution of a binder; the binder is one or more of sodium carboxymethyl cellulose and phenolic resin, wherein the wood chips account for 2% to 15% of the total mass of the additive, the aqueous solution of the binder accounts for 10% to 40% of the total mass of the additive, and the binder accounts for 10% to 50% of the mass of the aqueous solution of the binder.

2. The application of the modified carbon-based catalyst for the synergistic catalytic hydrolysis of COS and CS2 according to claim 1, characterized in that, The titanium alkoxide is one of titanium isopropoxide, titanium butoxide, and titanium ethoxide; The alcohol is one of isopropanol, butanol, or ethanol; The volume ratio of the alcohol to the titanium alkoxide is 2~4:

1.

3. The application of the modified carbon-based catalyst for the synergistic catalytic hydrolysis of COS and CS2 according to claim 1, characterized in that, The volume ratio of distilled water to precursor solution is 5~8:

1.

4. The application of the modified carbon-based catalyst for the synergistic catalytic hydrolysis of COS and CS2 according to claim 1, characterized in that, The acid solution is either nitric acid or acetic acid.

5. The application of the modified carbon-based catalyst for the synergistic catalytic hydrolysis of COS and CS2 according to claim 1, characterized in that, The aging temperature is 60-80℃ and the aging time is 15-20 hours.

6. The application of the modified carbon-based catalyst for the synergistic catalytic hydrolysis of COS and CS2 according to claim 1, characterized in that, The annealing temperature is 200~800℃.

7. The application of the modified carbon-based catalyst for the synergistic catalytic hydrolysis of COS and CS2 according to claim 1, characterized in that, The extrusion molding is carried out at room temperature using a single-screw extruder with an extrusion rate of 0.1~0.3m / min and a tube diameter of 2~6mm.

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