Manganese-containing graphene composite material, and preparation method and use thereof

Abstract

This disclosure relates to a manganese-containing graphene composite material, its preparation method, and its uses. The method includes: mixing graphite, potassium permanganate, and concentrated acid, heating and reacting them, then adding water and stirring to obtain a mixed solution; mixing the mixed solution with optional hydrogen peroxide, and refluxing it under intermittent ultrasonic stirring, so that the resulting material is separated into solid and liquid phases to obtain a solid product; calcining the solid product under an inert atmosphere; the intermittent ultrasonic stirring step includes: (1) ultrasonic stirring for 5-30 min and then stopping for 10-60 min; (2) repeating step (1). The manganese-containing graphene composite material provided by this invention contains elements such as manganese, potassium, and sulfur. By refluxing under intermittent ultrasonic stirring, this invention enables the manganese-containing graphene composite material to have a large specific surface area, exhibiting excellent performance in reactions such as the removal of sulfur-containing compounds. On the other hand, the content of manganese ions and other substances in the wastewater is significantly reduced during the preparation process, effectively solving the problem of wastewater discharge pollution.

Description

Technical Field

[0001] This disclosure pertains to the field of graphene materials, specifically relating to a manganese-containing graphene composite material, its preparation method, and its applications. Background Technology

[0002] Graphite is an important raw material and product of carbon materials, and a crucial raw material for the preparation of popular downstream products such as reduced graphene and graphene oxide. Currently, the main method for preparing graphene is to oxidize graphite using strong oxidants such as potassium permanganate. However, this method generates wastewater with high concentrations of manganese ions, which, if directly discharged, would cause environmental pollution and significant environmental pressure. Whether the manganese ions in the wastewater from graphene preparation can be transformed into a valuable resource is an important issue that scientists need to consider and solve. Furthermore, whether novel manganese-containing composite materials can be prepared through technological innovation during the graphene preparation process is another possible solution, but related reports are scarce. Summary of the Invention

[0003] The purpose of this invention is to provide a manganese-containing graphene composite material, its preparation method, and its applications. The manganese-containing graphene composite material prepared by this invention contains elements such as manganese, potassium, and sulfur, and has a large specific surface area. It exhibits excellent performance and good removal efficiency in reactions such as the removal of sulfur-containing compounds. The preparation method provided by this invention can effectively reduce the content of manganese ions in wastewater, solving a series of environmental pollution problems.

[0004] To achieve the above objectives, a first aspect of the present invention provides a method for preparing a manganese-containing graphene composite material, the method comprising: S1. Mix graphite, potassium permanganate and concentrated acid, heat and react, then add water and stir to obtain a mixed solution; S2. Mix the mixture with optional hydrogen peroxide and reflux it under intermittent ultrasonic stirring. Separate the resulting material into a solid product. S3. The solid product is calcined under an inert atmosphere; The intermittent ultrasonic stirring step includes: (1) ultrasonic stirring for 5-30 minutes and then stopping for 10-60 minutes; (2) repeating step (1) in a cycle.

[0005] Optionally, the graphite is one or more of natural flake graphite, natural cryptocrystalline graphite, and artificial graphite; The graphite has a carbon content of 95% or more by weight, an ash content of less than 5%, and a mesh size of 20 to 1000 mesh.

[0006] Optionally, the concentrated acid is selected from one or more of sulfuric acid, nitric acid, and perchloric acid; C0 is any concentration between C-10% and C+10%, preferably any concentration between C-5% and C+5%, where C0 is the concentration of the concentrated acid and C is the highest concentration of the concentrated acid in analytical grade reagent.

[0007] Optionally, in step S1, the mass ratio of concentrated acid, potassium permanganate and graphite is (25~80):(3~8):1.

[0008] Optionally, the method further includes: in step S2, mixing the mixture with hydrogen peroxide; the mass ratio of the mixture to hydrogen peroxide is 1:(0.1~10); the mass concentration of hydrogen peroxide is 0.1~5%, preferably 0.2~2%.

[0009] Optionally, in step S2, the intermittent ultrasonic stirring method is one or more of probe-type ultrasonic or water bath ultrasonic, with a power of 50~500W / h and a stirring time of 0.1~12h; the reflux reaction conditions include a temperature of 120~180℃ and a time of 6~48h.

[0010] Optionally, in step S1, the mixing temperature is below 30°C, preferably below 20°C, and more preferably below 10°C; the mixing time is 0.5~12h. The conditions for the heating reaction are: temperature 35~60℃, time 0.2~6h; The stirring time for adding water is 0.1~5h; the mass ratio of water to graphite is (50~250):1. In step S3, the calcination treatment is carried out at a temperature of 400~1000℃ for a time of 0.1~24h.

[0011] A second aspect of the present invention provides a manganese-containing graphene composite material prepared using the method provided in the first aspect of the present invention.

[0012] Optionally, the manganese-containing graphene composite material contains manganese, carbon, oxygen, potassium, and sulfur. Specifically, the content of Mn (calculated as MnO2) in the manganese-containing graphene composite material is 55-90% by weight; the content of sulfur (calculated as SO2) is 0.5-10% by weight; and the content of potassium (calculated as K2O) is 1-15% by weight. The XRD pattern of the manganese-containing graphene composite material contains characteristic peaks of α-MnO2 and graphene. The specific surface area of ​​the manganese-containing graphene composite material is 300~800 m². 2 / g, preferably 400~600m 2 / g, pore volume is 0.5~2ml / g, preferably 0.8~1.5ml / g, and average particle size is less than 1mm, preferably less than 0.2mm.

[0013] The third aspect of the present invention provides the use of the manganese-containing graphene composite material of the second aspect of the present invention in the removal of sulfur-containing compounds; The sulfur-containing raw material is brought into contact with the manganese-containing graphene composite material for reaction; the conditions for the contact reaction include: temperature of 30~80℃, pressure of 1~5MPa, and space velocity of 10~1000h. -1 Preferably, the pressure is 0.5~3.0 MPa and the space velocity is 50~500 h⁻¹. -1 The sulfur-containing compound content in the raw material is less than 25%, preferably less than 10%.

[0014] Through the above technical solution, this invention involves refluxing a mixture of graphite, potassium permanganate, and concentrated acid under intermittent ultrasonic stirring, followed by calcination under an inert atmosphere to obtain a manganese-containing graphene composite material. The manganese-containing graphene composite material prepared by the method provided by this invention contains elements such as manganese, potassium, and sulfur, exhibiting excellent performance and good removal efficiency in reactions such as the removal of sulfur-containing compounds. Furthermore, by using intermittent ultrasonic stirring and reflux, this invention enables the prepared manganese-containing graphene composite material to have a large specific surface area, allowing sulfur-containing compounds to more easily contact the active centers within the manganese-containing graphene composite material during the removal process, further enhancing the removal efficiency. On the other hand, the content of manganese ions and other pollutants in the wastewater is significantly reduced during the preparation process, solving a series of problems such as environmental pollution from wastewater discharge.

[0015] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0016] The following provides a detailed description of specific embodiments of this disclosure. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit this disclosure.

[0017] The first aspect of this disclosure provides a method for preparing a manganese-containing graphene composite material, the method comprising: S1. Mix graphite, potassium permanganate and concentrated acid, heat and react, then add water and stir to obtain a mixed solution; S2. Mix the mixture with optional hydrogen peroxide and reflux it under intermittent ultrasonic stirring. Separate the resulting material into a solid product. S3. The solid product is calcined under an inert atmosphere; The intermittent ultrasonic stirring step includes: (1) ultrasonic stirring for 5-30 minutes and then stopping for 10-60 minutes; (2) repeating step (1) in a cycle.

[0018] This disclosure involves refluxing a mixture of graphite, potassium permanganate, and concentrated acid under intermittent ultrasonic stirring, followed by calcination under an inert atmosphere to obtain a manganese-containing graphene composite material. The manganese-containing graphene composite material prepared by the method provided in this disclosure contains elements such as manganese, potassium, and sulfur, and exhibits excellent performance in reactions such as the removal of sulfur-containing compounds, demonstrating good removal efficiency. Furthermore, by using intermittent ultrasonic stirring and reflux, this disclosure enables the prepared manganese-containing graphene composite material to possess a large specific surface area.

[0019] In one specific embodiment, the graphite is one or more of natural flake graphite, natural cryptocrystalline graphite, and artificial graphite, preferably cryptocrystalline graphite; the carbon content of the graphite is 95% by weight or more, preferably 99% by weight or more, the ash content is 5% or less, preferably 1% or less, and the mesh size is 20 to 1000 mesh, preferably 50 to 800 mesh.

[0020] In one specific embodiment, the concentrated acid is selected from one or more of sulfuric acid, nitric acid, and perchloric acid, preferably concentrated sulfuric acid; CO is any concentration between C-10% and C+10%, preferably any concentration between C-5% and C+5%, where CO is the concentration of the concentrated acid, and C is the highest concentration of the concentrated acid at analytical reagent grade.

[0021] In one specific embodiment, in step S1, the mass ratio of concentrated acid, potassium permanganate, and graphite is (15~100):(1~10):1, preferably (25~80):(3~8):1. In the above embodiment, controlling the mass ratio of concentrated acid, potassium permanganate, and graphite within the preferred range of this application can further improve the performance of the prepared manganese-containing graphene composite material, resulting in superior performance when used in reactions such as the removal of sulfur-containing compounds, and further enhancing the removal effect.

[0022] In one specific embodiment, the mixture is mixed with optional hydrogen peroxide, wherein the mass ratio of the mixture to the optional hydrogen peroxide is 1:(0.1~10), preferably 1:(0.5~5). In a further specific embodiment, the mass ratio of the mixture to the optional hydrogen peroxide can be 1:1, 1:2, 1:3, 1:4, 1:5, or any value between the two.

[0023] In one specific embodiment, hydrogen peroxide is added in the form of an aqueous solution with a mass concentration of 0.1-5%, preferably 0.2-2%.

[0024] In a preferred embodiment, the intermittent ultrasonic stirring step includes: (1) ultrasonic stirring for 10-20 min followed by a 20-40 min pause; (2) repeating step (1). In the above embodiments, this disclosure employs preferred intermittent ultrasonic stirring conditions, which can effectively strip graphite oxide while suppressing excessive temperature rise in the material. Especially with the addition of hydrogen peroxide, it can effectively suppress the ineffective decomposition of hydrogen peroxide, thereby improving the effective utilization rate of hydrogen peroxide. This further enhances the performance of the material prepared according to this disclosure in removing sulfur compounds during the reaction process, thereby further improving the removal rate of sulfur compounds.

[0025] In one specific embodiment, the intermittent ultrasonic stirring method is one or more of probe-type ultrasonic or water bath ultrasonic, with a power of 50~500W / h, preferably 100~300W / h; the stirring time is 0.1~12h, preferably 1~8h.

[0026] In one specific embodiment, the reflux reaction temperature is 100~200℃ and the time is 2~72h; preferably, the temperature is 120~180℃ and the time is 6~48h.

[0027] In one specific embodiment, in step S1, the mixing temperature is below 30°C, preferably below 20°C, and more preferably below 10°C; the mixing time is 0.5~12h, preferably 1~8h.

[0028] In one specific embodiment, in step S1, the heating reaction conditions are: temperature 35~60℃, time 0.2~6h; preferably, temperature 40~50℃, time 1~4h.

[0029] In one specific embodiment, in step S1, the temperature of adding water and stirring is 40~100℃, preferably 60~99℃, and the time is 0.1~5h, preferably 0.5~2h; the mass ratio of the amount of water added to the amount of graphite added is (20~500):1, preferably (50~250):1.

[0030] In one specific embodiment, in step S3, the calcination temperature is 400~1000℃, the time is 0.1~24h, and the calcination atmosphere is an inert atmosphere or a rare gas atmosphere; preferably, the temperature is 600~850℃, the time is 0.5~6h, and the calcination atmosphere is a nitrogen atmosphere.

[0031] The second aspect of this disclosure provides a manganese-containing graphene composite material prepared using the method provided in the first aspect of this disclosure.

[0032] In one specific embodiment, the manganese-containing graphene composite material contains Mn, C, O, K, and S elements. Specifically, the Mn content (calculated as MnO2) in the manganese-containing graphene composite material is 55-90% by weight, preferably 60-85% by weight; the S content (calculated as SO2) is 0.5-10% by weight, preferably 1-6% by weight; the K content (calculated as K2O) is 1-15% by weight, preferably 5-10% by weight; and the balance is C. In the above embodiment, the manganese-containing graphene composite material prepared by the method provided in this disclosure contains elements such as Mn, K, and S, and exhibits excellent performance and good removal effect in reactions such as the removal of sulfur-containing compounds.

[0033] In one specific embodiment, the XRD pattern of the manganese-containing graphene composite material contains characteristic peaks of α-MnO2 and graphene; the specific surface area of ​​the manganese-containing graphene composite material is 300~800 m². 2 / g, preferably 400~600m 2 The pore volume is 0.5~2 ml / g, preferably 0.8~1.5 ml / g, and the average particle size is less than 1 mm, preferably less than 0.2 mm. In the above embodiments, the manganese-containing graphene composite material prepared by the method provided in this disclosure has a large specific surface area. During the removal of sulfur-containing compounds, the sulfur-containing compounds are more likely to contact the active centers in the manganese-containing graphene composite material, thereby further improving the removal effect.

[0034] This disclosure provides a third aspect regarding the use of the manganese-containing graphene composite material of the second aspect of this disclosure in the conversion of sulfur-containing compounds.

[0035] In one specific embodiment, a sulfur-containing compound raw material is brought into contact with and reacted with a manganese-containing graphene composite material provided in the second aspect of this disclosure.

[0036] In one specific embodiment, the conditions for the contact reaction include: a temperature of 30~80℃, a pressure of 1~5MPa, and a space velocity of 10~1000h⁻¹. -1 Preferably, the pressure is 0.5~3.0 MPa and the space velocity is 50~500 h⁻¹. -1 The sulfur-containing compound in the raw material has a mass content of less than 25%, preferably less than 10%. The types of sulfur-containing compounds in the raw material include hydrogen sulfide and carbonyl sulfide.

[0037] The present invention will be further illustrated by the following examples, but the present invention is not limited thereto.

[0038] All reagents used in this application are commercially available analytical grade reagents. The cryptocrystalline graphite has a carbon content of 99.1% by weight, an ash content of 0.9%, and a mesh size of 80 mesh.

[0039] Example 1 S1. In a three-necked flask, 25g of potassium permanganate, 150ml of concentrated sulfuric acid (mass concentration greater than 98%) and 5g of graphite are simultaneously stirred and mixed at 10°C for 1 hour. Then, the mixture is stirred and reacted under autogenous pressure at 40°C for 2 hours. After that, 150ml of water is added, and the mixture is stirred and reacted again at 95°C for 1 hour to obtain a mixed solution. The mass ratio of concentrated acid, potassium permanganate and graphite is 40:6:1. S2. The mixture is refluxed for 24 hours under intermittent ultrasonic stirring, and the resulting material is separated into solid and liquid phases to obtain a solid product. The intermittent ultrasonic stirring steps include: (1) ultrasonic stirring for 15 minutes and then stopping for 25 minutes; (2) repeating step (1); the intermittent ultrasonic stirring method is probe-type intermittent stirring with a power of 150W / h; the reflux reaction temperature is 130℃. S3. The solid product is calcined under a nitrogen atmosphere at a temperature of 700℃ for 3 hours to obtain a manganese-containing graphene composite material.

[0040] The XRD spectrum of the manganese-containing graphene composite material prepared in Example 1 shows characteristic peaks of α-MnO2 and characteristic peaks of graphene around 20-26° (2θ).

[0041] Example 2 The preparation method in Example 1 is used, except that in step S2, 100 ml of 0.5% hydrogen peroxide aqueous solution is added to the mixture before reflux.

[0042] Example 3 The preparation method in Example 1 is used, except that in step S2, 10 ml of 5% hydrogen peroxide aqueous solution is added to the mixture before reflux.

[0043] Example 4 The preparation method in Example 1 is used, except that the reflux reaction temperature is 100°C in step S2.

[0044] Example 5 The preparation method in Example 1 was used, except that in step S2, the reflux reaction time under ultrasonic stirring was 2 hours and the ultrasonic stirring power was 500W.

[0045] Example 6 The preparation method in Example 1 was used, except that 450 ml of water was added in step S1.

[0046] Example 7 The preparation method in Example 1 is used, except that in step S1, 150 ml of concentrated nitric acid is added instead of concentrated sulfuric acid.

[0047] Example 8 The preparation method in Example 1 is adopted, except that in step S2, the intermittent ultrasonic stirring step includes: (1) ultrasonic stirring for 5 min and then stopping for 50 min; (2) repeating step (1).

[0048] Comparative Example 1 The preparation method in Example 1 was used, except that ultrasonic stirring and reflux reaction was not performed in step S2.

[0049] Comparative Example 2 The preparation method in Example 1 is used, except that in step S2, the reflux reaction is not carried out under ultrasonic stirring conditions, but under conventional mechanical stirring conditions at a speed of 250 rpm.

[0050] Comparative Example 3 The preparation method in Example 1 was used, except that step S3 was not performed, and the composite material was obtained.

[0051] Comparative Example 4 The preparation method in Example 1 is used, except that in step S2, the ultrasonic stirring of the reflux reaction is carried out under continuous ultrasonic stirring conditions instead of intermittent conditions.

[0052] Test case 380 mg of the manganese-containing graphene composite materials prepared in Examples 1-8 and Comparative Examples 1-4 of this disclosure were used as a removal agent and loaded into the isothermal section of a passivated fixed-bed microreactor with an inner diameter of 10 mm and a length of 600 mm. The reactor was filled with quartz sand both above and below. The sulfur-containing raw material contained 12000 ppm of sulfide (the carrier gas was nitrogen, and the sulfide was a 1:1 molar ratio complex of hydrogen sulfide and carbonyl sulfide), and the reaction was carried out at 40 °C and 2 MPa with a space velocity of 80 h⁻¹. -1 The sulfide removal reaction was carried out by introducing the solution. The sulfide content before and after the removal reaction was analyzed online using an online chromatogram (Shimadzu Nexis-2030, Japan) and an SCD fluorescence detector (SCD-2030), and the sulfide removal rate was calculated. The sulfide removal rate after 5 hours is shown in Table 1.

[0053] The manganese-containing graphene composite materials provided in Example 1 and Comparative Example 1 were tested as follows: The elemental composition of the samples was determined by XPS on a VGESCA-LABS X-ray photoelectron spectrometer, with Mg as the prime mover. Kα Using X-rays as a laser source, the binding energy of each element in the species on the surface of the desulfurizer is calibrated by the C1s binding energy (284.6 eV) of the carbon contaminants on the surface.

[0054] The temperature nitrogen adsorption-desorption (BET) test was performed using a JW-BK200C specific surface area and pore size analyzer from Beijing Jingwei Gaobo Co., Ltd. Specific surface area and pore volume were calculated using the two-parameter BET equation, and pore distribution was calculated using the BJH method.

[0055] The average particle size of the samples was measured using a polarizing microscope (model DM2700P).

[0056] The characterization results are shown in Table 2.

[0057] Table 1

[0058] Table 2

[0059] As can be seen from the test results in Tables 1 and 2, the manganese-containing graphene composite material prepared by the method provided in this disclosure has a larger specific surface area and pore volume, and a smaller average particle size compared with the comparative example. It can react with sulfur compounds and exhibits excellent sulfur removal performance in the process of removing sulfur compounds from the material. The removal rate of mixed sulfur compounds in the material reaches more than 85%. At the same time, it reduces the manganese ion content in the wastewater generated during the preparation of graphene, and no sodium nitrate needs to be added during the reaction process, thus reducing the cost of the prepared material.

[0060] The test results of Comparative Examples 1-4 show that in Comparative Example 1, the graphene composite material was obtained directly through solid-liquid separation without reflux reaction under ultrasonic stirring, resulting in a smaller specific surface area and pore size, a larger average particle size, decreased product quality, and a significantly lower sulfide removal rate than in Example 1. In Comparative Example 2, the reflux reaction was carried out under conventional mechanical stirring conditions, which made it difficult to fully mix the materials, resulting in low material uniformity. This led to a smaller specific surface area and pore size, a larger average particle size, poor product performance, and a significantly lower sulfide removal rate than in Examples 1-8. In Comparative Example 3, no baking was performed. In the calcination process, the graphene oxide component in the material is not reduced to graphene, resulting in a graphene oxide composite material. This also causes instability in the particle structure of the obtained material, making the particles prone to breakage during subsequent use. Consequently, the performance of the prepared graphene oxide composite material product is poor, and the removal rate of sulfides in the material is reduced. In Comparative Example 4, continuous ultrasonic stirring is used, which damages the layered structure of the material, preventing the graphene and manganese oxide components from effectively combining. This, in turn, leads to instability in the particle structure of the obtained material, resulting in poor performance of the prepared graphene composite material product and a reduced removal rate of sulfides in the material.

[0061] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0062] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0063] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A method for preparing a manganese-containing graphene composite material, wherein, The method includes: S1. Mix graphite, potassium permanganate and concentrated acid, heat and react, then add water and stir to obtain a mixed solution; S2. Mix the mixture with optional hydrogen peroxide and reflux it under intermittent ultrasonic stirring. Separate the resulting material into a solid product. S3. The solid product is calcined under an inert atmosphere; The intermittent ultrasonic stirring step includes: (1) ultrasonic stirring for 5-30 minutes and then stopping for 10-60 minutes; (2) repeating step (1) in a cycle.

2. The method according to claim 1, wherein, The graphite is one or more of natural flake graphite, natural cryptocrystalline graphite, and artificial graphite. The graphite has a carbon content of 95% or more by weight, an ash content of less than 5%, and a mesh size of 20 to 1000 mesh.

3. The method according to claim 1, wherein, The concentrated acid is selected from one or more of sulfuric acid, nitric acid, and perchloric acid; C0 is any concentration between C-5% and C+5%, where C0 is the concentration of the concentrated acid and C is the highest concentration of the concentrated acid in analytical grade reagent.

4. The method according to claim 1, wherein, In step S1, the mass ratio of concentrated acid, potassium permanganate and graphite is (25~80):(3~8):

1.

5. The method according to claim 1, wherein, The method further includes: in step S2, mixing the mixture with hydrogen peroxide; the mass ratio of the mixture to hydrogen peroxide is 1:(0.1~10); the mass concentration of hydrogen peroxide is 0.1~5%, preferably 0.2~2%.

6. The method according to claim 1, wherein, In step S2, the intermittent ultrasonic stirring is performed using probe-type ultrasonic and / or water bath ultrasonic, with a power of 50~500W / h and a stirring time of 0.1~12h; the reflux reaction temperature is 120~180℃ and the time is 6~48h.

7. The method according to claim 1, wherein, In step S1, the mixing temperature is below 30°C, preferably below 20°C, and more preferably below 10°C; the mixing time is 0.5~12h. The conditions for the heating reaction are: temperature 35~60℃, time 0.2~6h; The temperature for adding water and stirring is 40~100℃, and the time is 0.1~5h; the mass ratio of water to graphite is (50~250):

1. In step S3, the calcination treatment is carried out at a temperature of 400~1000℃ for a time of 0.1~24h.

8. A manganese-containing graphene composite material prepared by the method according to any one of claims 1 to 7.

9. The manganese-containing graphene composite material according to claim 8, wherein, The manganese-containing graphene composite material contains Mn, C, O, K, and S elements. Specifically, the Mn content (calculated as MnO2) in the manganese-containing graphene composite material is 55-90% by weight; the S content (calculated as SO2) is 0.5-10% by weight; and the K content (calculated as K2O) is 1-15% by weight. The XRD pattern of the manganese-containing graphene composite material contains characteristic peaks of α-MnO2 and graphene. The specific surface area of ​​the manganese-containing graphene composite material is 300~800 m². 2 / g, preferably 400~600m 2 / g, pore volume is 0.5~2ml / g, preferably 0.8~1.5ml / g, and average particle size is less than 1mm, preferably less than 0.2mm.

10. The use of the manganese-containing graphene composite material according to claim 8 or 9 in the removal of sulfur-containing compounds; The sulfur-containing raw material is brought into contact with the manganese-containing graphene composite material for reaction; the conditions for the contact reaction include: Temperature: 30~80℃, pressure: 1~5MPa, space velocity: 10~1000h -1 Preferably, the pressure is 0.5~3.0 MPa and the space velocity is 50~500 h⁻¹. -1 The sulfur-containing compound content in the raw material is less than 25%, preferably less than 10%.

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