A method for preparing manganese-based adsorbent materials and a method for purifying hydrogen.

Abstract

This disclosure relates to a method for preparing manganese-based adsorbent materials and graphite oxide. The method includes: preparing graphite oxide using a modified Hummer method; performing solid-liquid separation on the obtained material to obtain a filtrate and graphite oxide; and subjecting the filtrate to hydrothermal treatment under hydrothermal autogenous pressure and atmosphere to recover the solid phase material, thereby obtaining the manganese-based adsorbent material. The preparation method of this invention, due to the higher amount of potassium permanganate used in the modified Hummer method, eliminates the need for adding a manganese source, thus reducing preparation costs. The manganese-based adsorbent material prepared by this invention exhibits excellent performance in hydrogen purification reactions, achieving the removal of macro-sulfides (volume content > 0.1%) from hydrogen at temperatures below 50°C. The purified hydrogen can then be directly used for fuel cell hydrogen supply.

Description

Technical Field

[0001] This disclosure pertains to the field of hydrogen purification, specifically relating to a method for preparing a manganese-based adsorbent material and a method for purifying hydrogen. Background Technology

[0002] Hydrogen is an important energy source. One of its uses is to supply hydrogen to fuel cells for power generation, thus realizing the utilization of hydrogen energy. However, the electrode catalysts of fuel cells are quite sensitive to sulfides; even trace amounts of sulfides can poison the fuel cell electrode catalyst, leading to a decrease in efficiency. Therefore, the sulfide content of hydrogen used in fuel cells is subject to strict requirements. Internationally, the requirement is that the sulfide content, calculated as hydrogen sulfide, must be less than 4 ppb, which is the most stringent requirement for impurities in hydrogen used in fuel cells. Ensuring that the sulfide content of hydrogen used in fuel cells meets the standards is a key technological challenge. Existing desulfurization technologies are mostly designed for gases such as natural gas, while methods for treating sulfides in hydrogen are limited and suffer from problems such as poor desulfurization efficiency, complex processing procedures, and high costs. Summary of the Invention

[0003] The purpose of this invention is to provide a method for preparing manganese-based adsorbent materials and a method for purifying hydrogen. The preparation method of this invention involves hydrothermal treatment of the graphite oxide filter stock prepared by the improved Hummer method (increasing the amount of potassium permanganate, but without adding sodium nitrate and hydrogen peroxide). Because the improved Hummer method uses a higher amount of potassium permanganate in the preparation of graphite oxide, no additional manganese source is needed to prepare the manganese-based adsorbent material, thus reducing the preparation cost. The manganese-based adsorbent material prepared by this invention exhibits excellent performance in the hydrogen purification reaction, achieving the removal of macro-sulfides (volume content > 0.1%) from hydrogen at temperatures below 50°C. The purified hydrogen can be directly used for hydrogen supply in fuel cells.

[0004] To achieve the above objectives, a first aspect of the present invention provides a method for preparing manganese-based adsorbent materials and graphite oxide, the method comprising:

[0005] S1 uses a modified Hummer method to prepare graphite oxide. The resulting material is subjected to solid-liquid separation to obtain a liquid phase and a solid phase, respectively. The liquid phase is the original filtrate, and the solid phase is recovered to obtain graphite oxide.

[0006] S2 performs hydrothermal treatment on the original filtrate under hydrothermal self-generated pressure and atmosphere and recovers the solid phase material to obtain manganese-based adsorbent material;

[0007] The mass ratio of potassium permanganate to graphite during the preparation of graphite oxide is 6.5 or higher.

[0008] Optionally, sodium nitrate and hydrogen peroxide are not added during the reaction process of the improved Hummer method.

[0009] Optionally, the oxygen content of the graphite oxide is 35-60% by weight, and the carbon content is 40-65% by weight. Optionally, the mass ratio of potassium permanganate to graphite during the preparation of graphite oxide is 8-15.

[0010] Optionally, the filtration solution of the graphite oxide contains 40-100 g / L of manganese ions (calculated as divalent manganese ions), 25-80 g / L of potassium ions (calculated as potassium ions), 10-200 g / L of sulfur ions (calculated as sulfate ions), and 5-50 g / L of carbon atoms.

[0011] Optionally, step S2 includes:

[0012] (1) The original filtration solution is mixed with water to obtain a mixture, wherein the mass ratio of the original filtration solution to water is 1:(0-10);

[0013] (2) The mixture is subjected to hydrothermal crystallization treatment, the solid product is taken out, and then washed, dried and optionally calcined to obtain the manganese-based adsorbent material;

[0014] The hydrothermal crystallization conditions include: a temperature of 100–200°C under autogenous pressure and a time of 2–72 hours.

[0015] The calcination conditions include: a temperature of 250–700°C, a time of 1–12 h, and a pressure of 0.1–1 MPa.

[0016] A second aspect of the present invention provides a method for preparing manganese-based adsorbent materials using the method provided in the first aspect of the present invention.

[0017] Optionally, the XRD pattern of the manganese-based adsorbent material has characteristic peaks at 2θ positions of 12.2±0.5°, 24.7±0.5°, 36.8±0.5° and 66.3±0.5°, respectively; the half-width of the diffraction peak at 12.2±0.5° is greater than 0.5°.

[0018] The specific surface area of ​​the manganese-based adsorbent material is 200–350 m². 2 / g, with a pore volume of 0.2–0.9 ml / g; preferably, with a specific surface area of ​​240–320 m² / g. 2 / g, with a pore volume of 0.4–0.7 ml / g.

[0019] Optionally, based on the mass of the manganese-based adsorbent material, the manganese-based adsorbent material contains 25-53% by weight of Mn, 1-15% by weight of S, and 2-20% by weight of K.

[0020] Preferably, the manganese-based adsorbent material contains 40-53% Mn, 2-12% S, and 6-15% K by weight.

[0021] The third aspect of the present invention provides a method for purifying hydrogen, the method comprising: contacting hydrogen with a manganese-based adsorbent material provided in the second aspect of the present invention at a temperature of 20 to 50°C to carry out a purification reaction.

[0022] Optionally, the reaction conditions for the hydrogen purification method include: a temperature of 20–50°C, a pressure of 0.1–5.0 MPa, and a space velocity of 50–10000 h⁻¹. -1 ;

[0023] The volume content of sulfides in the hydrogen is 0.1% to 1%, and the content of sulfides in the hydrogen is calculated as hydrogen sulfide.

[0024] Through the above technical solution, the preparation method of the present invention performs hydrothermal treatment on the graphite oxide filtration solution prepared by the improved Hummer method, and optionally calcination to obtain manganese-based adsorbent material. Since the improved Hummer method uses a higher amount of potassium permanganate in the preparation of graphite oxide, it accelerates the graphite oxide oxidation process, simplifies the preparation steps of the manganese-based adsorbent material, and eliminates the need for an additional manganese source, thus reducing the preparation cost of the manganese-based adsorbent material. The manganese-based adsorbent material prepared by the present invention exhibits excellent performance in the hydrogen purification reaction process, and can remove sulfides from hydrogen at temperatures below 50°C. The purified hydrogen meets the standard requirements for hydrogen used in fuel cells.

[0025] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0026] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof. In the drawings:

[0027] Figure 1 The image shows the XRD pattern of the manganese-based adsorbent material prepared in Example 1 of this invention. Detailed Implementation

[0028] The specific embodiments of this disclosure will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit this disclosure.

[0029] The first aspect of this invention provides a method for preparing manganese-based adsorbent materials and graphite oxide, the method comprising:

[0030] S1 uses a modified Hummer method to prepare graphite oxide. The resulting material is subjected to solid-liquid separation to obtain a liquid phase and a solid phase, respectively. The liquid phase is the original filtrate, and the solid phase is recovered to obtain graphite oxide.

[0031] S2 performs hydrothermal treatment on the original filtrate under hydrothermal self-generated pressure and atmosphere and recovers the solid phase material to obtain manganese-based adsorbent material;

[0032] The mass ratio of potassium permanganate to graphite during the preparation of graphite oxide is 6.5 or higher.

[0033] In one specific embodiment of the present invention, sodium nitrate and hydrogen peroxide are not added during the reaction process of the improved Hummer method.

[0034] In one specific embodiment of the present invention, the oxygen content of the graphite oxide is 35-60% by weight, preferably 40-55% by weight, and the carbon content is 40-65% by weight, preferably 45-60% by weight.

[0035] The graphite oxide prepared by this invention has a high oxygen content, is easy to disperse, has many lamellar defects, and has a strong chelating effect, which will have significant advantages in adsorbing heavy metal ions in wastewater and in soil remediation.

[0036] The preparation method of the present invention involves hydrothermal crystallization treatment of the filter solution of graphite oxide prepared by the improved Hummer method. Since the improved Hummer method uses a higher amount of potassium permanganate to prepare graphite oxide, the process of graphite oxide oxidation is accelerated, and no additional manganese source is required, thus reducing the preparation cost of manganese-based adsorbent materials.

[0037] In one specific embodiment of the present invention, the mass ratio of potassium permanganate to graphite during the preparation of graphite oxide is 8 to 15, preferably 9 to 12.

[0038] In one specific embodiment of the present invention, graphite and 98% concentrated sulfuric acid are added to a beaker placed in an ice-water bath (<5°C) and stirred until homogeneous. Potassium permanganate is then slowly added in batches while stirring. After the potassium permanganate is added, the reaction is continued to be stirred in a warm water bath at 40°C for 0.5 hours. Then, an appropriate amount of deionized water is added, and the temperature of the water bath is raised to 95-98°C and reacted for another 0.5 hours. The beaker is removed from the water bath, and deionized water at approximately 60°C is added. The mixture is stirred until the temperature drops below 30°C. After stirring until homogeneous, the solid graphite oxide is separated by filtration to obtain the graphite oxide filtrate. The ratio of the reactants is graphite:concentrated sulfuric acid:potassium permanganate:water = 1g:15-35ml:6.5-15g:50-500ml.

[0039] In one specific embodiment of the present invention, the filtration solution of the graphite oxide contains manganese in the form of divalent manganese ions at a concentration of 40-100 g / L, preferably 50-80 g / L; potassium in the form of potassium ions at a concentration of 25-80 g / L, preferably 35-60 g / L; sulfur in the form of sulfate ions at a concentration of 10-200 g / L, preferably 40-100 g / L; and carbon in the form of carbon atoms at a concentration of 5-50 g / L, preferably 8-20 g / L.

[0040] In a further preferred embodiment, the graphite oxide filtration solution is an aqueous solution, mainly containing elements such as manganese, potassium, sulfur, and carbon. The manganese content, calculated as divalent manganese ions, is 64 g / L; the potassium content, calculated as potassium ions, is 37 g / L; the sulfur content, calculated as sulfate ions, is 102 g / L; and the carbon content, calculated as carbon atoms, is 6.5 g / L. The carbon mainly comes from soluble graphite oxide remaining in the solution.

[0041] In this invention, the recovery process of obtaining graphite oxide from the solid phase in step S1 refers to drying after an optional washing step. Washing is a conventional operation in the art, such as water washing; the drying step is conventional drying, vacuum drying, or freeze drying, wherein the temperature of conventional drying is 80-200℃ and the time is 1-48h; the temperature of vacuum drying is 20-100℃ and the time is 1-24h; and the temperature of freeze drying is -60 to -20℃ and the time is 12-48h.

[0042] In one specific embodiment of the present invention, step S2 includes:

[0043] (1) The filter stock solution is mixed with water to obtain a mixture, wherein the mass ratio of the filter stock solution to water is 1:(0-10), preferably 1:(1-5);

[0044] (2) The mixture is subjected to hydrothermal crystallization treatment, the solid product is taken out, and then washed, dried and optionally calcined to obtain the manganese-based adsorbent material.

[0045] In one specific embodiment of the present invention, the hydrothermal crystallization conditions include: a temperature of 100-200°C under autogenous pressure, preferably 110-160°C, and a time of 2-72 hours, preferably 4-36 hours;

[0046] The calcination conditions include: a temperature of 250–700°C, preferably 300–500°C; a time of 1–12 h, preferably 2–6 h; and a pressure of 0.1–1 MPa, preferably 0.1–0.5 MPa.

[0047] A second aspect of the present invention provides a method for preparing manganese-based adsorbent materials using the method provided in the first aspect of the present invention.

[0048] In one specific embodiment of the present invention, the XRD pattern of the manganese-based adsorbent material has characteristic peaks at 2θ positions of 12.2±0.5°, 24.7±0.5°, 36.8±0.5° and 66.3±0.5°, respectively; the half-width of the diffraction peak at 12.2±0.5° is greater than 0.5°;

[0049] The specific surface area of ​​the manganese-based adsorbent material is 200–350 m². 2 / g, with a pore volume of 0.2–0.9 ml / g; preferably, with a specific surface area of ​​240–320 m² / g. 2 / g, with a pore volume of 0.4–0.7 ml / g.

[0050] In one specific embodiment of the present invention, based on the mass of the manganese-based adsorbent material, the manganese-based adsorbent material contains 25-53% by weight of Mn, 1-15% by weight of S, 2-20% by weight of K, and the balance is O.

[0051] Preferably, the manganese-based adsorbent material contains 40-53% Mn, 2-12% S, 6-15% K, and the balance is O.

[0052] The third aspect of the present invention provides a method for purifying hydrogen, the method comprising: contacting hydrogen with a manganese-based adsorbent material provided in the second aspect of the present invention at a temperature of 20 to 50°C to carry out a purification reaction.

[0053] In one specific embodiment of the present invention, the reaction conditions of the hydrogen purification method include: a temperature of 20–50°C, a pressure of 0.1–5.0 MPa, and a space velocity of 50–10000 h⁻¹. -1 Preferably, the temperature is 25–40°C, the pressure is 1–3 MPa, and the space velocity is 100–5000 h⁻¹. -1 .

[0054] The volume content of sulfides in the hydrogen is 0.1% to 1%, and the content of sulfides in the hydrogen is calculated as hydrogen sulfide.

[0055] In this invention, the hydrogen purification method is carried out under relatively low temperature, high concentration, and low space velocity conditions, which effectively removes sulfides from hydrogen at temperatures below 50°C. The sulfide content in the purified hydrogen can meet the requirements for sulfide impurity content in hydrogen used in fuel cells.

[0056] The present invention will be further illustrated by the following examples, but the present invention is not limited thereto.

[0057] All reagents used in this invention are commercially available analytical grade reagents.

[0058] Example 1

[0059] A modified Hummer method was used to prepare graphite oxide. 5g of graphite and 98% concentrated sulfuric acid were added to a beaker placed in an ice-water bath (~5℃) and stirred until homogeneous. Potassium permanganate was slowly added in five batches while stirring. After the potassium permanganate was added, the reaction was continued in a 40℃ warm water bath with stirring for 0.5h. Then, an appropriate amount of deionized water was added, and the temperature of the water bath was raised to 95-98℃ for another 0.5h. The beaker was removed from the water bath, and deionized water at approximately 60℃ was added. Stirring was continued until the temperature dropped below 30℃. After stirring until homogeneous, the graphite oxide solid was separated by filtration to obtain the graphite oxide filtrate. The ratio of the reactants was graphite:concentrated sulfuric acid:potassium permanganate:water = 1g:30ml:10g:100ml. The resulting material was subjected to solid-liquid separation to obtain the filtrate liquid phase and the graphite oxide solid phase. The graphite oxide solid phase was vacuum dried at 80℃ for 6h to obtain graphite oxide powder. The filtered raw solution contained 64 g / L of manganese (calculated as divalent manganese ions), 37 g / L of potassium (calculated as potassium ions), 102 g / L of sulfur (calculated as sulfate ions), and 6.5 g / L of carbon (calculated as carbon atoms); the graphite oxide contained 43% by weight of oxygen and 57% by weight of carbon.

[0060] b. Add 50 mL of water and 50 g of graphite oxide filtrate to a beaker and mix to obtain a mixture;

[0061] c. The mixture obtained in step b is subjected to hydrothermal crystallization treatment at 140°C and autogenous pressure for 12 hours.

[0062] The manganese-based adsorbent obtained after hydrothermal treatment was filtered, washed, dried at 80°C for 6 hours, and then calcined at 300°C for 4 hours.

[0063] Example 2

[0064] The preparation method in Example 1 was used, except that in step d, the calcination temperature was 700°C and the time was 1 hour.

[0065] Example 3

[0066] The preparation method in Example 1 is used, except that calcination is not performed in step d.

[0067] Example 4

[0068] The preparation method in Example 1 is used, except that in step c, the hydrothermal crystallization temperature is 180°C.

[0069] Example 5

[0070] The preparation method described in Example 1 is used, except that in step a, the ratio of the reactants is graphite:concentrated sulfuric acid:potassium permanganate:water = 1g:50ml:10g:150ml; the filtrate of graphite oxide contains 41g / L of manganese ions, 26g / L of potassium ions, 195g / L of sulfur ions, and 5.1g / L of carbon atoms; the oxygen content of graphite oxide is 48% by weight, and the carbon content is 52% by weight.

[0071] Comparative Example 1

[0072] The preparation method in Example 1 was used, except that in step a, the mass ratio of potassium permanganate to graphite was 6; the oxygen content of the graphite oxide was 33% by weight and the carbon content was 67% by weight.

[0073] Test case

[0074] The manganese-based adsorbent materials of Examples 1-5 and Comparative Example 1, as well as potassium permanganate, were tested as follows:

[0075] The XRD patterns of the samples were obtained using a Rigaku D / MaxA-ⅢA X-ray diffractometer (Japan). Test conditions: Cu target Kα radiation, tube voltage 30 kV, tube current 20 mA, step scan, scan range 5°–70°.

[0076] The average particle size of the prepared product was determined by scanning electron microscopy (ISI-60A electron microscope from ISI Corporation, USA, accelerating voltage 20kV), and random samples were taken for particle size statistics.

[0077] The elemental content of the samples was determined by XPS on a VGESCA-LABS X-ray photoelectron spectrometer, using Mg Kα X-rays as the laser source. The binding energy of each element in the species on the surface of the desulfurizer was calibrated by the C1s binding energy (284.6 eV) of the carbon contaminants on the surface.

[0078] Temperature nitrogen adsorption-desorption (BET) tests were performed on 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. The sulfide content in the hydrogen gas after adsorption by the adsorbent was analyzed using online chromatography (Shimadzu Nexis-2030, Japan) and an SCD fluorescence detector (SCD-2030).

[0079] 290 mg of the samples prepared according to the present invention (including the comparative examples) and potassium permanganate were loaded into the isothermal section of a passivated fixed-bed microreactor with an inner diameter of 12 mm and a length of 500 mm. Quartz sand was placed on both the top and bottom. The hydrogen feedstock standard gas contained 0.5% hydrogen sulfide by volume. The purification reaction was carried out by introducing hydrogen gas at 30 ml / min at 40 °C and 2.1 MPa. The hydrogen sulfide content in the purified hydrogen gas was analyzed online every 5 minutes. The breakthrough time was defined as the time from the start of hydrogen gas introduction until the hydrogen sulfide content in the purified hydrogen gas exceeded 0.004 ppm. The breakthrough time test results for each sample are shown in Table 1, and other characterization results for each sample are shown in Table 2. The XRD pattern of the manganese-based adsorbent material of Example 1 prepared according to the present invention is shown in Table 2. Figure 1 As shown.

[0080] Table 1

[0081]

[0082]

[0083] Table 2

[0084]

[0085] As can be seen from the test results in Tables 1 and 2, the manganese-based adsorbent material prepared by the method provided in this invention has a longer breakthrough time for hydrogen feed gas containing hydrogen sulfide compared with the comparative example, and exhibits superior performance in the hydrogen purification reaction. The sulfide content in the purified hydrogen can meet the requirements for sulfide impurities in hydrogen used in fuel cells, and fully utilizes the manganese element in the graphite oxide filter solution without the need to add an additional manganese source, thus reducing the preparation cost of manganese oxide.

[0086] As can be seen from the test results of Examples 1 to 6, when the preparation method of the filter stock solution of graphite oxide, the mass ratio of potassium permanganate to graphite during the preparation of graphite oxide, the element content in the filter stock solution of graphite oxide, the hydrothermal crystallization treatment conditions, and the calcination conditions are within the limits of this invention, the effect and performance of the product prepared by this invention can be further improved.

[0087] The test results of Comparative Example 1 and potassium permanganate as adsorbents show that, since the mass ratio of potassium permanganate to graphite in Comparative Example 1 is not within the scope of the claims, the hydrogen feed gas breakthrough time is significantly shorter than that in Examples 1-5. Therefore, the performance of the prepared manganese-based adsorbent in the hydrogen purification reaction is worse than that of the embodiments of the present invention. When potassium permanganate is used directly as an adsorbent, the hydrogen feed gas breakthrough time is even shorter, indicating that its adsorption performance in the hydrogen purification reaction is poor.

[0088] The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the specific details of 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.

[0089] 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.

[0090] 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 manganese-based adsorbent materials and graphite oxide, the method comprising: S1 uses the improved Hummer method to prepare graphite oxide. The obtained material is subjected to solid-liquid separation to obtain a liquid phase and a solid phase, respectively. The liquid phase is the original filtrate, and the solid phase is recovered to obtain graphite oxide. S2 The filter stock solution is subjected to hydrothermal treatment under hydrothermal self-generated pressure and atmosphere, and the solid phase material is recovered; The mass ratio of potassium permanganate to graphite during the preparation of graphite oxide is 6.5 or higher. The XRD pattern of the manganese-based adsorbent material shows characteristic peaks at 2θ positions of 12.2±0.5°, 24.7±0.5°, 36.8±0.5° and 66.3±0.5°, respectively; the half-width of the diffraction peak at 12.2±0.5° is greater than 0.5°.

2. The method according to claim 1, wherein, Sodium nitrate and hydrogen peroxide were not added during the reaction process of the improved Hummer method.

3. The method according to claim 1, wherein, The oxygen content of the graphite oxide is 35-60% by weight, and the carbon content is 40-65% by weight.

4. The method according to claim 1, wherein, The mass ratio of potassium permanganate to graphite during the preparation of graphite oxide is 8-15.

5. The method according to claim 1, wherein, The filtration solution of the graphite oxide contains 40-100 g / L of manganese ions, 25-80 g / L of potassium ions, 10-200 g / L of sulfur ions, and 5-50 g / L of carbon atoms.

6. The method according to claim 1, wherein, Step S2 includes: (1) The original filtration solution is mixed with water to obtain a mixture, wherein the mass ratio of the original filtration solution to water is 1:(0~10). (2) The mixture is subjected to hydrothermal crystallization treatment, the solid product is taken out, washed, dried and optionally calcined to obtain the manganese-based adsorbent material; The hydrothermal crystallization conditions include: a temperature of 100~200℃ under autogenous pressure and a time of 2~72h; The calcination conditions include: a temperature of 250~700℃, a time of 1~12h, and a pressure of 0.1~1Mpa.

7. A manganese-based adsorbent material prepared by the method described in any one of claims 1 to 6.

8. The manganese-based adsorbent material according to claim 7, wherein, The specific surface area of ​​the manganese-based adsorbent material is 200~350m². 2 / g, with a pore volume of 0.2~0.9ml / g.

9. The manganese-based adsorbent material according to claim 8, wherein, The specific surface area of ​​the manganese-based adsorbent material is 240~320 m². 2 / g, with a pore volume of 0.4~0.7ml / g.

10. The manganese-based adsorbent material according to claim 7, wherein, Based on the mass of the manganese-based adsorbent material, the manganese-based adsorbent material contains 25-53% by weight of Mn, 1-15% by weight of S, and 2-20% by weight of K.

11. The manganese-based adsorbent material according to claim 10, wherein, The manganese-based adsorbent material contains 40-53% Mn, 2-12% S, and 6-15% K by weight.

12. A method for purifying hydrogen, the method comprising: At a temperature of 20~50°C, hydrogen gas is brought into contact with the manganese-based adsorbent material according to any one of claims 7~11 to carry out a purification reaction. The reaction conditions for the hydrogen purification method include: a temperature of 20-50℃, a pressure of 0.1-5.0 MPa, and a space velocity of 50-10000 h⁻¹. -1 ; The volume content of sulfides in the hydrogen is 0.1-1%, and the content of sulfides in the hydrogen is calculated as hydrogen sulfide.

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