Manganese-based adsorption material, and preparation method therefor and use thereof

Abstract

The present invention relates to a manganese-based adsorption material, and a preparation method therefor and the use thereof. The manganese-based adsorption material shows good performance during a hydrogen purification reaction process, and can remove constant sulfide (having a volume content larger than 0.1%) from hydrogen at a temperature lower than 50ºC, and the purified hydrogen can be directly used for hydrogen supply of a fuel cell. The manganese-based adsorption material is an associated product of a graphite oxidation method, and during the process of preparing the manganese-based adsorption material, the content of manganese ions in the wastewater is also significantly reduced, thereby solving the problem of environmental pollution, etc. caused by wastewater discharge during the graphite oxidation process.

Description

Manganese-based adsorption material, preparation method thereof and use thereof Technical Field

[0001] The present disclosure relates to the field of gas purification, and more particularly to a manganese-based adsorbent material for gas purification, such as hydrogen purification. The manganese-based adsorbent material is a byproduct of a graphite oxidation process. The present disclosure also relates to methods for producing graphite oxide and the manganese-based adsorbent material, and to the use of the manganese-based adsorbent material for purifying gases, such as hydrogen. Background Art

[0002] Graphite oxide, formally known as graphite oxide or graphitic acid, is a compound composed of carbon, hydrogen, and oxygen in varying molar ratios. Graphite oxide is an important type of graphite product, used to produce popular downstream products such as expanded graphite and graphene. Currently, the primary method for producing graphite oxide is through a redox process using concentrated acid and strong oxidants such as potassium permanganate. However, existing methods generate manganese-containing wastewater that is difficult to treat, posing significant environmental challenges.

[0003] Hydrogen is an important new energy source. One of its uses is to supply hydrogen to fuel cells, generating electricity and realizing hydrogen energy utilization. However, fuel cell electrode catalysts are sensitive to trace impurities such as sulfides and formaldehyde, particularly sulfides. The presence of trace sulfides can poison the fuel cell electrode catalysts, leading to reduced efficiency. Therefore, strict requirements are placed on the sulfide content of hydrogen used in fuel cells. International standards require a sulfide content of less than 4 ppb, calculated as hydrogen sulfide, which is the most stringent requirement for impurity levels in fuel cell hydrogen. Ensuring acceptable sulfide content in fuel cell hydrogen is a key technical issue. Existing desulfurization technologies are mostly targeted at gases like natural gas, while treatment methods for sulfides in hydrogen are limited. These methods also suffer from poor desulfurization effectiveness, complex treatment processes, and high costs. Hydrogen sulfide and carbonyl sulfide are the main forms of sulfide impurities found in common gases, particularly hydrogen. Reports on desulfurization technologies for mixed sulfides, or on desulfurization technologies using manganese oxides for mixed sulfides, are limited.

[0004] Summary of the Invention

[0005] One objective of the present invention is to provide a manganese-based adsorbent material that can efficiently remove sulfides from gases, such as hydrogen, even in the presence of mixed sulfides. Advantageously, the manganese-based adsorbent material is a byproduct of the oxidation process for producing graphite oxide. The production process also significantly reduces the content of manganese ions and other substances in wastewater produced during the production process, thereby addressing environmental pollution caused by wastewater discharge.

[0006] In order to achieve the above object, a first aspect of the present invention provides a manganese-based adsorption material, wherein the manganese-based adsorption material comprises Mn element, C element, O element, and optionally S element and optional K element;

[0007] Based on the mass of the manganese-based adsorption material, the manganese-based adsorption material has an Mn content of 25-63% by weight, an S content of 0-15% by weight, an O content of 14-37% by weight, an K content of 0-20% by weight, and an C content of 0.01-5% by weight.

[0008] The manganese-based adsorption material contains Mn in the form of manganese oxide and C in the form of graphite oxide.

[0009] A second aspect of the present invention provides a method for co-producing graphite oxide and manganese-based adsorption material, wherein the method comprises:

[0010] S1: mixing graphite, Bronsted acid and permanganate, preferably potassium permanganate, and then heating the resulting mixture to react;

[0011] S2. adding water and / or hydrogen peroxide to the reaction material obtained in step S1, continuing the reaction, obtaining a separated stock solution and a solid phase through solid-liquid separation, and recovering the solid phase to obtain graphite oxide;

[0012] S3, with or without adding an auxiliary agent, performing a hydrothermal reaction on the separated stock solution obtained in step S2, separating the obtained solid product to obtain a manganese-based adsorption material;

[0013] The conditions for the hydrothermal reaction in step S3 include: a temperature of 100 to 200° C., preferably 120 to 200° C., more preferably 150 to 180° C., and a time of 1 to 72 hours, preferably 12 to 36 hours.

[0014] The third aspect of the present invention provides a manganese-based adsorption material prepared according to the second aspect of the present invention.

[0015] The fourth aspect of the present invention provides use of the manganese-based adsorption material obtained by the method of the first aspect or the second aspect for removing impurities such as sulfide and formaldehyde from gas.

[0016] A fifth aspect of the present invention provides a method for purifying hydrogen, the method comprising: contacting hydrogen with the manganese-based adsorption material provided by the first aspect of the present invention to perform a purification reaction.

[0017] The manganese-based adsorption material of the present invention exhibits excellent performance in the hydrogen purification reaction process and can remove sulfides in hydrogen at a temperature below 50° C. The purified hydrogen can meet the standard requirements for hydrogen used in fuel cells.

[0018] In the method of the present invention, since a relatively high amount of potassium permanganate is used during the preparation of graphite oxide, no additional manganese source needs to be added, and no sodium nitrate is added during the reaction process, thereby reducing the cost of preparing the manganese-based adsorption material. The present invention also produces the manganese-based adsorption material while preparing graphite oxide. Furthermore, the method exhibits excellent performance in treating wastewater produced during the preparation process, significantly reducing the content of manganese ions and other substances in the wastewater, thereby resolving issues such as wastewater discharge polluting the environment during the graphite oxide preparation process.

[0019] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the following detailed description, they are used to explain the present invention but do not constitute a limitation of the present invention. In the accompanying drawings:

[0021] FIG1 is an XRD pattern of the manganese-based adsorption material prepared in Example 1.1 of Experimental Series 1 of the present invention.

[0022] FIG2 is an XRD pattern of the manganese-based adsorption material prepared in Example 2.1 of Experimental Series 2 of the present invention.

[0023] FIG3 is an XRD pattern of the manganese-based adsorption material prepared in Example 3.1 of Experimental Series 3 of the present invention. DETAILED DESCRIPTION

[0024] The following describes the specific embodiments of the present disclosure in detail with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present disclosure and are not intended to limit the present disclosure.

[0025] Exemplary embodiments are provided so that this disclosure is thorough and will fully convey its scope to those skilled in the art. Many specific details, such as examples of specific compositions, components, devices, and methods, are set forth to provide a full understanding of the embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be used and that the exemplary embodiments may be embodied in many different forms, none of which should be construed as limiting the scope of the present disclosure. In some exemplary embodiments, well-known methods, well-known device structures, and well-known technologies are not described in detail.

[0026] The terms used herein are intended only to describe specific exemplary embodiments and are not intended to be limiting. Unless the context clearly indicates otherwise, the singular forms "a", "an" and "the" as used herein may be intended to include plural forms as well. The terms "comprising", "including", "containing" and "having" are inclusive, and thus illustrate the presence of the features, elements, compositions, steps, integers, operations and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or their collections. Although the open term "comprising" should be understood as a non-limiting term for describing and claiming the various embodiments described herein, in some aspects, the term may alternatively be understood as a more restrictive and limited term, such as "consisting of" or "consisting essentially of". Thus, for any given embodiment of a narration composition, material, component, element, feature, integer, operation and / or process step, the present disclosure also particularly includes an embodiment consisting of or consisting essentially of such a composition, material, component, element, feature, integer, operation and / or process step. In the case of "consisting of," alternative embodiments exclude any additional compositions, materials, components, elements, features, integers, operations and / or process steps, while in the case of "consisting essentially of," any additional compositions, materials, components, elements, features, integers, operations and / or process steps that materially affect the basic and novel characteristics are excluded from such embodiments, but any compositions, materials, components, elements, features, integers, operations and / or process steps that do not materially affect the basic and novel characteristics may be included in such embodiments.

[0027] Any method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as a certain order of performance. It is also to be understood that additional or alternative steps may be used unless otherwise specified.

[0028] Any specific numerical value disclosed herein (including the endpoints of a numerical range) is not limited to the exact value of the numerical value, but should be understood to also include values ​​close to the exact value, such as all possible values ​​within ±5% of the exact value. Moreover, for a disclosed numerical range, any combination of the endpoints of the range, between the endpoints and the specific points in the range, and between the specific points can be used to generate one or more new numerical ranges, and these new numerical ranges should also be considered to be specifically disclosed herein.

[0029] Furthermore, disclosure of ranges includes disclosure of all values ​​within the entire range and further subdivided ranges, including endpoints and subranges given within those ranges.

[0030] 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. To avoid unnecessary repetition, this application will not further describe various possible combinations.

[0031] In the context of the present invention, the terms "separation stock solution" and "filtration waste solution" are used interchangeably.

[0032] In the context of the present invention, the term "manganese-based adsorption material" refers to an adsorption material with manganese or a manganese-containing compound as the main functional component. It does not necessarily mean that the weight percentage of manganese or a manganese-containing compound in the manganese-based adsorption material exceeds 50%.

[0033] In the context of the present invention, the term "manganese-based adsorption material" is also referred to as "manganese oxide" for short.

[0034] In the context of the present invention, the term "specific surface area" is the BET specific surface area. The term "pore volume" is the pore volume determined by the BET method.

[0035] In the context of the present invention, the term "hydrothermal reaction" refers to a synthesis reaction that occurs in hot water under pressure. A hydrothermal reaction typically forms crystals of a mineral dissolved in the water. The term "hydrothermal reaction" is used interchangeably with "hydrothermal crystallization reaction."

[0036] Unless otherwise specified, percentages herein refer to % by weight.

[0037] Unless otherwise specified, the terms used herein have the same meaning as commonly understood by those skilled in the art. If a term is defined herein and its definition is different from the commonly understood meaning in the art, the definition herein shall prevail.

[0038] First aspect

[0039] A first aspect of the present invention provides a manganese-based adsorption material, which comprises Mn, C, O, and optionally S and K.

[0040] Based on the mass of the manganese-based adsorption material, the manganese-based adsorption material has an Mn content of 25-63% by weight, an S content of 0-15% by weight, an O content of 14-37% by weight, an K content of 0-20% by weight, and an C content of 0.01-5% by weight.

[0041] The manganese-based adsorption material contains Mn in the form of manganese oxide and C in the form of graphite oxide.

[0042] According to a first embodiment of the first aspect of the present invention, based on the mass of the manganese-based adsorbent material, the manganese content of the element Mn is 30-55% by weight; the S content is 0.8-10% by weight; the K content is 1-10% by weight; and the C content is 0.01-5% by weight. In a preferred embodiment, the remainder is primarily oxygen. Preferably, based on the mass of the manganese-based adsorbent material, the manganese content of the element Mn is 35-50% by weight; the S content is 1.2-6% by weight; the K content is 3-8% by weight; and the C content is 0.02-1% by weight. In a preferred embodiment, the remainder is primarily oxygen. In a preferred embodiment, the sum of the weight percentages of the elements Mn, C, O, S, and K in the manganese-based adsorbent material is 100% by weight. According to a first embodiment of the first aspect of the present invention, preferably, in the XRD pattern of the manganese-based adsorbent material, characteristic peaks are present at 2θ of 28.6±0.5°, 37.4±0.3°, 41.0±0.3°, 42.8±0.3°, 56.6±0.3°, 59.4±0.3°, 64.9±0.3° and 72.4±0.3°, respectively; and the half-maximum width of the diffraction peak at 28.6±0.5° is greater than 0.1°.

[0043] According to the first embodiment of the first aspect of the present invention, preferably, the specific surface area of ​​the manganese-based adsorption material is 10 to 100 m 2 / g, preferably 30 to 60m 2 / g, the pore volume is 0.05-0.5 ml / g, preferably 0.1-0.3 ml / g, and the pore diameter is 12-36 nm, preferably 15-30 nm.

[0044] According to a first embodiment of the first aspect of the present invention, preferably, the manganese in the manganese-based adsorbent material is primarily present in the form of manganese oxide, particularly MnO2, and more preferably primarily in the form of β-MnO2. The manganese-based adsorbent material is advantageously used for removing sulfur-containing impurities, such as hydrogen sulfide and carbonyl sulfide, from gases, such as hydrogen.

[0045] According to the first embodiment of the first aspect of the present invention, the manganese-based adsorption material has a large specific surface area and pore volume, a moderate pore size, and exhibits excellent performance in removing sulfur compounds during the reaction process of removing sulfides from the gas, with a removal rate of sulfur compounds in the material reaching more than 90%. At the same time, no sodium nitrate and hydrogen peroxide need to be added during the reaction process, thereby reducing the cost of preparing the materials. The manganese oxide-based material produced can significantly reduce the content of manganese ions and the like in the wastewater.

[0046] Alternatively, according to a second embodiment of the first aspect of the present invention, based on the mass of the manganese-based adsorbent material, the manganese-based adsorbent material has a Mn content of 25-53% by weight, a S content of 1-15% by weight, a K content of 2-20% by weight, and a C content of 0.01-2% by weight. In a preferred embodiment, the remainder is oxygen. Preferably, the manganese-based adsorbent material has a Mn content of 40-53% by weight, a S content of 2-12% by weight, and a K content of 6-15% by weight. In a preferred embodiment, the remainder is oxygen. In a preferred embodiment, the sum of the weight percentages of Mn, C, O, S, and K in the manganese-based adsorbent material is 100% by weight.

[0047] According to the second embodiment of the first aspect of the present invention, preferably, in the XRD spectrum of the manganese-based adsorbent material, characteristic peaks are present at 2θ positions of 12.2±0.5°, 24.7±0.5°, 36.8±0.5° and 66.3±0.5°, respectively; and the half-maximum width of the diffraction peak at 12.2±0.5° is greater than 0.5°.

[0048] According to the second embodiment of the first aspect of the present invention, preferably, the specific surface area of ​​the manganese-based adsorption material is 200 to 350 m 2 / g, pore volume is 0.2~0.9ml / g; preferably, specific surface area is 240~320m 2 / g, and the pore volume is 0.4~0.7ml / g.

[0049] According to a second embodiment of the first aspect of the present invention, the manganese in the manganese-based adsorbent material is primarily manganese oxide, particularly in the form of MnO2, more preferably primarily in the form of δ-MnO2. The manganese-based adsorbent material is advantageously used for removing sulfur-containing impurities, such as hydrogen sulfide and carbonyl sulfide, from gases, such as hydrogen.

[0050] According to a second embodiment of the first aspect of the present invention, the manganese-based adsorbent material has a long penetration time of hydrogen sulfide-containing hydrogen feed gas (the penetration time refers to the time when the hydrogen sulfide content exceeds the detection limit. The longer the penetration time, the better the adsorption desulfurization performance of the sample), and exhibits more excellent performance in the hydrogen purification reaction. The sulfide content in the purified hydrogen can meet the content requirements of sulfide impurities in hydrogen used in fuel cells, and fully utilizes the Mn element in the graphite oxide separation stock solution, without the need to add an additional manganese source, thereby reducing the preparation cost of the manganese-based adsorbent material.

[0051] Alternatively, according to a third embodiment of the first aspect of the present invention, preferably, based on the mass of the manganese-based adsorbent material, the mass content of the Mn element in the manganese-based adsorbent material is 55-63%, preferably 58-61%, and the mass content of the C element is 0.01-1%. The Mn content in the manganese-based adsorbent material accounts for more than 95%, preferably more than 98% of the Mn content in the separation stock solution.

[0052] According to a third embodiment of the first aspect of the present invention, preferably, in the XRD pattern of the manganese-based adsorbent material, characteristic peaks are present at 2θ positions of 12.1±0.5°, 24.6±0.4°, 36.9±0.4° and 66.2±0.4°, respectively; and the half-maximum width of the diffraction peak at 12.1±0.5° is greater than 0.4°.

[0053] According to the third embodiment of the first aspect of the present invention, preferably, the specific surface area of ​​the manganese-based adsorption material is 10 to 30 m 2 / g, preferably 15 to 25 m 2 / g, and the pore volume is 0.01-0.1 ml / g, preferably 0.02-0.08 ml / g.

[0054] According to a third embodiment of the first aspect of the present invention, preferably, the manganese in the manganese-based adsorbent material is primarily present in the form of manganese oxide, particularly MnO2, and more preferably primarily in the form of δ-MnO2. The manganese-based adsorbent material is advantageously used to remove formaldehyde impurities from gases, such as hydrogen, and can also be used to remove sulfur-containing impurities, such as hydrogen sulfide and carbonyl sulfide, from gases, such as hydrogen.

[0055] According to the third embodiment of the first aspect of the present invention, the manganese-based adsorption material has a moderate specific surface area and pore volume, can effectively remove formaldehyde from the material, and can continue to have excellent formaldehyde removal performance after 12 hours of reaction. No nitrate needs to be added during the reaction process, which reduces the cost of preparing the material. At the same time, the content of the Mn element in the separation solution is significantly reduced, solving the problem of wastewater discharge polluting the environment during the graphite oxidation process.

[0056] The manganese-based adsorbent material contains C element in the form of graphite oxide. The presence of the graphite oxide plays a positive role in the removal of impurities such as sulfide and formaldehyde from gas by the manganese-based adsorbent material.

[0057] Second aspect

[0058] A second aspect of the present invention provides a method for co-producing graphite oxide and manganese-based adsorption material, wherein the method comprises:

[0059] S1: mixing graphite, Bronsted acid and permanganate, preferably potassium permanganate, and then heating the resulting mixture to react;

[0060] S2. adding water and / or hydrogen peroxide to the reaction material obtained in step S1, continuing the reaction, obtaining a separated stock solution and a solid phase through solid-liquid separation, and recovering the solid phase to obtain graphite oxide;

[0061] S3, with or without adding an auxiliary agent, performing a hydrothermal reaction on the separated stock solution obtained in step S2, separating the obtained solid product to obtain a manganese-based adsorption material;

[0062] The conditions for the hydrothermal reaction in step S3 include: a temperature of 100 to 200° C., preferably 120 to 200° C., more preferably 150 to 180° C., and a time of 1 to 72 hours, preferably 12 to 36 hours.

[0063] Optionally, the graphite is one or more of natural flake graphite, natural cryptocrystalline graphite and artificial graphite, preferably artificial graphite;

[0064] The carbon content of the graphite is 95% by weight or more, preferably 98% by weight or more, more preferably 99% by weight or more, more preferably 99.9% by weight or more; the ash content is 5% or less, preferably 2% or less, more preferably 0.1% by weight or less; the mesh size is 20 to 2000 mesh, preferably 20 to 500 mesh, more preferably 50-200 mesh, and more preferably 50 to 100 mesh.

[0065] Optionally, the Bronsted acid is selected from one or more of sulfuric acid, nitric acid and perchloric acid;

[0066] The concentration A0 of the Bronsted acid is any concentration between M-10% and M+10%, preferably between M-5% and M+5%, where M is the maximum concentration of the Bronsted acid, preferably the maximum concentration of analytically pure reagent grade Bronsted acid. In this context, the above concentrations are the concentrations of the acid in water.

[0067] Optionally, the mass ratio of the Bronsted acid to the graphite is (10-200):1, preferably (20-150):1, further preferably (25-100):1, and more preferably (30-100):1.

[0068] In the above embodiments, the properties of the prepared graphite oxide are advantageously improved by selecting the preferred types of graphite and Bronsted, carbon content and concentration.

[0069] In step S1, the mass ratio of potassium permanganate to graphite is (1-15):1, (1-12):1, (1-9):1, or (2-8):1, or (1-6):1, or (3-6):1, or (3.5-5.5):1.

[0070] In the aforementioned embodiment, when the amount of potassium permanganate used is relatively low, for example, a mass ratio of potassium permanganate to graphite of (1-6):1, the method of the present invention does not require the addition of an additional manganese source, and no sodium nitrate is added during the reaction process, thereby reducing the cost of preparing manganese oxide. Furthermore, the manganese-based adsorbent material obtained during the preparation of graphite oxide exhibits excellent performance in treating wastewater produced during the preparation process, significantly reducing the content of manganese ions and other substances in the wastewater, thereby resolving issues such as environmental pollution caused by wastewater discharge.

[0071] No sodium nitrate is added during the reaction process, which greatly improves the process safety. It is also beneficial to the subsequent preparation of manganese oxides and wastewater treatment, and significantly reduces the cost of graphite oxidation and the preparation of manganese-based adsorption materials.

[0072] According to another embodiment, the mass ratio of potassium permanganate to graphite during the preparation of graphite oxide is greater than 6.5. For example, the mass ratio of potassium permanganate to graphite is (8-15):1, preferably (9-12):1. When the mass ratio of potassium permanganate to graphite is high, the amount of potassium permanganate used during the preparation of graphite oxide is high, resulting in a faster oxidation rate and better oxidation effect. Furthermore, no additional manganese source is required during the preparation of manganese oxide, reducing the production cost of manganese oxide.

[0073] According to a preferred embodiment, in step S1, the heating reaction temperature is 30-60°C, preferably 40-50°C, and the time is 0.2-6 hours, preferably 0.5-4 hours.

[0074] According to a preferred embodiment, in step S1, no sodium nitrate is added.

[0075] According to a preferred embodiment, in step S1, potassium permanganate is added in multiple batches. The mass ratio of potassium permanganate added in each batch to the graphite is (0.05-2):1, preferably (0.1-2):1, for example (0.05-1):1, more preferably (0.2-1):1, and even more preferably (0.1-0.5):1.

[0076] According to a preferred embodiment, in step S1, the temperature during mixing is controlled to below 40°C, preferably below 30°C, and more preferably below 20°C. The mixing time is 0.2 to 12 hours, for example, 0.1 to 10 hours, preferably 0.5 to 6 hours, for example, 0.5 to 5 hours. The heating reaction temperature is 30 to 60°C, preferably 40 to 50°C. No sodium nitrate is added during the reaction in step S1. The mixing can be performed with stirring.

[0077] In another 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 to mix thoroughly. Potassium permanganate is then slowly added in portions while stirring. After the addition of the potassium permanganate, the mixture is stirred in a 40°C water bath for 0.5 hours. The ratio of the reactants is: graphite: concentrated sulfuric acid: potassium permanganate = 1g: 15-35ml: 6.5-15g.

[0078] In step S2, the mass ratio of the added amount of water to the graphite is (50-2000):1, preferably (80-250):1.

[0079] In step S2, the reaction time is 0.1 to 5 hours, preferably 0.5 to 2 hours. Preferably, the reaction temperature is 70 to 120°C, more preferably 85 to 105°C.

[0080] Optionally, in step S2, hydrogen peroxide is added instead of or in addition to water. Optionally, the mass ratio of the added hydrogen peroxide to the graphite is (20-500):1, preferably (50-200):1, and the mass concentration of the hydrogen peroxide is 0.01-5%, preferably 0.05-1%.

[0081] Optionally, in step S2, the graphite and hydrogen peroxide are mixed and heated for a reaction time of 0.1 to 6 hours, preferably 0.5 to 3 hours, and the heating reaction temperature is 60 to 99° C., preferably 85 to 95° C.

[0082] Optionally, the carbon-oxygen molar ratio of the graphite oxide is 0.9-2.5, preferably 1.1-2.

[0083] In one embodiment of the present invention, the graphite oxide has an oxygen content of 35 to 60% by weight, preferably 40 to 55% by weight, and a carbon content of 40 to 65% by weight, preferably 45 to 60% by weight. In this case, the graphite oxide prepared by the present invention has a high oxygen content, is easy to disperse, has many sheet defects, and has a strong chelating effect, which will have significant advantages in adsorbing heavy metal ions in wastewater and soil remediation.

[0084] Optionally, the carbon-oxygen molar ratio of the graphite oxide is 2 to 4, preferably 2.5 to 3.5.

[0085] According to a specific embodiment of the present invention, the graphite oxide has an oxygen content of 15 to 40% by weight, preferably 20 to 35% by weight, and a carbon content of 60 to 85% by weight, preferably 65 to 80% by weight. In this case, the graphite oxide prepared by the present invention has a moderate oxygen content and exhibits significant advantages in fire resistance and other aspects after thermal expansion exfoliation.

[0086] In a specific embodiment of the present invention, in the separated raw solution of graphite oxide, the Mn element content calculated as divalent manganese ions is 40-100 g / L, preferably 50-80 g / L, the potassium element content calculated as potassium ions is 25-80 g / L, preferably 35-60 g / L, the sulfur element content calculated as sulfate ions is 10-200 g / L, preferably 40-100 g / L, and the C element content calculated as carbon atoms is 5-50 g / L, preferably 8-20 g / L.

[0087] In a further preferred embodiment, the graphite oxide separation stock solution is an aqueous solution, mainly containing elements such as manganese, potassium, sulfur, and carbon, wherein the Mn element content calculated as divalent manganese ions is 64 g / L, the potassium element content calculated as potassium ions is 37 g / L, the sulfur element content calculated as sulfate ions is 102 g / L, and the C element content calculated as carbon atoms is 6.5 g / L, wherein the main source of the carbon element is the soluble graphite oxide remaining in the stock solution.

[0088] According to one aspect of the present invention, the solid-liquid separation in step S2 produces a separated stock solution and a solid phase, and the solid phase is recovered to obtain graphite oxide. Recovering the solid phase refers to drying after an optional washing step. Washing is a conventional operation in the art, such as water washing. The drying step may be conventional drying, vacuum drying, or freeze drying. Conventional drying may be performed at a temperature of 80 to 200°C for 1 to 48 hours; vacuum drying may be performed at a temperature of 20 to 100°C for 1 to 24 hours; and freeze drying may be performed at a temperature of -60 to -20°C for 12 to 48 hours.

[0089] In step S3, the conditions for the hydrothermal treatment include: a temperature of 100 to 200° C., preferably 120 to 200° C., more preferably 150 to 180° C., and a time of 1 to 72 hours, preferably 12 to 36 hours.

[0090] Optionally, step S3 includes:

[0091] (1) mixing the separation stock solution with optional water to obtain a mixed solution, wherein the mass ratio of the separation stock solution to water is 1:(0-10), preferably 1:(1-5);

[0092] (2) subjecting the mixed solution to a hydrothermal (crystallization) treatment, taking out a solid product, washing, drying and optionally calcining it to obtain the manganese-based adsorption material.

[0093] In a 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 more preferably 100-150°C; a time of 1-72h, for example 2-72h, preferably 4-36h, and more preferably 2-24h.

[0094] In some preferred embodiments of the present invention, an auxiliary agent is added in step S3. The auxiliary agent is a persulfate or hypochlorite, preferably one or more of ammonium persulfate, sodium persulfate, potassium persulfate, and sodium hypochlorite, more preferably ammonium persulfate and potassium persulfate, and the mass ratio of the auxiliary agent to the graphite is (0.2-10):1, preferably (0.5-5):1, and more preferably (1-3):1.

[0095] In the above embodiment, the mass ratio of the additive to the graphite and the hydrothermal reaction conditions are controlled within the preferred ranges to carry out the reaction, which is beneficial to improving various properties of manganese oxide and graphite oxide.

[0096] In step S3, the calcination conditions include: temperature of 250-700°C, preferably 300-500°C, time of 1-12 hours, preferably 2-6 hours, and pressure of 0.1-1 MPa, preferably 0.1-0.5 MPa.

[0097] The present invention produces manganese oxide crystalline powder simultaneously while preparing graphite oxide. The method of the present invention can significantly reduce the content of manganese ions and the like in wastewater. Generally, the manganese ion content is less than 50 ppm and can be directly discharged, thereby solving the problem of wastewater discharge polluting the environment during the preparation of graphite oxide.

[0098] According to a first embodiment of the second aspect of the present invention, there is provided a method for co-producing graphite oxide and manganese-based adsorption material, wherein the method comprises:

[0099] S1: After mixing graphite and Bronsted acid, adding permanganate, preferably potassium permanganate, preferably adding potassium permanganate in batches, and then heating the resulting mixture to react;

[0100] S2. adding water to the reaction material obtained in step S1, performing solid-liquid separation to obtain a separated liquid and a solid phase, and recovering the solid phase to obtain graphite oxide;

[0101] S3, performing a hydrothermal reaction on the separated stock solution while adding an auxiliary agent, separating the obtained solid product to obtain a manganese-based adsorption material;

[0102] Wherein, the auxiliary agent is persulfate and hypochlorite, preferably one or more of ammonium persulfate, sodium persulfate, potassium persulfate and sodium hypochlorite, and the mass ratio of the auxiliary agent to the graphite is (0.2-10):1;

[0103] The conditions of the hydrothermal reaction include: temperature of 100-200° C. and time of 1-72 hours.

[0104] Optionally, the mass ratio of the additive to the graphite is (0.5-5):1;

[0105] Optionally, the conditions of the hydrothermal reaction include: temperature of 100-150° C. and time of 2-24 h.

[0106] Optionally, the graphite oxide has an oxygen content of 15 to 40% by weight and a carbon content of 60 to 85% by weight.

[0107] According to a first embodiment of the second aspect of the present invention, in step S1 of the method, the mass ratio of the potassium permanganate to the graphite is (2-8):1, preferably (3-6):1.

[0108] Wherein, when potassium permanganate is added in batches, the mass ratio of potassium permanganate to the graphite mixed in each batch is (0.05-1):1, preferably (0.1-0.5):1;

[0109] The mass ratio of the added amount of water to the graphite is (50-2000):1, preferably (80-250):1.

[0110] Optionally, the method further includes:

[0111] In step S1, potassium permanganate is added in batches and mixed, and the temperature is controlled to below 40° C., preferably below 30° C., more preferably below 20° C., and stirred for 0.2 to 12 hours. No sodium nitrate and hydrogen peroxide are added during the reaction. The heating reaction conditions include: temperature of 30 to 60° C. and time of 0.2 to 6 hours.

[0112] In step S2, the time for adding water is 0.1 to 5 hours.

[0113] The manganese-based adsorption material according to the first embodiment of the first aspect of the present invention is prepared according to the method of the first embodiment of the second aspect of the present invention.

[0114] According to a second embodiment of the second aspect of the present invention, there is provided a method for preparing a manganese-based adsorption material by oxidizing graphite and treating wastewater generated by the graphite oxidation, wherein the method comprises:

[0115] S1: mixing graphite, Bronsted acid and permanganate, preferably potassium permanganate, and heating the resulting mixture to react;

[0116] S2 adds water, stirs and continues to react, and obtains separated liquid and solid phase through solid-liquid separation, and the solid phase is recovered to obtain graphite oxide;

[0117] S3: hydrothermally treating the separated stock solution to separate the obtained solid phase material to obtain a manganese-based adsorption material;

[0118] In step S1, the mass ratio of potassium permanganate to graphite is greater than 6.5. Optionally, in step S1, the mass ratio of potassium permanganate to graphite is 8 to 15, preferably 9 to 12.

[0119] Optionally, sodium nitrate and hydrogen peroxide are not added during the reaction process of the method.

[0120] Optionally, the graphite oxide has an oxygen content of 35 to 60% by weight and a carbon content of 40 to 65% by weight.

[0121] Optionally, in the separated raw solution of graphite oxide, the Mn element content calculated as divalent manganese ions is 40-100 g / L, the potassium element content calculated as potassium ions is 25-80 g / L, the sulfur element content calculated as sulfate ions is 10-200 g / L, and the C element content calculated as carbon atoms is 5-50 g / L.

[0122] Optionally, step S3 includes:

[0123] (1) mixing the separation stock solution with optional water to obtain a mixed solution, wherein the mass ratio of the separation stock solution to water is 1:(0-10);

[0124] (2) subjecting the mixed solution to hydrothermal treatment, taking out a solid product, washing, drying and optionally calcining the solid product to obtain the manganese-based adsorption material;

[0125] The hydrothermal conditions include: a temperature of 100 to 200° C. under autogenous pressure and a time of 2 to 72 hours;

[0126] The calcination conditions include: temperature of 250-700° C., time of 1-12 hours, and pressure of 0.1-1 MPa.

[0127] In a 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 to mix uniformly. Potassium permanganate is slowly added in batches while stirring and mixed. After the addition of potassium permanganate, the mixture is stirred and reacted in a 40°C warm water bath for 0.5h. An appropriate amount of deionized water is then added and the water bath temperature is raised to 95-98°C for 0.5h. The beaker is removed from the water bath and deionized water of about 60°C is added. Stirring is continued until the temperature drops to below 30°C. After stirring uniformly, the graphite oxide solid is separated by filtration to obtain a graphite oxide separation stock solution. The usage ratio of the above reactants is graphite: concentrated sulfuric acid: potassium permanganate: water = 1g: 15-35ml: 6.5-15g: 50-500ml.

[0128] The manganese-based adsorption material according to the second embodiment of the first aspect of the present invention is prepared by the method of the second embodiment of the second aspect of the present invention.

[0129] According to a third embodiment of the second aspect of the present invention, there is provided a method for co-producing graphite oxide and manganese-based adsorption material, wherein the method comprises:

[0130] S1: mixing graphite, Bronsted acid and permanganate, preferably potassium permanganate, and heating the resulting mixture to react;

[0131] S2 adds hydrogen peroxide to the reaction material obtained in step S1, continues the reaction, obtains a separated liquid and a solid phase through solid-liquid separation, and recovers the solid phase to obtain graphite oxide;

[0132] S3: hydrothermally treating the separated stock solution obtained in step S2 to separate the obtained solid phase material to obtain a manganese-based adsorption material;

[0133] The mass ratio of the added amount of the hydrogen peroxide to the graphite is (20-500):1, preferably (50-200):1, and the mass concentration of the hydrogen peroxide is 0.01-5%, preferably 0.05-1%;

[0134] The mass ratio of potassium permanganate to graphite is (1-6):1, preferably (3-6):1, and more preferably (3.5-5.5):1.

[0135] According to a specific embodiment of the method of the third embodiment of the second aspect of the present invention, graphite is first mixed with concentrated acid and potassium permanganate and then heated to react for a certain period of time. Hydrogen peroxide is then added and heated to react for a certain period of time. After solid-liquid separation, the separated liquid is subjected to a hydrothermal reaction, thereby simultaneously oxidizing the graphite and preparing the manganese-based adsorbent material. During the graphite oxidation process, the amount of potassium permanganate used is relatively small, and no sodium nitrate is added during the reaction process, which greatly improves process safety and facilitates the subsequent preparation of the manganese-based adsorbent material and wastewater treatment, significantly reducing the costs of graphite oxidation and preparation of the manganese-based adsorbent material.

[0136] The graphite oxide prepared by the present invention has a moderate oxygen content and has significant advantages in fire resistance and flame retardancy after thermal expansion and exfoliation.

[0137] In a specific embodiment of the present invention, the method further comprises:

[0138] In step S1, potassium permanganate is added in batches to the mixture of graphite and Bronsted acid, the mass ratio of potassium permanganate added in each batch to the graphite is (0.1-2):1, preferably (0.2-1):1, the temperature is controlled to below 40°C, preferably below 30°C, more preferably below 20°C during the mixing process, and the mixing time is 0.1-10h, preferably 0.5-5h; the temperature of the heating reaction is 30-60°C, preferably 40-50°C; and no sodium nitrate is added during the reaction;

[0139] In step S2, the graphite and hydrogen peroxide are mixed and heated for a reaction time of 0.1 to 6 hours, preferably 0.5 to 3 hours, and the heating reaction temperature is 60 to 99° C., preferably 85 to 95° C.;

[0140] In step S3, the conditions for the hydrothermal treatment include: a temperature of 120 to 200° C., preferably 150 to 180° C., and a time of 1 to 72 hours, preferably 12 to 36 hours.

[0141] The manganese-based adsorption material according to the third embodiment of the first aspect of the present invention is prepared by the method of the third embodiment of the second aspect of the present invention.

[0142] The third aspect

[0143] The third aspect of the present invention provides a manganese-based adsorption material prepared according to the second aspect of the present invention.

[0144] According to a preferred embodiment, based on the mass of the manganese-based adsorption material, the manganese-based adsorption material has a Mn content of 30 to 55 weight %; a S content of 0.8 to 10 weight %; a K content of 1 to 10 weight %; and a C content of 0.01 to 5 weight %.

[0145] Alternatively, according to another preferred embodiment, based on the mass of the manganese-based adsorption material, the Mn element content in the manganese-based adsorption material is 25-53 weight %, the S element content is 1-15 weight %, the K element content is 2-20 weight %, and the C element content is 0.01-2 weight %;

[0146] Alternatively, according to another preferred embodiment, based on the mass of the manganese-based adsorption material, the content of Mn element in the manganese-based adsorption material is 55-63 wt%, and the content of C element is 0.01-1 wt%.

[0147] According to a preferred embodiment, the XRD pattern of the manganese-based adsorbent material has characteristic peaks at 2θ of 28.6±0.5°, 37.4±0.3°, 41.0±0.3°, 42.8±0.3°, 56.6±0.3°, 59.4±0.3°, 64.9±0.3° and 72.4±0.3°, respectively; and the half-maximum width of the diffraction peak at 28.6±0.5° is greater than 0.1°;

[0148] Alternatively, according to another preferred embodiment, 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-maximum width of the diffraction peak at 12.2±0.5° is greater than 0.5°;

[0149] Alternatively, according to another preferred embodiment, the XRD pattern of the manganese-based adsorbent material has characteristic peaks at 2θ positions of 12.1±0.5°, 24.6±0.4°, 36.9±0.4° and 66.2±0.4°, respectively; and the half-maximum width of the diffraction peak at 12.1±0.5° is greater than 0.4°.

[0150] According to a preferred embodiment, the specific surface area of ​​the manganese-based adsorption material is 10 to 100 m 2 / g, preferably 30 to 60m 2 / g, the pore volume is 0.05-0.5 ml / g, preferably 0.1-0.3 ml / g, and the pore diameter is 12-36 nm, preferably 15-30 nm.

[0151] Alternatively, according to another preferred embodiment, the specific surface area of ​​the manganese-based adsorption material is 200 to 350 m 2 / g, pore volume is 0.2~0.9ml / g; preferably, specific surface area is 240~320m 2 / g, pore volume is 0.4~0.7ml / g:

[0152] Alternatively, according to another preferred embodiment, the specific surface area of ​​the manganese-based adsorption material is 10 to 30 m 2 / g, preferably 15 to 25 m 2 / g, and the pore volume is 0.01-0.1 ml / g, preferably 0.02-0.08 ml / g.

[0153] The fourth aspect

[0154] The fourth aspect of the present invention provides use of the manganese-based adsorption material obtained by the method of the first aspect or the third aspect or the second aspect for removing impurities such as sulfide and formaldehyde from gas.

[0155] The fifth aspect

[0156] A fifth aspect of the present invention provides a method for purifying hydrogen, the method comprising: contacting hydrogen with the manganese-based adsorption material provided by the first aspect of the present invention to perform a purification reaction.

[0157] In a specific embodiment of the present invention, the reaction conditions of the hydrogen purification method include: temperature of 20-50°C, pressure of 0.1-5.0 MPa, space velocity of 50-10000 h -1 Preferably, the temperature is 25-40°C, the pressure is 1-3 MPa, and the air velocity is 100-5000 h -1 .

[0158] The volume content of sulfide in the hydrogen is 0.1% to 1%, and the content of sulfide in the hydrogen is calculated as hydrogen sulfide.

[0159] In the present invention, the hydrogen purification method is carried out under relatively low temperature, high concentration and low space velocity conditions, and the sulfide in the hydrogen is effectively removed at a temperature below 50°C. The sulfide content in the purified hydrogen can meet the requirements for the sulfide impurity content in hydrogen used in fuel cells.

[0160] The present invention is further illustrated below by way of examples, but the present invention is not limited thereto.

[0161] The reagents used in the present invention are all commercially available analytically pure reagents.

[0162] Experimental Series 1

[0163] Example 1.1

[0164] a First, add 150 ml of concentrated sulfuric acid (mass concentration greater than 98%) and 5 g of graphite into a beaker to obtain a mixed solution;

[0165] b. Then, 25 g of potassium permanganate was added into the mixed solution obtained in step a in 5 batches, and the mixture was stirred at 15° C. for 1 h to obtain a mixed material;

[0166] c. Stir the mixture obtained in step b at 45° C. under autogenous pressure for 2 h to obtain a mixed slurry after reaction;

[0167] d. Add 150 ml of 0.05% hydrogen peroxide to the mixed slurry after the reaction in step c, continue stirring and reacting at 88° C. for 1 hour, and then directly filter using a sand filter funnel to separate the solid and liquid to obtain graphite oxide solid and filtered waste liquid;

[0168] e. The filtered waste liquid in step d is hydrothermally treated at 160° C. and autogenous pressure for 24 hours to separate the manganese oxide from the solid.

[0169] The XRD spectrum of the prepared manganese oxide is shown in FIG1 .

[0170] Example 1.2

[0171] The preparation method in Example 1.1 was adopted, except that in step b, the amount of potassium permanganate used was 10 g.

[0172] Example 1.3

[0173] The preparation method of Example 1.1 was adopted, except that in step e, the reaction temperature was 120° C. and the hydrothermal treatment time was 2 h.

[0174] Example 1.4

[0175] The preparation method in Example 1.1 was adopted, except that, in step a, 100 ml of concentrated sulfuric acid was added.

[0176] Example 1.5

[0177] The preparation method in Example 1.1 was adopted, except that in step c, the reaction temperature was 30°C.

[0178] Example 1.6

[0179] The preparation method of Example 1.1 was adopted, except that in step d, 450 ml of hydrogen peroxide of the same concentration was added.

[0180] Example 1.7

[0181] The preparation method of Example 1.1 was adopted, except that, in step d, 150 ml of 1.5% hydrogen peroxide was added.

[0182] Example 1.8

[0183] The preparation method in Example 1.1 was adopted, except that, in step b, potassium permanganate was added to the mixed solution obtained in step a at one time.

[0184] Example 1.9

[0185] The preparation method in Example 1.1 was adopted, except that in step b, the amount of potassium permanganate used was 4 g.

[0186] Example 1.10

[0187] The preparation method of Example 1.1 was adopted, except that in step d, 15 ml of hydrogen peroxide of the same concentration was added.

[0188] Example 1.11

[0189] The preparation method in Example 1.1 was adopted, except that in step d, 150 ml of 6% hydrogen peroxide was added.

[0190] Test Case

[0191] The XRD patterns of the samples were obtained using a Rigaku D / MaxA-ⅢA X-ray diffractometer. The test conditions were: Cu target Kα radiation, voltage 30 kV, current 20 mA, step scan, and scanning range 5° to 80°.

[0192] The element content of the sample was determined by XPS on a VGESCA-LABS X-ray photoelectron spectrometer, using Mg Kα X-rays as the laser source and the C1s binding energy of surface contaminant carbon to calibrate the binding energy of each element in the desulfurizer surface species.

[0193] Warm nitrogen adsorption-desorption (BET) measurements were performed on a JW-BK200C surface area and pore size analyzer manufactured by Beijing Jingwei Gaobo Co., Ltd. The surface area and pore volume were calculated using the two-parameter BET equation, and the pore distribution was calculated using the BJH method.

[0194] The effectiveness of the manganese oxide prepared in the present invention as a formaldehyde adsorption and removal agent was determined. The specific steps were as follows: 500 mg of manganese oxide was placed in the middle of a fixed-bed reaction tube with a diameter of 10 mm at room temperature and atmospheric pressure. Quartz wool was filled at both ends. A 1.0 mg / m³ concentration of manganese oxide was introduced at a flow rate of 10 ml / min. 3 The formaldehyde removal rate was calculated by detecting the residual formaldehyde concentration after 1 hour and 12 hours of reaction. The results of the formaldehyde removal rate after 1 hour of reaction and the formaldehyde removal rate after 12 hours of reaction are shown in Table 1. Other characterization results of the prepared samples are shown in Table 2. The XRD pattern of the manganese oxide prepared in Example 1.1 of the present invention is shown in Figure 1.

[0195] Table 1.1

[0196] Table 1.2

[0197] According to the test results in Table 1.1 and Table 1.2, it can be seen that the manganese oxide material prepared by the method provided by the present invention has a moderate specific surface area and pore volume when it falls within the preferred range, can effectively remove formaldehyde from the material, and can continue to have excellent formaldehyde removal performance after 12 hours of reaction. No nitrate needs to be added during the reaction process, which reduces the cost of preparing the material. At the same time, it significantly reduces the content of Mn element in the filtered waste liquid, and solves the problem of wastewater discharge polluting the environment during the graphite oxidation process.

[0198] The test results of Examples 1.1 to 1.8 show that when the preparation method and the amounts of hydrogen peroxide and potassium permanganate are within the preferred ranges of the first aspect of the present invention, the effects and performance of the products prepared by the present invention can be improved. Comparison of Example 1.1 with Examples 1.2 to 1.8 shows that when the amount and mass concentration of hydrogen peroxide, the amount of potassium permanganate, the type and amount of concentrated acid, the amount and batch of potassium permanganate added, the heating temperature, and the stirring time are all within the preferred limited ranges of the present invention, the formaldehyde removal performance of the manganese oxide material prepared by the present invention can be further improved.

[0199] The test results of Examples 1.9 to 1.12 show that the amount of potassium permanganate used in Example 1.9 is too low, and the Mn element content provided by the graphite oxide filtration waste liquid is low, resulting in a low Mn element content in the prepared manganese oxide, a large specific surface area and pore volume, and poor product performance. The formaldehyde removal rate in the material after 1 hour of reaction is significantly worse than that in Example 1.1, and the performance of removing formaldehyde from the material is significantly reduced after 12 hours of reaction; the amount of hydrogen peroxide used in Example 1.10 is not within the preferred range of the first aspect of the present invention, resulting in insufficient oxidation reaction, resulting in a large specific surface area and pore volume of the prepared manganese oxide, a decrease in product quality, and the formaldehyde removal rate in the material after 1 hour of reaction and 12 hours of reaction is lower than that of Examples 1.1 to 1.9; the use of too high a concentration of hydrogen peroxide in Example 1.11 will result in the specific surface area and pore volume of the prepared manganese oxide being too small, and the formaldehyde removal rate after 1 hour of reaction and 12 hours of reaction is significantly reduced.

[0200] Experiment Series 2

[0201] Example 2.1

[0202] a. Graphite oxide was prepared using an improved Hummer method. 5 g of graphite and 98% concentrated sulfuric acid were added to a beaker placed in an ice-water bath (~5° C.) and stirred to mix uniformly. Potassium permanganate was slowly added in five batches while stirring. After the addition of potassium permanganate, the mixture was stirred in a 40° C. water bath for 0.5 h. An appropriate amount of deionized water was then added and the water bath temperature was raised to 95-98° C. for 0.5 h. The beaker was removed from the water bath and deionized water of about 60° C. was added. Stirring was continued until the temperature dropped below 30° C. After stirring uniformly, the graphite oxide solid was separated by filtration to obtain a graphite oxide filtrate stock solution. The ratio of the reactants was graphite: concentrated sulfuric acid: potassium permanganate: water = 1 g: 30 ml: 10 g: 100 ml. The resulting materials were subjected to solid-liquid separation to obtain a filtrate stock solution liquid phase and a graphite oxide solid phase, respectively. The graphite oxide solid phase was vacuum dried at 80° C. for 6 h to obtain graphite oxide powder. The filtered raw liquid contained 64 g / L of Mn element calculated as divalent manganese ions, 37 g / L of potassium element calculated as potassium ions, 102 g / L of sulfur element calculated as sulfate ions, and 6.5 g / L of C element calculated as carbon atoms. The oxygen content of the graphite oxide was 43% by weight, and the carbon content was 57% by weight.

[0203] b. Add 50 mL of water and 50 g of the filtered graphite oxide stock solution into a beaker and mix to obtain a mixed solution;

[0204] c. The mixed solution obtained in step b was subjected to hydrothermal crystallization treatment at 140° C. under autogenous pressure for 12 h;

[0205] d. The manganese-based adsorption material obtained after hydrothermal treatment was filtered, washed, dried at 80°C for 6 h, and then calcined at 300°C for 4 h.

[0206] Example 2.2

[0207] The preparation method in Example 2.1 was adopted, except that in step d, the calcination temperature was 700° C. and the calcination time was 1 h.

[0208] Example 2.3

[0209] The preparation method in Example 2.1 was adopted, except that in step d, calcination was not performed.

[0210] Example 2.4

[0211] The preparation method of Example 2.1 was adopted, except that in step c, the hydrothermal crystallization temperature was 180°C.

[0212] Example 2.5

[0213] The preparation method of Example 2.1 was used, except that in step a, the ratio of the reactants was graphite: concentrated sulfuric acid: potassium permanganate: water = 1 g: 50 ml: 10 g: 150 ml; the filtered stock solution of graphite oxide had a Mn content of 41 g / L as divalent manganese ions, a potassium content of 26 g / L as potassium ions, a sulfur content of 195 g / L as sulfate ions, and a C content of 5.1 g / L as carbon atoms; the graphite oxide had an oxygen content of 48 wt%, and a carbon content of 52 wt%.

[0214] Example 2.6

[0215] The preparation method of Example 2.1 was used, except that in step a, the mass ratio of potassium permanganate to graphite when preparing graphite oxide was 6; the oxygen content of the graphite oxide was 33% by weight, and the carbon content was 67% by weight.

[0216] Test Case

[0217] The manganese-based adsorption materials and potassium permanganate of Examples 2.1 to 2.5 and Example 2.6 were tested as follows:

[0218] The XRD patterns of the samples were obtained using a Rigaku D / MaxA-ⅢA X-ray diffractometer. The test conditions were: Cu target Kα radiation, tube voltage 30 kV, tube current 20 mA, step scan, and a scanning range of 5° to 70°.

[0219] The average particle size of the prepared product was measured by scanning electron microscopy (ISI-60A electron microscope, ISI Corporation, USA, accelerating voltage 20 kV), and random samples were taken for particle size statistics.

[0220] The element content of the sample was determined by XPS on a VGESCA-LABS X-ray photoelectron spectrometer, using Mg Kα X-rays as the laser source and the C1s binding energy of surface contamination carbon (284.6 eV) to calibrate the binding energy of each element in the desulfurizer surface species.

[0221] Warm nitrogen adsorption-desorption (BET) measurements were performed on a JW-BK200C surface area and pore size analyzer from Beijing Jingwei Gaobo. Surface area and pore volume were calculated using the two-parameter BET equation, and pore distribution was calculated using the BJH method. Sulfide content in hydrogen after adsorption was analyzed using an online chromatograph (Shimadzu Nexis-2030) and an SCD fluorescence detector (SCD-2030).

[0222] 290 mg of each of the manganese-based adsorption material prepared in the embodiment of the present invention and potassium permanganate as an adsorbent were loaded into the constant temperature section of the reactor of a passivated fixed-bed microreactor with an inner diameter of 12 mm and a length of 500 mm, and filled with quartz sand. The volume content of hydrogen sulfide in the hydrogen raw material standard gas was 0.5%. Hydrogen was introduced at a flow rate of 30 ml / min at 40°C and 2.1 MPa for purification reaction. The hydrogen sulfide content in the purified hydrogen was analyzed online, and the analysis cycle was once every 5 minutes. The time from the introduction of hydrogen to the time when the hydrogen sulfide content in the purified hydrogen exceeded 0.004 ppm was counted as the penetration time. The penetration time test results of each sample are shown in Table 2.1, and the other characterization results of each sample are shown in Table 2.2. The XRD pattern of the manganese-based adsorption material of Example 2.1 prepared by the present invention is shown in Figure 2.

[0223] Table 2.1

[0224] Table 2.2

[0225] According to the test results in Table 2.1 and Table 2.2, it can be seen that the manganese-based adsorption material prepared by the preparation method provided by the preferred embodiment of the present invention has a longer penetration time of hydrogen sulfide-containing hydrogen feed gas and exhibits better performance in the hydrogen purification reaction. The sulfide content in the purified hydrogen can meet the content requirements of sulfide impurities in hydrogen used in fuel cells, and fully utilizes the Mn element in the graphite oxide filtration stock solution, without the need to add additional manganese source, thereby reducing the preparation cost of manganese oxide.

[0226] The test results of Examples 2.1 to 2.5 show that when the method for preparing the filtered stock solution of graphite oxide, the mass ratio of potassium permanganate to graphite when preparing graphite oxide, the element content in the filtered stock solution of graphite oxide, the hydrothermal crystallization treatment conditions, and the calcination conditions are within the specified ranges of the present invention, the effect and performance of the product prepared by the present invention can be further improved.

[0227] The test results of Example 2.6 and potassium permanganate as an adsorbent show that since the mass ratio of potassium permanganate to graphite in Example 2.6 is not within the preferred range, the hydrogen feed gas breakthrough time is significantly shorter than that of Examples 2.1 to 2.5. Therefore, the performance of the prepared manganese-based adsorption material in the hydrogen purification reaction is worse than that of the preferred embodiment of the present invention. When potassium permanganate is directly used as an adsorbent, the hydrogen feed gas breakthrough time is even shorter, indicating that its adsorption performance in the hydrogen purification reaction is poor.

[0228] Experiment Series 3

[0229] Example 3.1

[0230] a. Add 150 ml of concentrated sulfuric acid (mass concentration greater than 98%) and 5 g of graphite into a beaker to obtain a mixed solution;

[0231] b. Add 25 g of potassium permanganate into the mixed solution obtained in step a in 5 equal batches, and stir at 10° C. for 1 h to obtain a mixed material;

[0232] c. Stir the mixture obtained in step b at 35°C under autogenous pressure for 2 h;

[0233] d. Add 150 ml of water to the mixture in step c, continue stirring and reacting at 90° C. for 1 hour, and then filter to obtain graphite oxide solid and separated stock solution;

[0234] e. At 120° C. and autogenous pressure, the separated stock solution in step d was mixed with 5 g of potassium persulfate, and subjected to hydrothermal treatment for 24 h. The solid-liquid separation was performed to remove the solid phase manganese oxide.

[0235] The XRD spectrum of the prepared manganese oxide is shown in FIG3 .

[0236] Example 3.2

[0237] The preparation method in Example 3.1 was adopted, except that in step e, the separated stock solution in step d was mixed with 1 g of potassium persulfate.

[0238] Example 3.3

[0239] The preparation method in Example 3.1 was adopted, except that in step e, the reaction temperature was 160° C. and the hydrothermal treatment time was 2 h.

[0240] Example 3.4

[0241] The preparation method in Example 3.1 was adopted, except that in step e, 5 g of potassium persulfate was replaced by 5 g of ammonium persulfate.

[0242] Example 3.5

[0243] The preparation method in Example 3.1 was adopted, except that in step a, 100 ml of concentrated sulfuric acid was added.

[0244] Example 3.6

[0245] The preparation method in Example 3.1 was adopted, except that 15 g of potassium permanganate was added in step b.

[0246] Example 3.7

[0247] The preparation method in Example 3.1 was adopted, except that in step c, the reaction temperature was 30°C.

[0248] Example 3.8

[0249] The preparation method in Example 3.1 was adopted, except that in step d, 450 ml of water was added.

[0250] Example 3.9

[0251] The preparation method in Example 3.1 was adopted, except that in step b, the mass ratio of potassium permanganate to graphite added in each batch was 5:3, that is, potassium permanganate was added in three batches.

[0252] Example 3.10

[0253] The preparation method in Example 3.1 was adopted, except that in step a, 150 ml of concentrated nitric acid was added instead of concentrated sulfuric acid.

[0254] Example 3.11

[0255] The preparation method in Example 3.1 was adopted, except that in step b, 25 g of potassium permanganate was added to the mixed solution obtained in step a at one time.

[0256] Example 3.12

[0257] The preparation method in Example 3.1 was adopted, except that in step e, the reaction temperature was 250° C. and the hydrothermal treatment time was 96 h.

[0258] Example 3.13

[0259] The preparation method in Example 3.1 was adopted, except that in step e, the separated stock solution in step d was mixed with 30 g of potassium persulfate.

[0260] Test Case

[0261] The XRD patterns of the samples were obtained using a Rigaku D / MaxA-ⅢA X-ray diffractometer. The test conditions were: Cu target Kα radiation, voltage 30 kV, current 20 mA, step scan, and scanning range 5° to 80°.

[0262] The element content of the sample was determined by XPS on a VGESCA-LABS X-ray photoelectron spectrometer, using Mg Kα X-rays as the laser source and the C1s binding energy of surface contamination carbon (284.6 eV) to calibrate the binding energy of each element in the desulfurizer surface species.

[0263] Warm nitrogen adsorption-desorption (BET) measurements were performed on a JW-BK200C surface area and pore size analyzer manufactured by Beijing Jingwei Gaobo Co., Ltd. The surface area and pore volume were calculated using the two-parameter BET equation, and the pore distribution was calculated using the BJH method.

[0264] 500 mg of the examples and comparative examples prepared in the present invention were loaded as desulfurizers into the constant temperature section of a passivated fixed-bed microreactor with an inner diameter of 12 mm and a length of 500 mm, topped and bottom with quartz sand. The sulfur-containing compound feedstock contained 5000 ppm of sulfide (the carrier gas was hydrogen, and the sulfide was a mixture of hydrogen sulfide and carbonyl sulfide in a 1:1 molar ratio). Desulfurization was carried out at 50°C and 2 MPa at a flow rate of 100 ml / min. The sulfide content in the post-desulfurization material was analyzed online, and the sulfide removal rate was calculated. The sulfide removal rate after 1 hour is shown in Table 3.1. Other characterization results of the prepared samples are shown in Table 3.2. The XRD pattern of the manganese oxide prepared in Example 3.1 is shown in Figure 3.

[0265] Table 3.1

[0266] Table 3.2

[0267] According to the test results in Table 3.1 and Table 3.2, it can be seen that the manganese oxide prepared by the preparation method provided by the preferred embodiment of the present invention has a large specific surface area and pore volume, a moderate pore size, and exhibits excellent performance in removing sulfur compounds in the reaction process of removing sulfides in the gas, with a removal rate of sulfur compounds in the material reaching more than 90%. At the same time, no sodium nitrate and hydrogen peroxide need to be added during the reaction process, thereby reducing the cost of preparing materials. The manganese oxide produced by the reaction can significantly reduce the content of manganese ions and the like in wastewater.

[0268] The test results of Examples 3.1 to 3.10 show that when the preparation method, type and amount of additives, and reaction conditions are within the preferred ranges of the present invention, the effects and performance of the products prepared by the present invention can be improved. A comparison of Example 3.1 with Examples 3.2 to 3.10 shows that when the type and amount of additives, hydrothermal reaction conditions, type and amount of concentrated acid, amount and batch of potassium permanganate, heating temperature, stirring time, and the mass ratio of water added to graphite added are all within the preferred limited ranges of the present invention, the sulfide removal performance of the manganese oxide prepared by the present invention can be further improved and the manganese ion content in the preparation wastewater can be significantly reduced.

[0269] From the test results of Examples 3.11 to 3.13, it can be seen that in Example 3.11, potassium permanganate is added to the graphite at one time, the reaction temperature rises rapidly to above 80°C, and part of the material splashes, resulting in uneven adsorption of potassium permanganate on the graphite, which leads to the prepared manganese oxide having too large a pore volume and a large pore diameter, poor adsorption effect on sulfides in the gas, low removal rate, and too high a manganese ion content in the wastewater; in Example 3.12, the hydrothermal treatment temperature is too high and the treatment time is too long. Too high a temperature will cause the oxygen-containing groups to be thermally decomposed, thereby affecting The influence of the product structure results in that the specific surface area, pore volume and pore diameter of the prepared manganese oxide are all small, resulting in that it cannot effectively remove sulfides in the gas, the removal rate is low, and the manganese ion content in the wastewater is higher than that in Examples 1 to 10; the dosage of potassium persulfate in Example 3.13 is too high, and the degree of oxidation is too high, which is not conducive to the formation of manganese oxide, resulting in that the specific surface area of ​​the prepared manganese oxide is small, the pore volume and pore diameter are too small, and the product performance is poor, resulting in that it cannot effectively remove sulfides in the gas, the removal rate is low, and the manganese ion content in the wastewater is too high.

[0270] Experiment Series 4

[0271] Example 4.1

[0272] a. Add 150 ml of concentrated sulfuric acid (mass concentration greater than 98%) and 5 g of graphite into a beaker to obtain a mixed solution;

[0273] b. Add 25 g of potassium permanganate into the mixed solution obtained in step a in 5 equal batches, and stir at 10° C. for 1 h to obtain a mixed material;

[0274] c. Stir the mixture obtained in step b at 35°C under autogenous pressure for 2 h;

[0275] d. Add 150 ml of water to the mixture in step c, continue stirring and reacting at 90° C. for 1 hour, and then filter to obtain graphite oxide solid and separated stock solution;

[0276] e. At 120° C. and autogenous pressure, the separated stock solution in step d was mixed with 5 g of potassium persulfate, and subjected to hydrothermal treatment for 24 h. The solid-liquid separation was performed to remove the solid phase manganese oxide.

[0277] The content of Mn in the solid phase manganese oxide was determined to be 49.8% by weight; S was 2.1% by weight; K was 5.2% by weight; C was 0.25% by weight, and the balance was O. Further infrared spectroscopy analysis showed that the sample had a peak at 1725 cm -1 、1630cm -1 、1110cm -1 There are absorption peaks near 1725cm -1 The absorption peak at 1630 cm is the stretching vibration peak of C=O. -1 The bending vibration absorption peak of C-OH is 1110 cm -1 The peak is the vibration absorption peak of COC, indicating that the carbon element in the sample exists in the form of graphite oxide.

[0278] Comparative Example 4.1

[0279] a. Add 150ml of concentrated sulfuric acid (mass concentration greater than 98%) into a beaker;

[0280] b. Add 25 g of potassium permanganate into the concentrated sulfuric acid in step a in 5 equal batches, and stir at 10° C. for 1 h to obtain a mixture;

[0281] c. Stir the mixture obtained in step b at 35°C under autogenous pressure for 2 h;

[0282] d. Add 150 ml of water to the mixture in step c, and continue stirring and reacting at 90° C. for 1 hour to obtain a mixed stock solution;

[0283] e. At 120° C. and autogenous pressure, the mixed solution in step d was mixed with 5 g of potassium persulfate, and subjected to hydrothermal treatment for 24 h. The solid-liquid separation was performed to remove the solid phase manganese oxide.

[0284] The content of Mn in the solid phase manganese oxide was determined to be 58.6% by weight, 3.0% by weight, 0.6% by weight, 0% by weight, and 0% by weight, with the remainder being O. Further infrared spectroscopy analysis revealed that the sample contained 58.6% by weight of Mn, 3.0% by weight of S, 0.6% by weight, and 0% by weight of C. -1 、1630cm -1 、1110cm -1 There is no absorption peak near the sample, indicating that the sample does not contain carbon and graphite oxide.

[0285] Comparative Example 4.2

[0286] The hydrogen purification performance was investigated using commercially available manganese dioxide (Sinopharm Chemical Reagent Co., Ltd., analytical grade) as the adsorbent.

[0287] Comparative Example 4.3

[0288] The preparation method of Comparative Example 4.1 was adopted, except that 0.25 wt % of graphite oxide was added to the solid phase manganese oxide after step e, and the mixture was uniformly mixed.

[0289] Comparative Example 4.4

[0290] 0.25 wt % of graphite oxide was added to commercially available manganese dioxide (Sinopharm Chemical Reagent Co., Ltd., analytical grade) and mixed uniformly.

[0291] Test Case

[0292] 500 mg of the samples prepared in Example 4.1 and Comparative Examples 4.1 to 4.4 were loaded as desulfurizers into the constant temperature section of a passivated fixed-bed microreactor with an inner diameter of 12 mm and a length of 500 mm, topped and bottomed with quartz sand. The sulfur-containing compound feedstock contained 5000 ppm of sulfide (the carrier gas was hydrogen, and the sulfide was a mixture of hydrogen sulfide and carbonyl sulfide in a 1:1 molar ratio). Desulfurization was performed at 30°C and 2 MPa at a flow rate of 100 ml / min. The sulfide content in the post-desulfurization material was analyzed online, and the sulfide removal rate was calculated. The sulfide removal rate after 1 hour is shown in Table 4.1.

[0293] Table 4.1

[0294] The preferred embodiments of the present invention are described in detail above in conjunction with the accompanying drawings. However, the present invention is not limited to the specific details in the above embodiments. Within 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 scope of protection of the present invention.

[0295] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0296] In addition, the various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A manganese-based adsorption material, comprising Mn element, C element, O element, and optionally S element and optionally K element; Wherein, based on the mass of the manganese-based adsorption material, the manganese-based adsorption material has a Mn content of 25 to 63% by weight, a S content of 0 to 15% by weight, an O content of 14 to 37% by weight, a K content of 0 to 20% by weight, and a C content of 0.01 to 5% by weight. The manganese-based adsorbent material contains Mn in the form of manganese oxide and C in the form of graphite oxide.

2. The manganese-based adsorption material according to claim 1, wherein Based on the mass of the manganese-based adsorption material, the manganese-based adsorption material has a Mn content of 30 to 55% by weight, an S content of 0.8 to 10% by weight, a K content of 1 to 10% by weight, and a C content of 0.01 to 5% by weight; Or based on the mass of the manganese-based adsorption material, the Mn element content in the manganese-based adsorption material is 25-53% by weight, the S element content is 1-15% by weight, the K element content is 2-20% by weight, and the C element content is 0.01-2% by weight; Or based on the mass of the manganese-based adsorption material, the content of Mn element in the manganese-based adsorption material is 55-63% by weight, and the content of C element is 0.01-1% by weight.

3. The manganese-based adsorption material according to claim 1 or 2, wherein: In the XRD spectrum of the manganese-based adsorbent material, characteristic peaks exist at 2θ positions of 28.6±0.5°, 37.4±0.3°, 41.0±0.3°, 42.8±0.3°, 56.6±0.3°, 59.4±0.3°, 64.9±0.3° and 72.4±0.3°, respectively; and the half-peak width of the diffraction peak at 28.6±0.5° is greater than 0.1°; or the XRD spectrum 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-peak width of the diffraction peak at 12.2±0.5° is greater than 0.5°; Alternatively, in the XRD spectrum of the manganese-based adsorbent material, characteristic peaks exist at 2θ positions of 12.1±0.5°, 24.6±0.4°, 36.9±0.4° and 66.2±0.4°, respectively; and the half-peak width of the diffraction peak at 12.1±0.5° is greater than 0.4°.

4. The manganese-based adsorption material according to any one of claims 1 to 3, wherein The specific surface area of ​​the manganese-based adsorption material is 10 to 100 m 2 / g, preferably 30 to 60 m 2 / g, pore volume is 0.05-0.5 ml / g, preferably 0.1-0.3 ml / g, pore diameter is 12-36 nm, preferably 15~30nm. Or the specific surface area of ​​the manganese-based adsorption material is 200 to 350 m 2 / g, pore volume is 0.2-0.9 ml / g; preferably, specific surface area is 240-320 m 2 / g, pore volume is 0.4~0.7ml / g: Or the specific surface area of ​​the manganese-based adsorption material is 10 to 30 m 2 / g, preferably 15 to 25 m 2 / g, and the pore volume is 0.01-0.1 ml / g, preferably 0.02-0.08 ml / g.

5. A method for co-producing graphite oxide and manganese-based adsorption material, wherein: The method includes: S1: mixing graphite, Bronsted acid and permanganate, preferably potassium permanganate, and then heating the resulting mixture to react; S2. adding water and / or hydrogen peroxide to the reaction material obtained in step S1, continuing the reaction, obtaining a separated stock solution and a solid phase through solid-liquid separation, and recovering the solid phase to obtain graphite oxide; S3, with or without adding an auxiliary agent, subjecting the separated stock solution obtained in step S2 to a hydrothermal reaction, separating the obtained solid product, and obtaining a manganese-based adsorption material; The conditions of the hydrothermal reaction in step S3 include: a temperature of 100 to 200° C., preferably 120 to 200° C., more preferably 150 to 180° C., and a time of 1 to 72 hours, preferably 12 to 36 hours.

6. The method according to claim 5, wherein: In step S1, one or more of the following features are present: The mass ratio of the permanganate to the graphite is (1-15):1, The graphite is one or more of natural flake graphite, natural cryptocrystalline graphite and artificial 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 2% or less, and the mesh size is 20 to 2000 mesh, preferably 50 to 200 mesh; The Bronsted acid is selected from one or more of sulfuric acid, nitric acid and perchloric acid; The concentration A0 of the Bronsted acid is any concentration between M-10% and M+10%, preferably A0 is any concentration between M-5% and M+5%, M is the maximum concentration of the Bronsted acid, and The mass ratio of the Bronsted acid to the graphite is (10-200):1, preferably (25-100):

1.

7. The method according to claim 5 or 6, wherein: In step S2, one or more of the following features are present: When hydrogen peroxide is added, the mass ratio of the added amount of the hydrogen peroxide to the graphite is (50-200):1, preferably (50-200):1, and the mass concentration of the hydrogen peroxide is 0.01-5%, preferably 0.05-1%; Alternatively, without adding hydrogen peroxide, the mass ratio of the added water to the graphite is (50-2000):1, preferably (80-250):

1.

8. The method according to any one of claims 5 to 7, wherein: The carbon-oxygen molar ratio of the graphite oxide is 2 to 4, preferably 2.5 to 3.

5. Alternatively, the oxygen content of the graphite oxide is 35 to 60% by weight, the carbon content is 40 to 65% by weight, Alternatively, the graphite oxide has an oxygen content of 15 to 40% by weight and a carbon content of 60 to 85% by weight.

9. The method according to any one of claims 5 to 8, wherein step S3 is carried out under the condition of adding an auxiliary agent, the auxiliary agent is a persulfate or hypochlorite, preferably one or more of ammonium persulfate, sodium persulfate, potassium persulfate and sodium hypochlorite, and the mass ratio of the auxiliary agent to the graphite is (0.2-10):

1.

10. The method according to any one of claims 5 to 9, wherein: The method has one or more of the following characteristics: In step S1, potassium permanganate is added to the graphite and the Bronsted acid in batches, and the mass ratio of potassium permanganate added in each batch to the graphite is (0.1-2):1, preferably (0.2-1):1, and the temperature is controlled to be below 40°C, preferably below 30°C, more preferably below 20°C during the mixing process, and the mixing time is 0.1-10h, preferably 0.5-5h; the temperature of the heating reaction is 30-60°C, preferably 40-50°C, and the time is 0.2-6h, preferably 0.5-4h; In step S2, without adding hydrogen peroxide, the reaction time is 0.1 to 5 hours, preferably 0.5 to 2 hours, preferably, the reaction temperature is 70 to 120°C, more preferably 85 to 105°C. In step S2, when hydrogen peroxide is added, the reaction time is 0.1 to 6 hours, preferably 0.5 to 3 hours, and the reaction temperature is 60 to 99° C., preferably 85 to 95° C.; In step S3, the conditions of the hydrothermal treatment include: a temperature of 120 to 200° C., preferably 150 to 180° C., and a time of 1 to 72 hours, preferably 12 to 36 hours.

11. The method according to any one of claims 5 to 10, wherein: Step S3 includes: (1) mixing the separation stock solution with optional water to obtain a mixed solution, wherein the mass ratio of the separation stock solution to water is 1:(0-10); (2) subjecting the mixed solution to hydrothermal treatment, taking out a solid product, washing, drying and optionally calcining the solid product to obtain the manganese-based adsorption material; The hydrothermal conditions include: a temperature of 100 to 200°C under autogenous pressure, a time of 2～72h； The calcination conditions include: temperature of 250-700° C., time of 1-12 hours, and pressure of 0.1-1 MPa.

12. A manganese-based adsorption material prepared by the method according to any one of claims 5 to 11.

13. The manganese-based adsorption material according to claim 12, wherein Based on the mass of the manganese-based adsorption material, the manganese-based adsorption material has a Mn content of 30 to 55 weight percent, a S content of 0.8 to 10 weight percent, a K content of 1 to 10 weight percent, and a C content of 0.01 to 5 weight percent. Or based on the mass of the manganese-based adsorption material, the Mn element content in the manganese-based adsorption material is 25-53% by weight, the S element content is 1-15% by weight, the K element content is 2-20% by weight, and the C element content is 0.01-2% by weight; Or based on the mass of the manganese-based adsorption material, the content of Mn element in the manganese-based adsorption material is 55-63% by weight, and the content of C element is 0.01-1% by weight.

14. The manganese-based adsorption material according to claim 12, wherein In the XRD spectrum of the manganese-based adsorbent material, characteristic peaks exist at 2θ positions of 28.6±0.5°, 37.4±0.3°, 41.0±0.3°, 42.8±0.3°, 56.6±0.3°, 59.4±0.3°, 64.9±0.3° and 72.4±0.3°, respectively; and the half-peak width of the diffraction peak at 28.6±0.5° is greater than 0.1°; Or in the XRD spectrum of the manganese-based adsorbent material, characteristic peaks exist at 2θ positions of 12.2±0.5°, 24.7±0.5°, 36.8±0.5° and 66.3±0.5°, respectively; the half-peak width of the diffraction peak at 12.2±0.5° is greater than 0.5°; Alternatively, in the XRD spectrum of the manganese-based adsorbent material, characteristic peaks exist at 2θ positions of 12.1±0.5°, 24.6±0.4°, 36.9±0.4° and 66.2±0.4°, respectively; and the half-peak width of the diffraction peak at 12.1±0.5° is greater than 0.4°.

15. The manganese-based adsorption material according to claim 12, wherein The specific surface area of ​​the manganese-based adsorption material is 10 to 100 m 2 / g, preferably 30 to 60 m 2 / g, the pore volume is 0.05-0.5 ml / g, preferably 0.1-0.3 ml / g, and the pore diameter is 12-36 nm, preferably 15-30 nm. Or the specific surface area of ​​the manganese-based adsorption material is 200 to 350 m 2 / g, pore volume is 0.2-0.9 ml / g; preferably, specific surface area is 240-320 m 2 / g, pore volume is 0.4~0.7ml / g: Or the specific surface area of ​​the manganese-based adsorption material is 10 to 30 m 2 / g, preferably 15 to 25 m 2 / g, and the pore volume is 0.01-0.1 ml / g, preferably 0.02-0.08 ml / g.

16. Use of the manganese-based adsorption material according to any one of claims 1 to 4 and 12 to 15 for removing sulfides, especially hydrogen sulfide and carbonyl sulfide, from gases, and / or for removing formaldehyde from gases.

17. A method for purifying hydrogen, the method comprising: Contacting hydrogen with the manganese-based adsorption material according to any one of claims 1 to 4 and 12 to 15 to perform a purification reaction; The reaction conditions of the hydrogen purification method include: temperature of 20-50°C, pressure of 0.1-5.0 MPa, and space velocity of 50-10000 h -1 ; The volume content of sulfide in the hydrogen is 0.1-1%, and the content of sulfide in the hydrogen is calculated as hydrogen sulfide.

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