Dual active component carbon monoxide adsorbent, method of making and method of adsorbing carbon monoxide

Abstract

The present application relates to the field of adsorbing material, discloses a dual active component carbon monoxide adsorbent, a preparation method thereof and a carbon monoxide adsorption method.The carbon monoxide adsorbent comprises a carrier and an active component loaded on the carrier, the carrier is a porous carbon material, and the active component is Cu (I) and Mn (II). The dual active component carbon monoxide adsorbent provided by the present application uses a porous carbon material as a carrier, and loads the active components Cu (I) and Mn (II) on the carrier, so that the carbon monoxide adsorption breakthrough time is long, the carbon monoxide adsorption capacity is high, the use condition is mild, the preparation method is simple, and the dual active component carbon monoxide adsorbent has a good industrial application prospect.

Description

Technical Field

[0001] This invention relates to the field of adsorption materials, specifically to a dual-active-component carbon monoxide adsorbent, its preparation method, and a method for adsorbing carbon monoxide. Background Technology

[0002] Refineries possess abundant and diverse hydrogen resources, primarily from natural gas reforming and refining byproducts, which hold promise for use in fuel cell vehicles. However, these hydrogen sources all contain carbon monoxide impurities; even trace amounts of CO can poison precious metal catalysts. Standards for hydrogen used in fuel cell vehicles limit CO content to below 0.2 ppm to protect precious metal catalysts. Therefore, developing adsorbents capable of separating CO from refinery hydrogen is of significant industrial importance.

[0003] CN110270303A discloses a high-efficiency CO adsorbent and its preparation method, the raw material being a mixture of copper chloride and basic copper salt with a high specific surface area support. Literature (Yin,Y.;Wen,Z.;Shi,L.;Zhang,Z.;Yang,Z.;Xu,C.;Sun,H.;Wang,S.;Yuan,A.,Acs Sustainable Chemistry & Engineering 2019,7(13),11284-11292.) reports a method for preparing a CO adsorbent by loading Cu active components and V stabilizing agents onto a MIL-101 support to improve the stability of the adsorbent. Literature (Xue,C.;Hao,W.;Cheng,W.;Ma,J.;Li,R.,Materials 2019,12(10),1605.) reports a method for preparing a CO adsorbent by physically mixing copper salt with activated carbon powder followed by vacuum calcination.

[0004] However, the aforementioned adsorbents have limited CO adsorption capacity due to their low specific surface area, narrow micropores, and single active component. Therefore, there is an urgent need to develop more efficient CO adsorbents. Summary of the Invention

[0005] The purpose of this invention is to overcome the problem of low adsorption capacity of carbon monoxide adsorbents in the prior art, and to provide a dual-active-component carbon monoxide adsorbent, its preparation method and adsorption method, which has mild operating conditions and high carbon monoxide adsorption capacity.

[0006] To achieve the above objectives, the first aspect of the present invention provides a dual-active-component carbon monoxide adsorbent, the carbon monoxide adsorbent comprising a support and an active component loaded on the support, wherein the support is a porous carbon material and the active component is Cu(I) and Mn(II).

[0007] A second aspect of the present invention provides a method for preparing a dual-active-component carbon monoxide adsorbent, the method comprising:

[0008] (1) Provide an active component solution containing copper and manganese salts;

[0009] (2) The porous carbon material is impregnated with the active component solution and then calcined under an inert atmosphere;

[0010] The copper salt is copper chloride, and the manganese salt is divalent manganese salt.

[0011] A third aspect of the present invention provides a method for adsorbing carbon monoxide, the method comprising:

[0012] A gas containing carbon monoxide is brought into contact with an adsorbent to adsorb the carbon monoxide contained in the gas onto the adsorbent.

[0013] The adsorbent is either the carbon monoxide adsorbent described in the first aspect or the carbon monoxide adsorbent prepared according to the method described in the second aspect.

[0014] Through the above technical solution, the dual-active-component carbon monoxide adsorbent provided by the present invention uses porous carbon material as a carrier, and loads the active components Cu(I) and Mn(II) on the carrier. It not only has a long CO adsorption breakthrough time and high CO adsorption capacity, but also has mild operating conditions and a simple preparation method, and has good prospects for industrial application. Attached Figure Description

[0015] Figure 1 This is an XPS plot of the Cu 2p energy level of the carbon monoxide adsorbent prepared in Example 1;

[0016] Figure 2 This is an XPS plot of the Mn 2p energy level of the carbon monoxide adsorbent prepared in Example 1;

[0017] Figure 3 This is the XRD pattern of the carbon monoxide adsorbent prepared in Example 1;

[0018] Figure 4 These are the CO adsorption breakthrough curves of the carbon monoxide adsorbents prepared in Examples 1-5 and the comparative examples. Detailed Implementation

[0019] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0020] The first aspect of the present invention provides a dual-active-component carbon monoxide adsorbent, the carbon monoxide adsorbent comprising a support and an active component loaded on the support, wherein the support is a porous carbon material and the active component is Cu(I) and Mn(II).

[0021] According to some embodiments of the present invention, the active components are Cu(I) and Mn(II), and the aforementioned dual active components are beneficial for improving the carbon monoxide adsorption capacity of the adsorbent. Cu(I) refers to monovalent copper, such as CuCl; Mn(II) refers to divalent manganese. The valence state of the active components can be determined by X-ray photoelectron spectroscopy (XPS). The X-ray photoelectron spectroscopy (XPS) instrument used is a Qtac-100 LEISXPS instrument, and measurements are taken using monochromatic Al target Kα radiation (1486.6 eV).

[0022] According to some embodiments of the present invention, the carrier is a porous carbon material, which can be any porous carbon material conventionally used in the art for preparing carbon monoxide adsorbents. To further improve the carbon monoxide adsorption capacity of the adsorbent, preferably, the porous carbon material is selected from at least one of activated carbon, graphene, carbon, and carbon black, more preferably activated carbon. The activated carbon can be shaped activated carbon or powdered activated carbon.

[0023] According to some embodiments of the present invention, preferably, the BET specific surface area of ​​the porous carbon material is 800-1800 m². 2 / g, preferably 1000-1500m 2 / g. Using the aforementioned porous carbon material with a specific BET surface area as a support is beneficial for the uniform dispersion and loading of the active components.

[0024] According to some embodiments of the present invention, the pore structure properties of porous carbon materials are detected by the BET test method. Specifically, a Quantachrome AS-6B analyzer is used for measurement, and the specific surface area of ​​the porous carbon material is obtained by the Brunauer-Emmett-Taller (BET) method.

[0025] According to some embodiments of the present invention, preferably, the loading of Cu(I) on the porous carbon material in the carbon monoxide adsorbent is 4-12 mmol / g, more preferably 6-8 mmol / g.

[0026] According to some embodiments of the present invention, preferably, the loading of Mn(II) on the porous carbon material in the carbon monoxide adsorbent is 0.1-4 mmol / g, more preferably 0.5-2 mmol / g.

[0027] According to some embodiments of the present invention, preferably, the molar ratio of Cu(I) to Mn(II) in the carbon monoxide adsorbent is 3-30:1, more preferably 3-12:1. Limiting the molar ratio of the two active components to the above range is beneficial for the dispersed loading of the active components, enabling a synergistic effect and further extending the CO adsorption breakthrough time of the adsorbent.

[0028] According to some embodiments of the present invention, the components of the carbon monoxide adsorbent are determined based on the amount of each raw material fed into it.

[0029] According to some embodiments of the present invention, preferably, XRD analysis shows that the carbon monoxide adsorbent has no sharp peaks in the range of 2θ angles from 20° to 30° and / or in the range of 2θ angles from 40° to 50°. That is, no obvious diffraction peaks of CuCl (at 2θ = 28.5° and 47.4°, corresponding to the characteristic diffraction peaks of CuCl) are observed in the XRD pattern of the carbon monoxide adsorbent, indicating that the active component Cu(I) in the carbon monoxide adsorbent is highly dispersed on the surface of the support. Specifically, "no sharp peaks in the 2θ angle range of 20° to 30°" means that in the XRD pattern of the carbon monoxide adsorbent, if the 2θ range value corresponding to a single characteristic peak in the 2θ = 20° to 30° range is greater than 2°, it can be considered that no sharp peaks exist in the 2θ angle range of 20° to 30°. Similarly, "no sharp peaks in the 2θ angle range of 40° to 50°" means that in the XRD pattern of the carbon monoxide adsorbent, if the 2θ range value corresponding to a single characteristic peak in the 2θ = 40° to 50° range is greater than 2°, it can be considered that no sharp peaks exist in the 2θ angle range of 40° to 50°.

[0030] According to some embodiments of the present invention, information such as the composition, internal atomic or molecular structure or morphology of a carbon monoxide adsorbent is obtained by XRD. The XRD diffractometer used is a Bruker D8 ADVANCE, employing a Cu target, Kα rays, and a tube voltage (40 kV) scanning range of 10°–60°.

[0031] A second aspect of the present invention provides a method for preparing a dual-active-component carbon monoxide adsorbent, the method comprising:

[0032] (1) Provide an active component solution containing copper and manganese salts;

[0033] (2) The porous carbon material is impregnated with the active component solution and then calcined under an inert atmosphere;

[0034] The copper salt is copper chloride, and the manganese salt is divalent manganese salt.

[0035] According to some embodiments of the present invention, in step (1), the copper salt is copper chloride, which may be copper chloride containing water of crystallization or copper chloride without water of crystallization. Preferably, the copper salt is copper chloride dihydrate.

[0036] According to some embodiments of the present invention, in step (1), the manganese salt can be selected from a wide range, and can be a water-soluble divalent manganese salt conventionally used in the art, preferably at least one of manganese acetate, manganese formate, and manganese chloride, more preferably manganese acetate. The divalent manganese salt can be a divalent manganese salt containing water of crystallization or a divalent manganese salt without water of crystallization. More preferably, the manganese salt is manganese acetate tetrahydrate.

[0037] According to some embodiments of the present invention, in step (1), the molar ratio of the copper salt to the manganese salt is 3-30:1, preferably 3-12:1, based on the metal element.

[0038] According to some embodiments of the present invention, the porous carbon material may be selected as described above, and will not be repeated here.

[0039] According to some embodiments of the present invention, in step (1), the method of forming the active component solution is not particularly limited, as long as a homogeneous active component solution can be formed. Preferably, copper salt and manganese salt are dissolved in a solvent to form the active component solution; more preferably, the solvent is water.

[0040] According to some embodiments of the present invention, in step (2), the porous carbon material is impregnated with the active component solution. The present invention does not particularly limit the impregnation method; any impregnation method known in the art can be used, as long as it enables the active component to be loaded onto the porous carbon material. To better load the active component onto the porous carbon material and improve the uniformity of the active component loading, it is preferable to use an equal-volume impregnation method. More preferably, the ratio of the active component solution to the porous carbon material is 5-12 mL:5 g, and more preferably 8-10 mL:5 g.

[0041] According to some embodiments of the present invention, preferably, after impregnating the porous carbon material with the active component solution and before calcination, a drying step is further included. The drying method and conditions can refer to the prior art, for example, the drying temperature can be 60-80°C and the drying time can be 12-24 hours.

[0042] According to some embodiments of the present invention, preferably, in step (2), the calcination conditions include: a calcination temperature of 200-500℃, preferably 300-360℃; a calcination time of 2-10h, preferably 4-8h; and a heating rate of 2-10℃ / min, preferably 4-5℃ / min.

[0043] According to some embodiments of the present invention, preferably, the inert atmosphere is provided by at least one inert gas selected from nitrogen, helium and argon; more preferably, the flow rate of the inert gas is 40-120 mL / min, and more preferably 50-80 mL / min.

[0044] According to some embodiments of the present invention, preferably, the amount of copper salt, manganese salt and porous carbon material is such that the loading of Cu(I) on the porous carbon material in the prepared carbon monoxide adsorbent is 4-12 mmol / g, preferably 6-8 mmol / g.

[0045] According to some embodiments of the present invention, preferably, the amount of copper salt, manganese salt and porous carbon material is such that the loading of Mn(II) on the porous carbon material in the prepared carbon monoxide adsorbent is 0.1-4 mmol / g, preferably 0.5-2 mmol / g.

[0046] According to a particularly preferred embodiment of the present invention, the method for preparing a dual-active-component carbon monoxide adsorbent comprises:

[0047] (S1) Provide an active component solution containing copper and manganese salts;

[0048] (S2) The porous carbon material is impregnated with the active component solution and then calcined under an inert atmosphere;

[0049] The copper salt is copper chloride dihydrate, the manganese salt is manganese acetate tetrahydrate, and the BET specific surface area of ​​the porous carbon material is 800-1800 m². 2 / g; calculated by metal element, the molar ratio of the copper salt to the manganese salt is 3-30:1; the ratio of the active component solution to the porous carbon material is 5-12mL:5g; the calcination conditions include: calcination temperature of 200-500℃ and calcination time of 2-10h.

[0050] According to some embodiments of the present invention, the method for preparing a dual-active-component carbon monoxide adsorbent is simple to operate and the active components are well dispersed on the surface of porous carbon materials.

[0051] A third aspect of the present invention provides a method for adsorbing carbon monoxide, the method comprising:

[0052] A gas containing carbon monoxide is brought into contact with an adsorbent to adsorb the carbon monoxide contained in the gas onto the adsorbent.

[0053] The adsorbent is either the carbon monoxide adsorbent described in the first aspect or the carbon monoxide adsorbent prepared according to the method described in the second aspect.

[0054] According to some embodiments of the present invention, preferably, the contact conditions include a temperature of 25-60°C and a pressure of 1-21 Bar; more preferably, the contact is carried out at room temperature (25°C) and normal pressure (100 kPa (1 Bar)). During the contact process, the adsorption of carbon monoxide by the carbon monoxide adsorbent causes a pressure drop, and gradually reaches adsorption equilibrium, thereby obtaining an adsorbent containing carbon dioxide.

[0055] According to some embodiments of the present invention, in order to improve the adsorption effect of the carbon monoxide adsorbent on carbon monoxide, preferably, the adsorption method further includes activating the adsorbent in an inert gas environment or a reducing gas environment before the contact, wherein the activation can remove impurities such as water and air adsorbed in the adsorbent. Preferably, the activation conditions include: a temperature of 200-350°C and a time of 1-2 hours.

[0056] According to some embodiments of the present invention, preferably, the gas containing carbon monoxide is a mixture of hydrogen and carbon monoxide; more preferably, the concentration of carbon monoxide in the mixture is 1-50 ppm. Even more preferably, the mixture is a fuel gas used in a fuel cell. The carbon monoxide adsorbent provided by the present invention is particularly suitable for the removal of carbon monoxide from hydrogen used as fuel cell fuel.

[0057] According to some embodiments of the present invention, preferably, the adsorption method further includes heating and / or depressurizing the adsorbent containing carbon dioxide, wherein the heating and / or depressurization enables the carbon monoxide adsorbed on the carbon monoxide adsorbent to desorb, thereby recovering the carbon monoxide adsorbent and recycling it for the adsorption of carbon monoxide.

[0058] According to some embodiments of the present invention, preferably, the heating conditions include: a temperature of 60-100°C and a time of 1-3 hours.

[0059] According to some embodiments of the present invention, preferably, the decompression conditions include: a pressure of 50-100 kPa and a time of 1-3 hours.

[0060] According to some embodiments of the present invention, for hydrogen gas with a carbon monoxide concentration of 5 ppm, under the conditions of adsorption temperature of 40°C and adsorption pressure of 2.1 MPa, the CO adsorption breakthrough time of the carbon monoxide adsorbent provided by the present invention can reach up to 590 min.

[0061] The present invention will be described in detail below through embodiments. In the following embodiments and comparative examples:

[0062] Unless otherwise specified, all reagents used in this invention are of analytical grade and are commercially available.

[0063] The activated carbon was purchased from Beijing Inokai Technology Co., Ltd. (supplier), model / brand Norit ROW, with a BET specific surface area of ​​1400 m². 2 / g.

[0064] The specific surface area of ​​porous carbon materials was determined using the BET test method. Specifically, a Quantachrome AS-6B analyzer was used, and the specific surface area of ​​the porous carbon materials was obtained by the Brunauer-Emmett-Taller (BET) method.

[0065] The X-ray photoelectron spectroscopy (XPS) used was a Qtac-100 LEISSXPS instrument, and measurements were taken using monochromatic Al target Kα radiation (1486.6 eV).

[0066] The XRD diffractometer used was a Bruker D8 ADVANCE, with a Cu target, Kα rays, tube voltage (40kV), and a scanning range of 10°-60°.

[0067] In the following examples and comparative examples, the loading of the active component of the carbon monoxide adsorbent was calculated and determined based on the amount of each raw material fed.

[0068] Examples 1-5 illustrate the carbon monoxide adsorbent and its preparation method.

[0069] Example 1

[0070] (1) Dissolve 5.11g of copper chloride dihydrate in 9mL of deionized water, add 1.23g of manganese acetate tetrahydrate and stir to dissolve to obtain an active component solution. The molar ratio of copper chloride dihydrate to manganese acetate tetrahydrate, calculated by metal element, is approximately 6:1.

[0071] (2) Add 5g of activated carbon and immerse it in the active component solution in an equal volume, and let it stand for 0.5h.

[0072] (3) Place the product obtained in step (2) in a 60°C oven and dry it overnight to obtain material one.

[0073] (4) The material was placed in a tube furnace and roasted under nitrogen protection. The nitrogen flow rate was 50 mL / min, the heating rate was 4℃ / min, the roasting temperature was 360℃, and the roasting time was 8h to obtain carbon monoxide adsorbent. The loading of Cu(I) on activated carbon was 6 mmol / g, and the loading of Mn(II) on activated carbon was 1 mmol / g.

[0074] Example 2

[0075] (1) Dissolve 10.23g of copper chloride dihydrate in 14mL of deionized water, add 0.49g of manganese acetate tetrahydrate and stir to dissolve to obtain an active component solution. The molar ratio of copper chloride dihydrate to manganese acetate tetrahydrate, calculated as metal elements, is approximately 3:0.1.

[0076] (2) Add 10g of activated carbon and immerse it in the active component solution in an equal volume, and let it stand for 0.5h.

[0077] (3) Place the product obtained in step (2) in a 60°C oven and dry it overnight to obtain material one.

[0078] (4) The material was placed in a tube furnace and roasted under nitrogen protection. The nitrogen flow rate was 50 mL / min, the heating rate was 4℃ / min, the roasting temperature was 360℃, and the roasting time was 4h to obtain carbon monoxide adsorbent. The loading of Cu(I) on activated carbon was 6 mmol / g, and the loading of Mn(II) on activated carbon was 0.2 mmol / g.

[0079] Example 3

[0080] (1) Dissolve 10.23g of copper chloride dihydrate in 14mL of deionized water, add 1.23g of manganese acetate tetrahydrate and stir to dissolve to obtain an active component solution. The molar ratio of copper chloride dihydrate to manganese acetate tetrahydrate, calculated as metal elements, is approximately 6:0.5.

[0081] (2) Add 10g of activated carbon and immerse it in the active component solution in an equal volume, and let it stand for 0.5h.

[0082] (3) Place the product obtained in step (2) in a 60°C oven and dry it overnight to obtain material one.

[0083] (4) The material was placed in a tube furnace and roasted under nitrogen protection. The nitrogen flow rate was 50 mL / min, the heating rate was 4℃ / min, the roasting temperature was 360℃, and the roasting time was 4h to obtain carbon monoxide adsorbent. The loading of Cu(I) on activated carbon was 6 mmol / g, and the loading of Mn(II) on activated carbon was 0.5 mmol / g.

[0084] Example 4

[0085] (1) Dissolve 10.23g of copper chloride dihydrate in 14mL of deionized water, add 2.45g of manganese acetate tetrahydrate and stir to dissolve to obtain an active component solution. The molar ratio of copper chloride dihydrate to manganese acetate tetrahydrate, calculated as metal elements, is approximately 6:1.

[0086] (2) Add 10g of activated carbon and immerse it in the active component solution in an equal volume, and let it stand for 0.5h.

[0087] (3) Place the product obtained in step (2) in a 60°C oven and dry it overnight to obtain material one.

[0088] (4) The material was placed in a tube furnace and roasted under nitrogen protection. The nitrogen flow rate was 50 mL / min, the heating rate was 4℃ / min, the roasting temperature was 360℃, and the roasting time was 4h to obtain carbon monoxide adsorbent. The loading of Cu(I) on activated carbon was 6 mmol / g, and the loading of Mn(II) on activated carbon was 1 mmol / g.

[0089] Example 5

[0090] (1) Dissolve 5.11g of copper chloride dihydrate in 7mL of deionized water, add 2.45g of manganese acetate tetrahydrate and stir to dissolve to obtain an active component solution. The molar ratio of copper chloride dihydrate to manganese acetate tetrahydrate, calculated as metal elements, is approximately 3:1.

[0091] (2) Add 5g of activated carbon and immerse it in the active component solution in an equal volume, and let it stand for 0.5h.

[0092] (3) Place the product obtained in step (2) in a 60°C oven and dry it overnight to obtain material one.

[0093] (4) The material was placed in a tube furnace and roasted under nitrogen protection. The nitrogen flow rate was 50 mL / min, the heating rate was 4℃ / min, the roasting temperature was 360℃, and the roasting time was 4h to obtain carbon monoxide adsorbent. The loading of Cu(I) on activated carbon was 6 mmol / g, and the loading of Mn(II) on activated carbon was 2 mmol / g.

[0094] Comparative Example

[0095] (1) Dissolve 10.23g of copper chloride dihydrate in 14mL of deionized water to obtain the active component solution.

[0096] (2) Add 10g of activated carbon and immerse it in the active component solution in an equal volume, and let it stand for 0.5h.

[0097] (3) Place the product obtained in step (2) in a 60°C oven and dry it overnight to obtain material one.

[0098] (4) The material was placed in a tube furnace and roasted under nitrogen protection. The nitrogen flow rate was 50 mL / min, the heating rate was 4℃ / min, the roasting temperature was 360℃, and the roasting time was 4h to obtain carbon monoxide adsorbent. The loading of Cu(I) on activated carbon was 6 mmol / g.

[0099] Material characterization:

[0100] XPS is used to characterize the valence states of copper and manganese in the prepared adsorbent. For example... Figure 1 As shown, the carbon monoxide adsorbent prepared in Example 1 exhibits two strong peaks at 931.8 eV and 951.6 eV, which can be attributed to Cu 2p. 3 / 2 and Cu 2p 1 / 2 The binding energy, Figure 1 The inset in the upper right corner shows the Cu LMM spectrum of the carbon monoxide adsorbent prepared in Example 1, with a binding energy peak of 915.9 eV, and the binding energy of Cu. + Cu LMM spectrum Figure 1 To. (As) Figure 2 As shown, the carbon monoxide adsorbent prepared in Example 1 exhibits two peaks at 641.7 eV and 652.9 eV, which can be attributed to Mn. 2+ 2p 3 / 2 and Mn 2+ 2p 1 / 2 The binding energy. For example... Figure 3 As shown, the XRD pattern of the carbon monoxide adsorbent prepared in Example 1 shows no diffraction peaks of CuCl, indicating that CuCl is highly dispersed on the activated carbon surface. The XPS and XRD characterization results of the carbon monoxide adsorbents prepared in Examples 2 to 5 are similar to those in Example 1.

[0101] Test case

[0102] Test method for dynamic adsorption capacity of carbon monoxide: The carbon monoxide adsorbents prepared in Examples 1-5 and the comparative example were loaded into a stainless steel fixed-bed reactor and activated at 300°C for 2 hours under a nitrogen atmosphere. Hydrogen gas with a carbon monoxide concentration of 5 ppm was introduced, the adsorption temperature was 40°C, the adsorption pressure was 2.1 MPa, and the volume hourly space velocity was 3000 h⁻¹. -1 The concentration of CO in the hydrogen gas of the product was detected by gas chromatography. When the concentration of CO in the product gas exceeded 0.2 ppm, it was determined that the adsorbent had broken through.

[0103] Depend on Figure 4As shown in Table 1, the CO adsorption breakthrough time of the carbon monoxide adsorbent in the comparative example was 170 min, the CO adsorption breakthrough time of the carbon monoxide adsorbent in Example 1 was 320 min, the CO adsorption breakthrough time of the carbon monoxide adsorbent in Example 2 was 180 min, the CO adsorption breakthrough time of the carbon monoxide adsorbent in Example 3 was 280 min, the CO adsorption breakthrough time of the carbon monoxide adsorbent in Example 4 was 380 min, and the CO adsorption breakthrough time of the carbon monoxide adsorbent in Example 5 was 590 min. The CO adsorption breakthrough time of the carbon monoxide adsorbents prepared in Examples 1-5 was longer than that of the carbon monoxide adsorbent prepared in the comparative example, indicating that the introduction of the second active component Mn(II) in this invention, combined with Cu(I) and porous carbon materials, effectively improved the CO adsorption capacity of the carbon monoxide adsorbent.

[0104] Table 1

[0105] Adsorbent CO adsorption breakthrough time (min) Example 1 320 Example 2 180 Example 3 280 Example 4 380 Example 5 590 Comparative Example 170

[0106] The results above show that, compared with single-active-component carbon monoxide adsorbents, the dual-active-component carbon monoxide adsorbent provided by this invention has a longer CO adsorption breakthrough time and a higher CO adsorption capacity.

[0107] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for adsorbing carbon monoxide, the adsorption method comprising: A gas containing carbon monoxide is brought into contact with an adsorbent to adsorb the carbon monoxide contained in the gas onto the adsorbent. The adsorbent is a carbon monoxide adsorbent; The carbon monoxide adsorbent includes a support and an active component loaded on the support, wherein the support is a porous carbon material and the active component is Cu(I) and Mn(II); The porous carbon material is selected from at least one of activated carbon, graphene, carbon, and carbon black; In the carbon monoxide adsorbent, the loading of Cu(I) on the porous carbon material is 6-8 mmol / g; In the carbon monoxide adsorbent, the loading of Mn(II) on the porous carbon material is 0.5-2 mmol / g; In the carbon monoxide adsorbent, the molar ratio of Cu(I) to Mn(II) is 3-12:1; The preparation method of the carbon monoxide adsorbent includes: (1) Provide an active component solution containing copper and manganese salts; (2) The porous carbon material is impregnated with the active component solution and then calcined under an inert atmosphere; Wherein, the copper salt is copper chloride, and the manganese salt is manganese acetate tetrahydrate; The adsorption method further includes activating the adsorbent in an inert gas environment or a reducing gas environment before the contact.

2. The carbon monoxide adsorption method according to claim 1, wherein, The porous carbon material has a BET specific surface area of ​​800-1800 m². 2 / g.

3. The carbon monoxide adsorption method according to claim 2, wherein, The porous carbon material is activated carbon; and / or The porous carbon material has a BET specific surface area of ​​1000-1500 m². 2 / g.

4. The carbon monoxide adsorption method according to any one of claims 1-3, wherein, XRD analysis showed that the carbon monoxide adsorbent did not exhibit any spikes in the range of 2θ angles from 20° to 30° and / or from 40° to 50°.

5. The carbon monoxide adsorption method according to claim 4, wherein, In step (1), the copper salt is copper chloride dihydrate; And / or, in step (2), the ratio of the active component solution to the porous carbon material is 5-12 mL: 5 g.

6. The carbon monoxide adsorption method according to claim 5, wherein, In step (2), the ratio of the active component solution to the porous carbon material is 8-10 mL: 5 g.

7. The carbon monoxide adsorption method according to claim 4, wherein, In step (2), the calcination conditions include: a calcination temperature of 200-500℃; a calcination time of 2-10h; a heating rate of 2-10℃ / min; and / or The inert atmosphere is provided by at least one inert gas selected from nitrogen, helium, and argon; and / or The flow rate of the inert gas is 40-120 mL / min.

8. The carbon monoxide adsorption method according to claim 7, wherein, In step (2), the calcination conditions include: a calcination temperature of 300-360℃; a calcination time of 4-8h; a heating rate of 4-5℃ / min; and / or The flow rate of the inert gas is 50-80 mL / min.

Images