WO2023184935A1 - 一种精脱氢气中co的脱除剂及其制备方法和应用 - Google Patents

一种精脱氢气中co的脱除剂及其制备方法和应用 Download PDF

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WO2023184935A1
WO2023184935A1 PCT/CN2022/126098 CN2022126098W WO2023184935A1 WO 2023184935 A1 WO2023184935 A1 WO 2023184935A1 CN 2022126098 W CN2022126098 W CN 2022126098W WO 2023184935 A1 WO2023184935 A1 WO 2023184935A1
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removal agent
removal
metal oxide
composite metal
components
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French (fr)
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郭秀盈
何广利
刘聪敏
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国家能源投资集团有限责任公司
北京低碳清洁能源研究院
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Publication of WO2023184935A1 publication Critical patent/WO2023184935A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • C01B3/54—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids including a catalytic reaction
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/583—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being the selective oxidation of carbon monoxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0668—Removal of carbon monoxide or carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide

Definitions

  • the present invention relates to the technical field of removing CO from hydrogen gas, and in particular to a removal agent for removing CO from hydrogen gas and its preparation method and application.
  • CN109499261A discloses a system and method for removing CO from hydrogen used in proton exchange membrane fuel cells.
  • the removal system includes a hydrogen storage tank, a CO adsorption purifier, a hydrogen heat exchanger and a fuel cell anode that are connected in sequence.
  • This document provides a method for CO removal using a removal system, which uses CuCl as the CO adsorbent.
  • hydrogen for fuel cell vehicles has strict requirements for Cl ions ( ⁇ 0.05ppm), so the adsorbent has the risk of introducing Cl ions. .
  • the catalyst is a carrier carrying active components and additives; the active component is Pt, and the additive is one or a combination of two of Zn, Cu, La, Ce, Pr, Fe, Sn and Co; the active component
  • the loading amount is 0.01 to 0.1 (wt%) of the catalyst, and the loading amount of the auxiliary agent is 0.5% to 5% (wt%) of the catalyst.
  • This document provides a precious metal catalyst that can remove carbon monoxide from hydrogen at 100°C to 200°C. At high temperatures, on the one hand, the energy consumption is high, and on the other hand, hydrogen and CO compete with each other to form H 2 O by-products.
  • the present invention provides a removal agent for CO in refined dehydrogenation gas and its preparation method and application.
  • the removal agent provided by the present invention can remove CO from hydrogen gas at a relatively low temperature, such as room temperature, This enables it to meet the stringent requirements of fuel cells for CO content in hydrogen.
  • the present invention provides the following technical solutions:
  • the invention provides a removal agent for CO in refined dehydrogenation gas.
  • the active component of the removal agent includes a composite metal oxide.
  • the metal elements in the composite metal oxide are Cu, Ce, Mn and Bi. Therefore,
  • the general expression formula of the composite metal oxide is Cu x Ce 3-xyz Mn y Bi z O 4+ ⁇ , where the subscript value of each metal element is the number of atoms of the corresponding metal element in the composite metal oxide, "4+ ⁇ " is the number of oxygen atoms required to satisfy the oxidation state of other elements, 0.2 ⁇ x ⁇ 2, 0.05 ⁇ y ⁇ 2.8, 0.05 ⁇ z ⁇ 1, and x+y+z ⁇ 3.
  • the active components of the removal agent optionally include other active components, and the other active components are selected from one of Ca oxides, K oxides, and La oxides. or more, and the content of the other active components is 0.2wt% to 20wt% based on the weight of the composite metal oxide.
  • the removal agent further includes other components, and the other components include silicon oxide and/or aluminum oxide.
  • the weight percentage of the other components in the removal agent is 2-30%.
  • the present invention also provides a preparation method of the above-mentioned removal agent, which includes the following steps:
  • the filter cake is mixed and uniformly formed with optional other components;
  • the other components include a carrier and/or binder containing silicon and/or aluminum; preferably, the other components One or more selected from silica sol, potassium silicate, aluminum sol, pseudo-boehmite;
  • the roasting conditions include: a roasting temperature of 200-600°C and a roasting time of 2-12 hours.
  • the present invention also provides a method for removing CO from hydrogen gas, using the removal agent described above to remove CO from the hydrogen gas.
  • the removal agent of the present invention can remove CO at low temperatures. In some embodiments, removal of CO from hydrogen gas is performed below 100° C., preferably at room temperature. Further, the removal is performed in the presence of oxygen or in the absence of oxygen.
  • the removal agent provided by the invention can remove CO from hydrogen at room temperature, converting CO into CO 2 that is easily removed and has weak toxicity to fuel cells. During the CO removal process, it can be used at no (or extremely low) The purpose of removal is achieved under the condition of consuming hydrogen.
  • the removal process based on the removal agent of the present invention is simple and easy to implement, and has low operating cost; CO conversion can be achieved under oxygen-free conditions, and the risk of explosion caused by the introduction of oxygen into hydrogen can be avoided.
  • the removal agent of the present invention has an excellent removal effect of CO in hydrogen and can remove CO to 0 ppm.
  • the removal agent of the present invention can adapt to the removal of CO at different concentration levels.
  • the active component of the CO removal agent in refined dehydrogenation gas provided by the present invention mainly includes the following composite metal oxide.
  • the metal elements in the composite metal oxide are Cu, Ce, Mn and Bi, that is, the composite metal oxide It is composed of Cu oxide, Ce oxide, Mn oxide and Bi oxide.
  • the active components thereof may only include the above-mentioned composite metal oxides.
  • the general expression formula of the composite metal oxide is Cu x Ce 3-xyz Mn y Bi z O 4+ ⁇ , where the subscript values of each metal element are such as , z are respectively the number of atoms of the corresponding metal element in the composite metal oxide, and "4+ ⁇ " is the number of oxygen atoms required to satisfy the oxidation state of other elements.
  • the remover provided by the present invention mainly uses a combination of Cu, Ce, Mn and Bi oxides as active ingredients.
  • a combination of Cu, Ce, Mn and Bi oxides as active ingredients.
  • lattice defects are easily formed at the interface, which is conducive to the removal of electrons. transfer, forming more oxygen vacancies, enhancing the ability to release or capture oxygen molecules, increasing CO removal activity, and facilitating the reduction of CO at low temperatures.
  • the oxide removal agent in the general expression formula of the composite metal oxide, 0.2 ⁇ x ⁇ 2, 0.05 ⁇ y ⁇ 2.8, 0.05 ⁇ z ⁇ 1, and x+y+z ⁇ 3, based on the composite metal
  • the oxide removal agent can more completely remove CO from hydrogen at relatively low temperatures, such as room temperature.
  • 1 ⁇ x ⁇ 2 is beneficial to extending the usable time of the removal agent for CO removal.
  • 0.05 ⁇ z ⁇ 0.5 can improve the usable time of CO removal by the removal agent.
  • 0.5 ⁇ y ⁇ 2, preferably 0.5 ⁇ y ⁇ 1.5 which can help extend the usable time of the removal agent for CO removal.
  • the removal agent can obtain a longer usable time for CO removal. In some preferred embodiments, 0.5 ⁇ y ⁇ 2, and 2.1 ⁇ x+y+z ⁇ 2.97, the removal agent can obtain a longer usable time for CO removal.
  • the active component of the removal agent of the present invention in addition to the above-mentioned composite metal oxide, may optionally include other active components.
  • the other active components are selected from the group consisting of Ca oxides and K oxides.
  • One or more of the oxides and La oxides, and the content of other active components is 0.2wt% to 20wt% of the weight of the composite metal oxide (that is, the composite metal oxide of Cu, Ce, Mn and Bi).
  • the additional introduction of these active ingredients will help enhance CO adsorption, promote the conversion of CO into CO 2 , and inhibit the generation of H 2 O.
  • the removal agent of the present invention may only contain the above-mentioned active ingredients, or the above-mentioned active ingredients may be compounded with other components to obtain the removal agent of the present invention.
  • the other components include, for example, silicon oxides and/or aluminum oxides. Specific examples include SiO 2 and/or Al 2 O 3 .
  • the weight percentage of other components in the remover of the present invention is 2-30%, and the balance is the active component and optional other active components.
  • SiO 2 and/or Al 2 O 3 can be derived from a carrier and/or binder containing silicon element and/or aluminum element, for example derived from one of silica sol, potassium silicate, aluminum sol, pseudo-boehmite One or more kinds, these carriers and/or binders can directly use corresponding commercially available raw materials.
  • the introduction of SiO 2 and/or Al 2 O 3 can increase the dispersion of the active phase of the remover and the strength of the molded particles.
  • the present invention also provides a preparation method for the above-mentioned removal agent, which specifically includes the following steps:
  • the filter cake is mixed and uniformly formed with optional other components;
  • the other components include carriers and/or binders containing silicon and/or aluminum, such as silica sol, potassium silicate , aluminum sol, pseudo-boehmite, etc.; thereby introducing the corresponding silicon oxide and/or aluminum oxide into the removal agent;
  • soluble salts of metal elements corresponding to each oxide in the active component specifically refer to soluble salts of Cu element, Ce element, Mn element and Bi element, as well as the Ca element that may be contained , soluble salts of K element and La element; soluble salts can be but are not limited to nitrates, sulfates, acetates, oxalates and their hydrates, etc. Examples include copper nitrate trihydrate, cerium nitrate hexahydrate, Manganese nitrate hexahydrate, bismuth nitrate pentahydrate, etc.
  • the molar concentration of the aqueous solution prepared by mixing the soluble salts is 0.05-2 mol/L.
  • the alkaline substance used to adjust the pH to 6-9 is not particularly limited.
  • it can be a sodium hydroxide aqueous solution, a sodium carbonate aqueous solution or an ammonia aqueous solution.
  • the alkaline substance used can be, for example, a concentration of 0.05-2 mol/L. in the form of aqueous solution.
  • deionized water is used for washing, mainly to remove sodium and other ions.
  • the roasting conditions specifically include: a roasting temperature of 200-600°C and a roasting time of 2-12 hours.
  • the present invention also provides a method for removing CO from hydrogen gas, using the removal agent described above to remove CO from hydrogen gas.
  • the removal agent of the present invention can remove CO from hydrogen gas at temperatures below 100°C. Specifically, for example, CO can be removed at room temperature, and effective removal can be achieved without additional heating treatment.
  • the removal agent of the present invention can remove CO from hydrogen gas in the presence of oxygen or without oxygen.
  • the removal of CO from hydrogen gas is preferably carried out under anaerobic conditions.
  • the removal of CO from hydrogen gas cannot be completed in the presence of oxygen under aerobic conditions. The problem of conversion introduces additional oxygen impurities.
  • nitrate solution A with a concentration of 0.2 mol/L (based on Cu, Mn, Calculate the molar sum of Ce and Bi ions); then prepare a NaOH aqueous solution with a concentration of 0.2mol/L; under stirring, add NaOH aqueous solution to nitrate solution A to adjust the pH to 7.5 to produce a coprecipitate; add the coprecipitate After the material is aged for 60 minutes, the coprecipitate is filtered and washed until sodium ions are removed to obtain a filter cake; the filter cake is roasted at 400°C for 10 hours to obtain a removal agent, which is Cu, Ce, Mn and Bi oxides.
  • the removal agent can be expressed as CuCe 0.4 Mn 1.5 Bi 0.1 O 4+ ⁇ according to the ratio of the number of atoms of each element, where 4+ ⁇ is required to satisfy the oxidation state of other elements in the general formula The number of oxygen atoms (the same is true for the value of 4+ ⁇ in subsequent embodiments, which will not be described again).
  • the removal agents of Examples 2-6 were prepared with reference to the preparation method of Example 1. The only difference from Example 1 is to adjust the dosage of copper nitrate trihydrate, cerium nitrate hexahydrate, manganese nitrate hexahydrate, and bismuth nitrate pentahydrate. Finally, a removal agent whose general formula is Cu x Ce 3-xyz Mn y Bi z O 4+ ⁇ is obtained, and the values of x, y, and z are the corresponding values in Table 1 respectively.
  • nitrate solution A with a concentration of 0.2 mol/L (in the form of Cu, Mn, Ce , calculated as the molar sum of Bi ions); then prepare a NaOH aqueous solution with a concentration of 0.2mol/L; under stirring, add a NaOH aqueous solution to the nitrate solution A to adjust the pH to 7.5 to produce a co-precipitate; remove the co-precipitate After aging for 60 minutes, the coprecipitate was filtered and washed until sodium ions were removed to obtain a filter cake; 8% pseudo-boehmite was added to the filter cake on a dry basis, kneaded evenly, extruded into strips, and roasted at 400°C for 10 hours.
  • the removal agent is obtained, expressed as 92% CuCe 0.4 Mn 1.5 Bi 0.1 O 4+ ⁇ +8% Al 2 O 3 ; it is composed of alumina and active components, in which alumina accounts for 8wt%, and the active component The proportion is 92wt%, and the active component is a mixture of Cu, Ce, Mn and Bi oxides (i.e. composite metal oxide).
  • the ratio of each element in the active component in terms of atomic number is expressed as CuCe 0.4 Mn 1.5 Bi 0.1 O 4 + ⁇ .
  • the removal agent is prepared.
  • the preparation process is basically the same as in Example 7, except that the pseudo-hybrid aluminum is replaced with silica sol.
  • the obtained removal agent is expressed as 92% CuCe 0.4 Mn 1.5 Bi 0.1 O 4+ ⁇ +8% SiO 2 , which is composed of silica and active components, of which silica accounts for 8wt% and active components account for 8%. It is 92wt%.
  • the active component is a mixture of Cu, Ce, Mn and Bi oxides (i.e. composite metal oxide).
  • the ratio of each element in the active component in terms of atomic number is expressed as CuCe 0.4 Mn 1.5 Bi 0.1 O 4+ ⁇ .
  • the removal agent is prepared.
  • the preparation process is basically the same as in Example 7, except that potassium nitrate is added to the nitrate solution A.
  • the obtained removal agent is expressed as 91%CuCe 0.4 Mn 1.5 Bi 0.1 O 4+ ⁇ +8%Al 2 O 3 +K 2 O 1%, which is composed of alumina and active components, of which alumina accounts for 8wt% , the active components include composite metal oxides of Cu, Ce, Mn, Bi and K oxide, in which the composite metal oxide of Cu, Ce, Mn, Bi accounts for 91wt%, and the K oxide accounts for 1wt%.
  • CO breakthrough time refers to: starting from the time when the raw material gas is introduced into the reaction tube, and monitoring the CO content at the outlet end of the reaction tube.
  • the time span is the time span for the CO breakthrough time.
  • the CO content was detected using Agilent portable chromatography Micro-GC.
  • x, y, and z correspond to x, y, and z in the general formula of the removal agent: Cu x Ce 3-xyz Mn y Bi z O 4+ ⁇ .
  • Example 3 has the best effect and the removal agent can be used for the longest time. Comparing Example 2 and Example 3, it can be seen that when the values of y and z are the same, the larger x is, the longer the removal agent penetration time is; the best preferred range of x is 1 ⁇ x ⁇ 2, and z is the Bi element (molecular weight Larger), to ensure the activity per unit mass of the agent, this component cannot be too high, preferably 0.05 ⁇ z ⁇ 0.5;
  • Example 3 Comparing Example 3 and Example 4, it can be seen that when the x value is the same, the removal agent penetration time is significantly shortened when the y value decreases, indicating that the y value cannot be too low.
  • the preferred range of y value is 0.5 ⁇ y ⁇ 1.5.
  • Example 9 Comparing Example 9 with Example 7, it can be seen that the further introduction of K 2 O on the basis of the introduction of Al 2 O 3 not only maintains good strength, but also increases the CO penetration time from 78 min to 82 min. It can be seen that K The introduction is beneficial to further enhance the CO removal ability of the removal agent.
  • Table 3 shows the evaluation results of Example 1 under different CO concentrations at 25°C and 1 bar. It can be seen that as the CO concentration of the removal agent decreases, the dew point of the product gas increases slightly and the penetration time prolongs; indicating that the removal agent provided by the present invention The remover can remove CO at different concentration levels from hydrogen at room temperature with almost no hydrogen consumption.

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Abstract

本发明提供一种精脱氢气中CO的脱除剂及其制备方法和应用，本发明提供的脱除剂能够在相对较低的温度下例如室温下较为彻底的脱除氢气中的CO，使其满足燃料电池对氢气中CO含量的苛刻要求。本发明提供的精脱氢气中CO的脱除剂，所述脱除剂的活性组分包括复合金属氧化物，所述复合金属氧化物中的金属元素为Cu、Ce、Mn和Bi，所述复合金属氧化物的表达通式为Cu xCe 3-x-y-zMn yBi zO 4+δ，其中，各金属元素的下标数值为对应金属元素在所述复合金属氧化物中的原子数，"4+δ"为满足其他元素氧化态所需的氧原子数，0.2<x<2、0.05<y<2.8、0.05<z<1，且x+y+z＜3。

Description

一种精脱氢气中CO的脱除剂及其制备方法和应用 技术领域
本发明涉及氢气中CO的脱除技术领域，特别涉及一种精脱氢气中CO的脱除剂及其制备方法和应用。
背景技术
由于质子交换膜燃料电池对氢气中杂质十分敏感，氢燃料电池使用的氢气要求纯度达到ISO14687-2标准和SAE J2719燃料电池驱动车辆氢燃料质量要求。国标对纯氢的要求是生产的氢气中CO小于5ppm，对高纯氢的要求是生产的氢气中CO小于1ppm，而燃料电池中规定CO要小于0.2ppm。
工业纯氢、高纯氢CO杂质含量无法满足燃料电池用氢气品质要求，需要进行深度CO脱除。目前氢气中CO脱除/分离用PSA及TSA方法，该方法一般用于高浓度CO的分离，使用前需要原位还原后使用，且有引入Cl离子风险，H 2O与CO 2会影响其吸附性能，其在燃料电池车用氢气纯化中的使用仍存在争议。传统PSA纯化工艺中，CO含量难以脱除至0.2ppm。此外，传统催化氧化剂需要在有O 2存在的情况下在近100℃将CO氧化，氢气中引入O 2存在爆炸风险，且易发生与氢气的副反应。
CN109499261A公开了一种质子交换膜燃料电池用氢气中CO的脱除系统及方法，该脱除系统包括依次连通的储氢罐，CO吸附净化器，氢气换热器以及燃料电池阳极。该文献提供了利用脱除系统进行CO脱除的方法，其采用CuCl作为CO吸附剂，然而燃料电池车用氢气对Cl离子有严格要求(<0.05ppm)，因此该吸附剂存在引入Cl离子风险。
CN201210402065.X公开了一种氢气中一氧化碳的氧化脱除催化剂及其制备方法，该文献提供了一种适用于高浓度氢气中的一氧化碳的选择性氧化 脱除催化剂及其制备和使用方法。催化剂为负载活性组分及助剂的载体；活性组分为Pt，助剂为Zn、Cu、La、Ce、Pr、Fe、Sn和Co中的一种或两种的组合；活性组分的担载量为催化剂的0.01～0.1(wt％)，助剂的担载量为催化剂的0.5％-5％(wt％)。该文献提供的是一种贵金属催化剂，能将氢气中的一氧化碳在100℃～200℃下脱除。高温下一方面能耗高，另一方面会导致氢气与CO竞争的反应，生成H 2O副产物。
发明内容
有鉴于此，本发明提供一种精脱氢气中CO的脱除剂及其制备方法和应用，本发明提供的脱除剂能够在相对较低的温度下例如室温下脱除氢气中的CO，使其满足燃料电池对氢气中CO含量的苛刻要求。
为达到本发明的目的，本发明提供如下技术方案：
本发明提供一种精脱氢气中CO的脱除剂，所述脱除剂的活性组分包括复合金属氧化物，所述复合金属氧化物中的金属元素为Cu、Ce、Mn和Bi，所述复合金属氧化物的表达通式为Cu xCe 3-x-y-zMn yBi zO 4+δ，其中，各金属元素的下标数值为对应金属元素在所述复合金属氧化物中的原子数，“4+δ”为满足其他元素氧化态所需的氧原子数，0.2<x<2、0.05<y<2.8、0.05<z<1，且x+y+z＜3。
一些实施方式中，所述脱除剂的活性组分还任选地包括其他活性组分，所述其他活性组分选自Ca的氧化物、K的氧化物、La的氧化物中的一种或多种，所述其他活性组分的含量为所述复合金属氧化物重量的0.2wt％～20wt％。
一些实施方式中，所述脱除剂中还包括其他组分，所述其他组分包括硅的氧化物和/铝的氧化物。
一些实施方式中，所述其他组分在所述脱除剂中的重量百分比为2-30％。
优选的，所述复合金属氧化物的表达通式中，1<x<2；
优选的，所述复合金属氧化物的表达通式中，0.05<z<0.5。
优选的，所述复合金属氧化物的表达通式中，0.5<y≤2，优选0.5<y≤1.5；
优选的，所述复合金属氧化物的表达通式中，2.1≤x+y+z≤2.97；
优选的，所述复合金属氧化物的表达通式中，0.5<y≤2，且2.1≤x+y+z≤2.97。
本发明还提供上文所述的脱除剂的制备方法，包括如下步骤：
1)将与活性组分中的各氧化物相对应的金属元素的可溶性盐混合配成水溶液，向该水溶液中加入碱性物质，调节pH至6-9以产生共沉淀，将共沉淀物进行老化、过滤和洗涤，得到滤饼；
2)任选地，将滤饼与任选的其他组分混合均匀成型；所述其他组分包括含有硅元素和/或铝元素的载体和/或粘结剂；优选的，所述其他组分选自硅溶胶、硅酸钾、铝溶胶、拟薄水铝石中的一种或多种；
3)焙烧，得到所述脱除剂。
一些实施方式中，所述焙烧的条件包括：焙烧温度200～600℃，焙烧时间2-12h。
本发明还提供一种脱除氢气中CO的方法，使用上文所述的脱除剂对所述氢气中的CO进行脱除。本发明的脱除剂能在低温脱除CO，一些实施方式中，在100℃以下优选在室温下进行所述氢气中CO的脱除。进一步的，所述脱除在有氧气或无氧气的存在下进行。
本发明提供的技术方案具有如下有益效果：
本发明提供的脱除剂能够在室温下脱除氢气中的CO，使CO转变成容易被脱除且对燃料电池毒性弱的CO 2，在脱除CO过程中可在不(或极低)消耗氢气的情形下达到脱除目的。基于本发明的脱除剂的脱除工艺简单易行，且运行成本低；可在无氧气条件下实现CO转化，避免氢气中引入氧气带来爆炸风险。本发明的脱除剂对氢气中CO的脱除效果优异，能够将其中的CO脱除至0ppm，本发明脱除剂能够适应不同浓度水平CO的脱除。
具体实施方式
为了便于理解本发明，下面将结合实施例对本发明作进一步的说明。应当理解，下述实施例仅是为了更好的理解本发明，并不意味着本发明仅局限于以下实施例。
除非另有定义，本文所使用的所有的技术和科学术语与本发明所属技术领域的技术人员通常理解的含义相同。本文可能使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
实施例中未注明具体实验步骤或条件之处，可按照本技术领域中相应的常规实验步骤的操作或条件进行即可。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
本发明提供的精脱氢气中CO的脱除剂，其活性组分主要包括如下复合金属氧化物，该复合金属氧化物中的金属元素为Cu、Ce、Mn和Bi，即该复合金属氧化物为Cu的氧化物、Ce的氧化物、Mn的氧化物和Bi的氧化物组成。在一些实施方式中，其活性组分可以仅包括上述复合金属氧化物。本发明提供的脱除剂中，复合金属氧化物的表达通式为Cu xCe 3-x-y-zMn yBi zO 4+δ，其中，各金属元素的下标数值例如x、3-x-y-z、y、z分别为对应金属元素在复合金属氧化物中的原子数，“4+δ”为满足其他元素氧化态所需的氧原子数。其中，0.2<x<2、0.05<y<2.8、0.05<z<1，且x+y+z＜3。
本发明提供的脱除剂，主要以Cu、Ce、Mn和Bi的氧化物组合复配作为活性成分，通过基于这四种金属元素的复合金属氧化物，界面易形成晶格缺 陷，利于电子的转移，形成更多的氧空位，增强释放或捕获氧气分子能力，增加了CO脱除活性，利于低温下CO的还原。
本发明的脱除剂，其中的复合金属氧化物的表达通式中，0.2<x<2、0.05<y<2.8、0.05<z<1，且x+y+z＜3，基于该复合金属氧化物的脱除剂，能够在相对较低的温度下例如室温下较为彻底的脱除氢气中的CO。一些较佳的实施方式中，复合金属氧化物的表达通式中，1<x<2，有利于延长脱除剂脱除CO的可使用时间。一些较佳实施方式中，0.05<z<0.5，可以改善脱除剂脱除CO的可使用时间。一些较佳实施方式中，0.5<y≤2，优选0.5<y≤1.5，可利于延长脱除剂脱除CO的可使用时间。一些较佳实施方式中，2.1≤x+y+z≤2.97，脱除剂能获得更长的脱除CO的可使用时间。一些较佳实施方式中，0.5<y≤2，且2.1≤x+y+z≤2.97，脱除剂能获得更长的脱除CO的可使用时间。
一些实施方式中，本发明的脱除剂，其活性组分除了包括上述复合金属氧化物之外，还可任选的包括其他活性组分，其他活性组分选自Ca的氧化物、K的氧化物、La的氧化物中的一种或多种，其他活性组分的含量为复合金属氧化物(即Cu、Ce、Mn和Bi的复合金属氧化物)重量的0.2wt％～20wt％。额外引入这些活性成分，有利于增强CO吸附，促进CO转化成CO 2，抑制H 2O的生成。
本发明的脱除剂可以仅包含上述活性成分，也可以将上述活性成分与其他组分复配得到本发明的脱除剂，其他组分例如包括硅的氧化物和/或铝的氧化物，具体的例如SiO 2和/或Al 2O 3。在一些实施方式中，其他组分在本发明的脱除剂中的重量百分比为2-30％，余量则为活性组分和任选存在的其他活性组分。SiO 2和/或Al 2O 3可以衍生自含有硅元素和/或铝元素的载体和/或粘结剂，例如衍生自硅溶胶、硅酸钾、铝溶胶、拟薄水铝石中的一种或多种，这些载体和/或粘结剂可以直接采用市售相应原料，引入SiO 2和/或Al 2O 3可以增加脱除剂活性相分散度及成型颗粒强度。
本发明还提供上述脱除剂的制备方法，其具体包括如下步骤：
1)将与活性组分中的各氧化物相对应的金属元素的可溶性盐混合配成水溶液，向该水溶液中加入碱性物质，调节pH至6-9以产生共沉淀，将共沉淀物进行老化(例如老化10min～300min)、过滤和洗涤，得到滤饼；
2)任选地，将滤饼与任选的其他组分混合均匀成型；所述其他组分包括含有硅元素和/或铝元素的载体和/或粘结剂，例如硅溶胶、硅酸钾、铝溶胶、拟薄水铝石等中的一种或多种；从而向脱除剂中引入对应的硅的氧化物和/或铝的氧化物；
3)焙烧，得到脱除剂。
其中，步骤1)中，“与活性组分中的各氧化物相对应的金属元素的可溶性盐”具体是指Cu元素、Ce元素、Mn元素和Bi元素的可溶性盐，以及可能含有的Ca元素、K元素、La元素的可溶性盐；可溶性盐可以为但不限于硝酸盐、硫酸盐、醋酸盐、草酸盐及其水合物等，示例的，例如三水硝酸铜、六水硝酸铈、六水硝酸锰、五水硝酸铋等。一些实施方式中，步骤1)中，可溶性盐混合配成的水溶液的摩尔浓度为0.05-2mol/L。
步骤1)中，调节pH至6-9所用的碱性物质没有特别限制，例如可以为氢氧化钠水溶液、碳酸钠水溶液或氨水溶液等，所用的碱性物质例如可以为浓度0.05-2mol/L的水溶液形式。一些实施方式中，步骤1)中，洗涤具体采用去离子水进行，主要是为了除去钠等离子。
一些实施方式中，步骤3)中，焙烧条件具体包括：焙烧温度200～600℃，焙烧时间2-12h。
本发明还提供脱除氢气中CO的方法，使用上文所述的脱除剂对氢气中的CO进行脱除。本发明的脱除剂可以在100℃以下进行氢气中CO的脱除，具体的，例如可以在室温下进行CO的脱除，无需额外的加热处理即可达到有效的脱除。本发明的脱除剂可以在有氧气或无氧气的存在下进行氢气中CO的脱除，较佳的，优选在无氧条件下进行氢气中CO的脱除，有氧条件下存在氧气不能完全转化的问题，额外引入了氧杂质。
下面通过具体实施例对本发明进行示例性说明。
实施例1：
分别称取计算量的三水硝酸铜、六水硝酸铈、六水硝酸锰、五水硝酸铋，用去离子水溶解，得到硝酸盐溶液A，浓度为0.2mol/L(以Cu、Mn、Ce、Bi离子的摩尔总和算)；然后配置NaOH水溶液，浓度为0.2mol/L；在搅拌状态下，向硝酸盐溶液A中加入NaOH水溶液调节pH值至7.5，产生共沉淀物；将共沉淀物进行老化60min后，将共沉淀物进行过滤和洗涤至钠离子除去，得到滤饼；将滤饼在400℃下焙烧10h，得到脱除剂，其为Cu、Ce、Mn和Bi氧化物的混合物(即复合金属氧化物)，该脱除剂按各元素原子数之比可表达为CuCe 0.4Mn 1.5Bi 0.1O 4+δ，其中4+δ为满足通式中其他元素的氧化态所需的氧原子数(后续实施例中的4+δ取值亦是如此，后续不再赘述)。
实施例2-6
参照实施例1的制备方法制备实施例2-6的脱除剂，和实施例1的不同仅在于调整三水硝酸铜、六水硝酸铈、六水硝酸锰、五水硝酸铋的用量，以最终得到表达通式为Cu xCe 3-x-y-zMn yBi zO 4+δ且x、y、z的取值分别为表1中相应取值的脱除剂。
实施例7：
分别称取计算量的三水硝酸铜、六水硝酸铈、六水硝酸锰、五水硝酸铋，用去离子水溶解，得到硝酸盐溶液A，浓度0.2mol/L(以Cu、Mn、Ce、Bi离子的摩尔总和算)；然后配置NaOH水溶液，浓度为0.2mol/L；在搅拌状态下，向硝酸盐溶液A中加入NaOH水溶液调节pH值至7.5，产生共沉淀物；将共沉淀物进行老化60min后，将共沉淀物进行过滤和洗涤至钠离子除去，得到滤饼；将滤饼按干基质量加入8％拟薄水铝石捏合均匀后挤条成型，在400℃下焙烧10h，得到脱除剂，表示为92％CuCe 0.4Mn 1.5Bi 0.1O 4+δ+8％Al 2O 3；其为氧化铝和活性组分构成，其中氧化铝占比为8wt％，活性组分占比为92wt％，活性组分为Cu、Ce、Mn和Bi氧化物的混合物(即复合金属氧化物)，活性组 分中各元素按原子数之比表达为CuCe 0.4Mn 1.5Bi 0.1O 4+δ。
实施例8
制备脱除剂，制备过程与实施例7基本相同，不同仅在于将其中的拟薄水铝替换为硅溶胶。所得脱除剂表示为92％CuCe 0.4Mn 1.5Bi 0.1O 4+δ+8％SiO 2，其为二氧化硅和活性组分构成，其中二氧化硅占比为8wt％，活性组分占比为92wt％，活性组分为Cu、Ce、Mn和Bi氧化物的混合物(即复合金属氧化物)，活性组分中各元素按原子数之比表达为CuCe 0.4Mn 1.5Bi 0.1O 4+δ。
实施例9
制备脱除剂，制备过程与实施例7基本相同，不同仅在于在硝酸盐溶液A中还添加了硝酸钾。所得脱除剂表示为91％CuCe 0.4Mn 1.5Bi 0.1O 4+δ+8％Al 2O 3+K 2O 1％，其为氧化铝和活性组分构成，其中氧化铝占比为8wt％，活性组分包括Cu、Ce、Mn、Bi的复合金属氧化物和K氧化物，其中Cu、Ce、Mn、Bi的复合金属氧化物占比为91wt％，K氧化物占比为1wt％。
性能考察
在室温(25℃)、常压下，以0.5％(v/v)CO+H 2为原料气，将各实施例的脱除剂不经过预处理直接装填于反应管中，在无氧气条件下测试不同组成的脱除剂对原料气中CO的脱除效果，结果如下表1、2所示。
其中，“CO穿透时间”是指：从向反应管中通入原料气开始计时，监测反应管出口端CO含量，当反应管出口端监测到CO时，该时间跨度为所述CO穿透时间。CO含量的检测采用安捷伦便携色谱Micro-GC。
表2中，“强度”为采用自动数显颗粒强度仪得到的脱除剂的抗压碎力除以被检测的脱除剂的长度所得的值。
表1样品组成与脱除CO性能关系
Figure PCTCN2022126098-appb-000001
Figure PCTCN2022126098-appb-000002
表1中，x、y、z对应于脱除剂表达通式Cu xCe 3-x-y-zMn yBi zO 4+δ中的x、y、z。
由表1可以看出实施例3的效果最佳，脱除剂可使用时间最长。对比实施例2、实施例3可以看出，y、z值相同时，x越大脱除剂穿透时间越长；x的最佳优选范围为1<x<2，z为Bi元素(分子量较大)，要保证单位质量剂的活性，该组分不能过高，优选0.05<z<0.5；
对比实施例3与实施例4可以看出相同x值时，y值降低脱除剂穿透时间明显缩短，说明y值不能过低。较佳的，y取值优选范围为0.5<y≤1.5。
对比实施例3与实施例5可以看出，当x+y+z＝3，无Ce时吸附剂有活性，但穿透时间由102min降低至62min；对比实施例2与实施例6可以看出，当Z＝0，无Bi时吸附剂有活性，但穿透时间由含Bi为0.3时的78min降低至65min；说明几种金属有协调效应，缺少某一种后效果不佳。
表2粘结剂改进强度
Figure PCTCN2022126098-appb-000003
从表2可见，引入氧化铝/二氧化硅后，脱除剂的强度均有所改善，Al 2O 3的引入对强度提高幅度较大，但会导致活性有所下降；SiO 2的引入效果较好， 不仅强度有所改进，且活性也有所提高。
实施例9与实施例7对比可以看出，在引入Al 2O 3的基础上进一步引入K 2O，不仅依然维持较好的强度，CO穿透时间也由78min提高至82min，可见，K的引入有利于进一步增强脱除剂对CO的脱除能力。
表3实施例1在25℃、1bar条件下在不同CO浓度下的脱除CO效果评价
Figure PCTCN2022126098-appb-000004
表3为实施例1在25℃、1bar不同CO浓度下的评价结果，可以看出该脱除剂随着CO浓度降低，产品气露点略有增高，穿透时间延长；说明本发明提供的脱除剂能够在室温几乎不消耗氢气的情况下脱除氢气中不同浓度水平的CO。
本领域技术人员可以理解，在本说明书的教导之下，可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。

Claims (10)

  1. 一种精脱氢气中CO的脱除剂，其特征在于，所述脱除剂的活性组分包括复合金属氧化物，所述复合金属氧化物中的金属元素为Cu、Ce、Mn和Bi，所述复合金属氧化物的表达通式为Cu xCe 3-x-y-zMn yBi zO 4+δ，其中，各金属元素的下标数值为对应金属元素在所述复合金属氧化物中的原子数，“4+δ”为满足其他元素氧化态所需的氧原子数，0.2<x<2、0.05<y<2.8、0.05<z<1，且x+y+z＜3。
  2. 根据权利要求1所述的精脱氢气中CO的脱除剂，其特征在于，所述脱除剂的活性组分还任选地包括其他活性组分，所述其他活性组分选自Ca的氧化物、K的氧化物、La的氧化物中的一种或多种。
  3. 根据权利要求2所述的精脱氢气中CO的脱除剂，其特征在于，所述其他活性组分的含量为所述复合金属氧化物重量的0.2wt％～20wt％。
  4. 根据权利要求1-3任一项所述的精脱氢气中CO的脱除剂，其特征在于，所述脱除剂中还包括其他组分，所述其他组分包括硅的氧化物和/铝的氧化物。
  5. 根据权利要求4所述的精脱氢气中CO的脱除剂，其特征在于，所述其他组分在所述脱除剂中的重量百分比为2-30％。
  6. 根据权利要求1-3任一项所述的精脱氢气中CO的脱除剂，其特征在于，所述复合金属氧化物的表达通式中，1<x<2；
    和/或，0.05<z<0.5；
    和/或，0.5<y≤2，优选0.5<y≤1.5；
    和/或，2.1≤x+y+z≤2.97；
    和/或，0.5<y≤2，且2.1≤x+y+z≤2.97。
  7. 权利要求1-6任一项所述的脱除剂的制备方法，其特征在于，包括如下步骤：
    1)将与所述活性组分中的各氧化物相对应的金属元素的可溶性盐混合配成水溶液，向该水溶液中加入碱性物质，调节pH至6-9以产生共沉淀，将共沉淀物进行老化、过滤和洗涤，得到滤饼；
    2)任选地，将滤饼与任选的其他组分混合均匀成型；所述其他组分包括含有硅元素和/或铝元素的载体和/或粘结剂；优选的，所述其他组分选自硅溶胶、硅酸钾、铝溶胶、拟薄水铝石中的一种或多种；
    3)焙烧，得到所述脱除剂。
  8. 根据权利要求7所述的制备方法，其特征在于，所述焙烧的条件包括：焙烧温度200～600℃，焙烧时间2-12h。
  9. 一种脱除氢气中CO的方法，其特征在于，使用权利要求1-6任一项所述的脱除剂或权利要求7-8任一项所述的制备方法制得的脱除剂对所述氢气中的CO进行脱除。
  10. 根据权利要求9所述的脱除氢气中CO的方法，其特征在于，在100℃以下优选在室温下进行所述氢气中CO的脱除；
    所述脱除在有氧气或无氧气的存在下进行。
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