A removal agent for finely removing CO from hydrogen, a method for preparing the same, and its use.

Abstract

The present invention provides a remover for CO in purified hydrogen, as well as a preparation method thereof and its use. The remover provided in the present invention can thoroughly remove CO in hydrogen at a relatively low temperature, such as room temperature, so as to meet the strict requirements of fuel cells for the CO content in hydrogen. According to the remover for CO in purified hydrogen provided in the present invention, the active component of the remover comprises a complex metal oxide, the metal elements in the complex metal oxide are Cu, Ce, Mn and Bi, and the general formula of the complex metal oxide is Cu, Ce, Mn and Bi. X Ce 3-x-y-z Mn y Bi z O 4+δ where the value of the subscript for each metal element is the number of atoms of the corresponding metal element in the composite metal oxide, "4+δ" is the number of oxygen atoms required to satisfy the oxidation state of the other element, and 0.2

Description

Detailed description of the invention

[0001] [Technical field] The present invention relates to the art of removing CO from hydrogen, and more particularly to a removal agent for finely removing CO from hydrogen, as well as a method for preparing the same and its use.

[0002] [Background technology] Proton exchange membrane fuel cells are highly sensitive to impurities in hydrogen; therefore, the purity of hydrogen used in hydrogen fuel cells must meet the requirements of ISO 14687-2 and SAE J2719 Hydrogen Quality Standard for Fuel Cell Vehicles. The national standard requirement for pure hydrogen is that the CO content in the generated hydrogen is less than 5 ppm, and the requirement for high-purity hydrogen is that the CO content in the generated hydrogen is less than 1 ppm, but for fuel cells, it is stipulated that the CO content should be less than 0.2 ppm.

[0003] The CO impurity content of industrial-grade pure hydrogen and high-purity hydrogen cannot meet the quality requirements for hydrogen used in fuel cells, thus necessitating excessive CO removal. Currently, PSA and TSA methods are used for CO removal / separation from hydrogen. These methods are generally used to separate high concentrations of CO, and the removal agents used in these methods must be reduced in situ before use, carrying the risk of introducing Cl ions. Since H2O and CO2 affect the adsorption performance of these methods, the application of H2O and CO2 to hydrogen purification for fuel cell vehicles is still debatable. Conventional PSA purification processes struggle to remove CO content down to 0.2 ppm. Furthermore, conventional catalytic oxidizers can only oxidize CO at approximately 100°C in the presence of O2, and introducing O2 into hydrogen carries the risk of explosion and is prone to side reactions with hydrogen.

[0004] CN109499261A discloses a system and method for removing CO from hydrogen for 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, which are interconnected in sequence. This document provides a method for removing CO using a removal system that uses CuCl as the CO adsorbent. However, hydrogen for fuel cell vehicles has a strict requirement for Cl ions (less than 0.05 ppm), and there is a risk that this adsorbent will introduce Cl ions.

[0005] Document CN201210402065.X discloses a catalyst for oxidative removal of carbon monoxide in hydrogen and a method for preparing the same. This document provides a catalyst for selective oxidative removal of carbon monoxide in high concentrations of hydrogen, as well as a method for preparing and using the same. The catalyst is a support carrying an active component and an additive; 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 amount of the active component supported is 0.01-0.1% (wt%) of the catalyst, and the amount of the additive supported is 0.5-5% (wt%) of the catalyst. This document provides a noble metal catalyst capable of removing carbon monoxide in hydrogen at 100°C-200°C. While energy consumption is high at high temperatures, on the other hand, competitive reactions between hydrogen and CO are promoted, producing H2O byproducts.

[0006] [overview] In this regard, the present disclosure provides a scavenger for finely removing CO from hydrogen, a method for preparing the same, and its use. The scavenger provided by the present disclosure can remove CO from hydrogen at relatively low temperatures, such as room temperature, to meet the stringent requirements of fuel cells regarding the CO content in hydrogen.

[0007] To achieve the objectives of this disclosure, this disclosure provides the following technical solutions.

[0008] The present disclosure provides a remover for finely removing CO in hydrogen. The active component of the remover contains a composite metal oxide. The metal elements in the composite metal oxide are Cu, Ce, Mn, and Bi. The general formula of the composite metal oxide is Cu x Ce 3-x-y-z Mn y Bi z O 4+δ , where the value of the subscript of each metal element is the number of atoms of the corresponding metal element in the composite metal oxide, and "4 + δ" is the number of oxygen atoms required to satisfy the oxidation states of other elements, 0.2 < x < 2, 0.05 < y < 2.8, 0.05 < z < 1, and x + y + z < 3.

[0009] In some embodiments, the active component of the remover may further optionally contain other effective components. The other effective components are selected from one or more of the oxides of Ca, the oxides of K, and the oxides of La. The content of the other effective components is 0.2 to 20 wt% based on the weight of the composite metal oxide.

[0010] In some embodiments, the remover further contains other components, and the other components include silicon oxide and / or aluminum oxide.

[0011] In some embodiments, the weight percentage of the other components based on the remover is 2 to 30%.

[0012] Preferably, in the general formula of the composite metal oxide, 1 < x < 2.

[0013] Preferably, in the general formula of the composite metal oxide, 0.05 < z < 0.5.

[0014] Preferably, in the general formula of the composite metal oxide, 0.5 < y ≤ 2, more preferably 0.5 < y ≤ 1.5.

[0015] Preferably, in the general formula of the composite metal oxide, 2.1 ≦ x + y + z ≦ 2.97.

[0016] Preferably, in the general formula of the composite metal oxide, 0.5 < y ≦ 2, and 2.1 ≦ x + y + z ≦ 2.97.

[0017] The present disclosure further provides a method for preparing a removing agent, including the following steps: 1) Mixing soluble salts of metal elements corresponding to the oxides in the active ingredient to prepare an aqueous solution, adding an alkaline substance to the aqueous solution, adjusting the pH to 6 - 9 to form a coprecipitate, aging, filtering and washing the coprecipitate to obtain a filter cake; 2) Optionally, uniformly mixing the filter cake with any other components and shaping the mixture; here, the other components include a carrier and / or a binder, the carrier and / or the binder contain silicon element and / or aluminum element; preferably, the other components are selected from one or more of silica sol, potassium silicate, alumina sol and pseudoboehmite; 3) Calcining to obtain the removing agent.

[0018] In some embodiments, the calcination conditions include a calcination temperature of 200 - 600°C and a calcination time of 2 - 12 hours.

[0019] The present disclosure further provides a method for removing CO in hydrogen, and the CO in hydrogen is removed using the above-mentioned removing agent. CO can be removed at a low temperature by the removing agent in the present disclosure. In some embodiments, the CO in hydrogen is removed at 100°C or lower, preferably at room temperature. Further, the removal is carried out in the presence or absence of oxygen.

[0020] The technical solutions provided by the present disclosure have the following beneficial effects.

[0021] The removal agent provided in this disclosure can remove CO from hydrogen at room temperature, thereby converting CO to CO2, which is easily removed and has low toxicity to fuel cells, and achieving the removal objective without (or with very little) consumption of hydrogen in the CO removal process. The removal process based on the removal agent in this disclosure is simple and easy and has low operating costs. In addition, CO conversion can be achieved without using oxygen, thus avoiding the risk of explosion caused by introducing oxygen into hydrogen. The removal agent in this disclosure has excellent efficacy in removing CO from hydrogen and can remove CO down to 0 ppm, and the removal agent in this disclosure can be adapted for CO removal at different concentration levels.

[0022] [Detailed explanation] To facilitate understanding of this disclosure, the disclosure will be further described in conjunction with examples. It should be understood that the following examples are provided for better understanding of this disclosure and do not imply that this disclosure is limited to these examples.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art in which this disclosure pertains. The terms “and / or” as used herein include any and all combinations of one or more related enumerated items.

[0024] The endpoints and any values ​​of the ranges disclosed herein are not limited to exact ranges or values, and these ranges or values ​​should be understood to include values ​​close to them. For numerical ranges, one or more new numerical ranges can be obtained by combining endpoint values ​​of various ranges, combining endpoint values ​​of various ranges with individual point values, or combining individual point values, and these numerical ranges should be considered as specifically disclosed herein.

[0025] When specific experimental procedures or conditions are not specified in the examples, operations or conditions corresponding to conventional experimental procedures in the relevant technical field can be followed. When the manufacturer of the reagents or instruments used is not specified, all reagents or instruments are commercially available conventional products.

[0026] The present disclosure provides a remover for finely removing CO in hydrogen. The active ingredient of the remover mainly includes the following composite metal oxides. The metal elements in the composite metal oxides are Cu, Ce, Mn, and Bi. That is, the composite metal oxide consists of oxides of Cu, oxides of Ce, oxides of Mn, and oxides of Bi. In some embodiments, the active ingredient may contain only the above composite metal oxides. In the remover provided by the present disclosure, the general formula of the composite metal oxide is Cu x Ce 3-x-y-z Mn y Bi z O 4+δ where the values of the subscripts of each metal element such as x, 3 - x - y - z, y, and z are the number of atoms of the corresponding metal element in the composite metal oxide, and "4 + δ" is the number of oxygen atoms required to satisfy the oxidation states of other elements, and 0.2 < x < 2, 0.05 < y < 2.8, 0.05 < z < 1, and x + y + z < 3.

[0027] [[ID=IP=18]]The remover provided by the present disclosure mainly takes a combination of oxides of Cu, Ce, Mn, and Bi as the active ingredient. Through the composite metal oxide based on these four metal elements, lattice defects are easily formed at the interface. This is beneficial for electron transfer, forms more oxygen vacancies, enhances the ability to release or capture oxygen molecules, increases the CO removal activity, and promotes the reduction of CO at low temperatures.

[0028] According to the removing agent of the present disclosure, in the general formula of the composite metal oxide, 0.2 < x < 2, 0.05 < y < 2.8, 0.05 < z < 1, and x + y + z < 3. CO in hydrogen can be more thoroughly removed by the removing agent based on the composite metal oxide at a relatively low temperature such as room temperature. In some preferred embodiments, in the general formula of the composite metal oxide, 1 < x < 2, which is beneficial for extending the usable time of the removing agent for CO removal. In some preferred embodiments, 0.05 < z < 0.5, which can improve the usable time of the removing agent for CO removal. In some preferred embodiments, 0.5 < y ≤ 2, preferably 0.5 < y ≤ 1.5, which is beneficial for extending the usable time of the removing agent for CO removal. In some preferred embodiments, 2.1 ≤ x + y + z ≤ 2.97, and the removing 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, and the removing agent can obtain a longer usable time for CO removal.

[0029] In some embodiments, in addition to the above composite metal oxide, the active component of the removing agent of the present disclosure can optionally contain other effective components, and the other effective components are selected from one or more of the oxides of Ca, the oxides of K, and the oxides of La, and the content of the other active components is 0.2 to 20 wt% based on the weight of the composite metal oxide (that is, the composite metal oxide of Cu, Ce, Mn, and Bi). The introduction of additional effective components is beneficial for promoting the adsorption of CO, promoting the conversion of CO to CO2, and suppressing the generation of H2O.

[0030] The remover of this disclosure may consist solely of the active ingredient, or it may be obtained by compounding the active ingredient with other ingredients, such as silicon oxides and / or aluminum oxides, specifically SiO2 and / or Al2O3. In some embodiments, the weight percentage of the other ingredients in the remover of this disclosure is 2-30%, with the remainder being the active ingredient and optionally other existing effective ingredients. SiO2 and / or Al2O3 may be derived from one or more carriers and / or binders containing silicon and / or aluminum elements, such as silica sol, potassium silicate, alumina sol, and boehmite pseudo. These carriers and / or binders can be directly derived from commercially available corresponding raw materials, and the introduction of SiO2 and / or Al2O3 can improve the dispersibility of the active phase of the remover and the strength of the molded particles.

[0031] This disclosure also provides a method for preparing the above-mentioned removal agent, which specifically includes the following steps: 1) Prepare an aqueous solution by mixing soluble salts of metal elements corresponding to oxides in the active ingredient, add an alkaline substance to this aqueous solution to adjust the pH to 6-9 to generate a coprecipitate, age it (e.g., for 10-300 minutes), filter and wash the coprecipitate to obtain a filter cake; 2) Optionally, uniformly mix the filtration cake with any other components and form the mixture; the other components include a carrier and / or binder, the carrier and / or binder including one or more elements of silicon and / or aluminum, such as silica sol, potassium silicate, alumina sol and boehmite; thereby introducing the corresponding silicon oxide and / or aluminum oxide into the scavenger; 3) Calcining to obtain the removal agent.

[0032] In step 1), "soluble salts of metal elements corresponding to oxides in the active ingredient" specifically refer to soluble salts of Cu, Ce, Mn, and Bi elements, as well as soluble salts of Ca, K, and La elements that may be included; the soluble salts may be, but are not limited to, nitrates, sulfates, acetates, oxalates, and their hydrates, such as copper nitrate trihydrate, cerium nitrate hexahydrate, manganese nitrate hexahydrate, bismuth nitrate pentahydrate, etc. In some embodiments, the molar concentration of the aqueous solution prepared by mixing the soluble salts in step 1) is 0.05 to 2 mol / L.

[0033] In step 1), the alkaline substance used to adjust the pH to 6-9 is not particularly limited and can be, for example, an aqueous solution of sodium hydroxide, an aqueous solution of sodium carbonate, or an aqueous solution of ammonia. The alkaline substance used can be, for example, an aqueous solution with a concentration of 0.05-2 mol / L. In some embodiments, in step 1), deionized water is used for washing, specifically to remove sodium ions and the like.

[0034] In some embodiments, in step 3), the firing conditions specifically include a firing temperature of 200 to 600°C and a firing time of 2 to 12 hours.

[0035] This disclosure further provides a method for removing CO from hydrogen, wherein the CO from hydrogen is removed by using the removal agent described above. The CO from hydrogen can be removed by the removal agent of this disclosure at temperatures below 100°C, specifically, for example, at room temperature. Effective removal can be achieved without requiring additional heat treatment. The removal agent of this disclosure can remove CO from hydrogen in the presence or absence of oxygen, preferably in the absence of oxygen. Using conditions in the presence of oxygen results in the problem that the oxygen cannot be completely converted, and oxygen impurities are further introduced.

[0036] This disclosure is illustrated by specific embodiments.

[0037] Example 1: The calculated amounts of copper nitrate trihydrate, cerium nitrate hexahydrate, manganese nitrate hexahydrate, and bismuth nitrate pentahydrate were weighed and dissolved in deionized water to obtain 0.2 mol / L nitrate solution A (calculated using the molar sum of Cu, Mn, Ce, and Bi ions). Next, a 0.2 mol / L NaOH aqueous solution was prepared, and under stirring, the NaOH aqueous solution was added to nitrate solution A to raise the pH to 7.5 to generate a coprecipitation. After aging this coprecipitation for 60 minutes, the coprecipitation was filtered off and washed until sodium ions were removed to obtain a filtration cake. This filtration cake was calcined at 400°C for 10 hours to obtain a removal agent which is a mixture of oxides of Cu, Ce, Mn, and Bi (i.e., a complex metal oxide). This removal agent was prepared according to the atomic ratio of each element, such as CuCe 0.4 Mn 1.5 Bi 0.1 O 4+δ It can be expressed as follows, where 4+δ is the number of oxygen atoms required to satisfy the oxidation states of the other elements in the general formula (the same applies to the values ​​of 4+δ in the following examples, and no further details will be given).

[0038] Examples 2-6: The removal agents of Examples 2-6 were prepared according to the preparation method of Example 1, the only difference from Example 1 being the adjustment of the amounts used for copper nitrate trihydrate, cerium nitrate hexahydrate, manganese nitrate hexahydrate, and bismuth nitrate pentahydrate, and finally Cu x Ce 3-x-y-z Mn y Bi z O 4+δ A removal agent having the general formula was obtained, and the values ​​of x, y, and z were the corresponding values ​​in Table 1.

[0039] Example 7: The calculated amounts of copper nitrate trihydrate, cerium nitrate hexahydrate, manganese nitrate hexahydrate, and bismuth nitrate pentahydrate were weighed and dissolved in deionized water to obtain a 0.2 mol / L nitrate solution A (calculated using the molar sum of Cu, Mn, Ce, and Bi ions). Next, a 0.2 mol / L NaOH aqueous solution was prepared, and under stirring, the NaOH aqueous solution was added to nitrate aqueous solution A to adjust the pH to 7.5 to generate a coprecipitation. This coprecipitation was aged for 60 minutes, then filtered off and washed until sodium ions were removed to obtain a filtration cake. 8% pseudo-boehmite was added to the filtration cake according to the dry basis mass, kneaded uniformly, extruded, and baked at 400°C for 10 hours to obtain a removal agent. This removal agent was 92% CuCe 0.4 Mn 1.5 Bi 0.1 O 4+δ Expressed as +8%Al2O3; this remover consists of aluminum oxide and an active ingredient, with aluminum oxide accounting for 8 wt% and the active ingredient accounting for 92 wt%. The active ingredient is a mixture of oxides of Cu, Ce, Mn, and Bi (i.e., a composite metal oxide), with each element in the active ingredient present in the order of atomic ratios of CuCe 0.4 Mn 1.5 Bi 0.1 O 4+δ It was expressed as follows.

[0040] Example 8: The preparation process for the removal agent was basically the same as in Example 7, the only difference being that the pseudo-boehmite was replaced with silica sol. The resulting removal agent was 92% CuCe 0.4 Mn 1.5 Bi 0.1 O 4+δ It was expressed as +8%SiO2, which consisted of silicon dioxide and an active ingredient, with silicon dioxide at 8 wt% and the active ingredient at 92 wt%. The active ingredient was a mixture of oxides of Cu, Ce, Mn, and Bi (i.e., a composite metal oxide), with each element in the active ingredient being CuCe in atomic ratio. 0.4 Mn 1.5 Bi 0.1 O 4+δ It is expressed as follows.

[0041] Example 9: The preparation process for the removal agent was basically the same as in Example 7, except that potassium nitrate was added to nitric acid solution A. The resulting removal agent was 91% CuCe 0.4 Mn 1.5 Bi 0.1 O 4+δ Expressed as +8%Al2O3+K2O 1%, this consists of aluminum oxide and active components, with aluminum oxide accounting for 8 wt%, and the active components consisting of composite metal oxides of Cu, Ce, Mn, and Bi, as well as K oxide, with the composite metal oxides of Cu, Ce, Mn, and Bi accounting for 91 wt%, and the K oxide accounting for 1 wt%.

[0042] [Performance Test] Under room temperature (25°C) and atmospheric pressure, using 0.5% (v / v) CO + H2 as the supply gas, the removal agents from each example were directly packed into the reaction tube without pretreatment, and the removal effect of removal agents with different compositions on CO in the supply gas was tested under oxygen-free conditions. The results are shown in Tables 1 and 2 below.

[0043] Here, "CO penetration time" refers to monitoring the CO content at the outlet end of the reaction tube. The timer starts when the supply gas is introduced into the reaction tube and stops when CO is detected at the outlet end of the reaction tube. The time between these two stops is called the CO penetration time. The CO content was detected using Agilent's portable chromatograph, Micro-GC.

[0044] In Table 2, "strength" refers to the crush resistance force of the removal agent (obtained by an automatic digital particle intensity meter) divided by the length of the removal agent being detected.

[0045] [Table 1]

[0046] In Table 1, x, y, and z are the general formula of the removal agent Cu x Ce 3-x-y-z Mn y Bi zO 4+δ corresponds to x, y, and z thereof.

[0047] From Table 1, it can be recognized that the effect of Example 3 is the most excellent, and it can be seen that the scavenger can be used for the longest time. Comparing Example 2 and Example 3, when the values of y and z are the same, the larger the x, the longer the passing time of the scavenger, and it can be recognized that the optimal range of x is 1 < x < 2. z represents the Bi element (with a relatively large molecular weight), and in order to ensure the activity of the scavenger per unit mass, the content of this element should not be too high, preferably 0.05 < z < 0.5.

[0048] Comparing Example 3 and Example 4, when the value of x is the same, reducing the value of y clearly shortens the passing time of the scavenger, indicating that the value of y should not be too low. Preferably, 0.5 < y ≤ 1.5 is the preferred value range of y.

[0049] Comparing Example 3 and Example 5, when x + y + z = 3, it can be recognized that the adsorbent shows activity without Ce, but the passing time is shortened from 102 minutes to 62 minutes. Comparing Example 2 and Example 6, when z = 0, it can be recognized that the adsorbent shows activity without Bi, but the passing time is shortened from 78 minutes (when the Bi content is 0.3) to 65 minutes. This indicates that some metals exhibit a synergistic effect, and the effect is not good when any of the metals is absent.

[0050]

Table 2

[0051] From Table 2, it can be recognized that the strength values of the scavenger all improve after the introduction of aluminum oxide / silicon dioxide. The introduction of Al2O3 increases the strength but leads to a certain decrease in activity. The introduction of SiO2 has a more excellent effect of not only improving the strength but also improving the activity.

[0052] Comparing Example 9 with Example 7, it can be seen that K2O is further introduced in addition to Al2O3. This not only maintains good strength but also extends the CO passage time from 78 minutes to 82 minutes. The introduction of K may be beneficial in further enhancing the CO removal capacity of the removal agent.

[0053] [Table 3]

[0054] Table 3 shows the evaluation results of Example 1 at different CO concentrations, 25°C, and 1 bar. As the CO concentration decreases, it can be observed that the dew point of the product gas increases slightly and the transit time is extended. This indicates that the scavenger provided by this disclosure can remove CO at different concentrations in hydrogen at room temperature with little to no hydrogen consumption.

[0055] Those skilled in the art will understand that certain modifications or adjustments can be made to this disclosure in light of the instructions herein. These modifications or adjustments shall also be within the scope defined by the claims of this disclosure.

Claims

1. A removal agent for removing CO from hydrogen, wherein the active component of the removal agent contains a composite metal oxide, the metal elements in the composite metal oxide are Cu, Ce, Mn and Bi, and the general formula of the composite metal oxide is Cu ｘ Ce ３－ｘ－ｙ－ｚ Mn ｙ Bi ｚ O ４＋δ The formula is such that, in the equation, the subscript value of each metal element is the number of atoms of the corresponding metal element in the composite metal oxide, and "4 + δ" is the number of oxygen atoms required to satisfy the oxidation state of the other elements, with 0.2 < x < 2, 0.05 < y < 2.8, 0.05 < z < 1, and x + y + z < 3, and is used as a remover.

2. The removal agent for removing CO from hydrogen according to claim 1, wherein the active component of the removal agent further optionally comprises another effective component, the other effective component being selected from one or more of Ca oxides, K oxides, and La oxides.

3. The removal agent for removing CO from hydrogen according to claim 2, wherein the content of the other effective component is 0.2 to 20 wt% based on the weight of the composite metal oxide.

4. The removal agent for removing CO from hydrogen according to claim 1, wherein the removal agent further comprises other components, the other components comprising silicon oxide and / or aluminum oxide.

5. The removal agent for removing CO from hydrogen according to claim 4, wherein the weight percentage of the other components based on the removal agent is 2 to 30%.

6. In the general formula for the composite metal oxide, 1 < x < 2 The removal agent for removing CO from hydrogen as described in claim 1.

7. In the general formula of the composite metal oxide, 0.05 < z < 0.5 The removal agent for removing CO from hydrogen as described in claim 1.

8. In the general formula of the composite metal oxide, 0.5 < y ≤ 2 The removal agent for removing CO from hydrogen as described in claim 1.

9. In the general formula of the composite metal oxide, 0.5 < y ≤ 1.5 The removal agent for removing CO from hydrogen according to claim 8.

10. In the general formula of the composite metal oxide, 2.1 ≤ x + y + z ≤ 2.97 The removal agent for removing CO from hydrogen as described in claim 1.

11. A method for preparing a removal agent according to any one of claims 1 to 10, comprising the following steps: 1) Prepare an aqueous solution by mixing a soluble salt of a metal element corresponding to the oxide in the active ingredient, add an alkaline substance to the aqueous solution, adjust the pH to 6-9 to generate a coprecipitate, age the solution, filter and wash the coprecipitate to obtain a filter cake; 3) To obtain the removal agent, calcination is performed.

12. The preparation method according to claim 11, further comprising the following steps between steps 1) and 3): 2) Mix the filtered cake uniformly with any other components and form it; the other components include a carrier and / or binder, and the carrier and / or binder contains silicon and / or aluminum.

13. The preparation method according to claim 12, wherein the other component is selected from one or more silica sol, potassium silicate, alumina sol, and pseudoboehmite.

14. The preparation method according to claim 11, wherein the firing conditions include a firing temperature of 200 to 600°C and a firing time of 2 to 12 hours.

15. The preparation method according to claim 12, wherein the firing conditions are a firing temperature of 200 to 600°C and a firing time of 2 to 12 hours.

16. A method for removing CO from hydrogen, comprising using a removal agent described in any one of claims 1 to 10.

17. The CO in the hydrogen is removed at a temperature of 100°C or lower; The method for removing CO from hydrogen according to claim 16, wherein the removal is performed regardless of the presence or absence of oxygen.

18. The method for removing CO from hydrogen according to claim 17, wherein the CO from the hydrogen is removed at room temperature.

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