A method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation and hydrogen purified by this method.

Abstract

This invention discloses a method for removing carbon monoxide from crude hydrogen gas via low-temperature methanation. The method involves contacting a catalyst supported on carbon-modified alumina microspheres with the crude hydrogen gas to perform a methanation reaction to remove carbon monoxide. The catalyst supported on carbon-modified alumina microspheres comprises a carbon-modified alumina microsphere composite support and an active component supported on the composite support. The carbon content is 0.01–10 wt% (based on 100% weight of the composite support), and the active component content is 20–60 wt% (based on 100% weight of the catalyst). This invention utilizes a catalyst supported on carbon-modified alumina microspheres to remove trace amounts of CO via methanation under gas-solid two-phase conditions, reducing CO in crude hydrogen gas to below 1 ppm.

Description

Technical Field

[0001] This invention relates to the field of industrial catalyst technology, and more specifically, to a method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation and the hydrogen purified by this method. Background Technology

[0002] Methanation catalysts are mainly used for the deep removal of trace carbon oxides (mainly CO) from crude hydrogen in ethylene or ammonia synthesis plants. Generally, the carbon oxides in the crude hydrogen must be reduced to less than 5 ppm after passing through the methanation reactor. Methanation catalysts are classified into high-temperature catalysts and low-temperature catalysts. In ethylene plants, high-temperature catalysts typically operate at temperatures of 280-350℃, while low-temperature catalysts typically operate at temperatures of 150-200℃.

[0003] Imported low-temperature methanation catalysts have been applied in a domestic petrochemical ethylene plant. These catalysts are still based on traditional nickel-supported catalysts, characterized by low reaction temperatures (below 200℃) and low gas space velocities (2000 h⁻¹). -1 about).

[0004] The domestically produced low-temperature methanation catalyst is the BC-H-10 catalyst developed by the Beijing Research Institute of Chemical Industry of Sinopec. This catalyst exhibits very high low-temperature activity, with an operating temperature range of 150-200℃. A more significant advantage is that its space velocity can reach 5000 h⁻¹ at low temperatures. -1 about.

[0005] Based on research literature and application data, methanation catalysts mainly include noble metal Ru catalysts and nickel metal catalysts. Due to the high cost of Ru metal, there are currently very few applications of noble metal Ru catalysts, both domestically and internationally. The methanation catalysts used both domestically and internationally are primarily based on supported nickel metal catalysts.

[0006] Low-temperature methanation catalysts offer advantages such as energy saving, environmental friendliness, safety, and economy, and high-temperature methanation processes will gradually be replaced by low-temperature methanation processes. However, low-temperature catalysts require extremely high catalyst activity; to obtain high activity at low temperatures, high nickel content is generally required, resulting in high raw material and processing costs.

[0007] Therefore, developing a catalyst supported on carbon-modified monodisperse alumina microspheres is of great significance for broadening the variety of methanation catalysts and improving catalytic reaction performance. Summary of the Invention

[0008] To address the problems in existing technologies, this invention proposes a method for removing carbon monoxide from crude hydrogen gas via low-temperature methanation, and the hydrogen purified using this method. This invention employs a catalyst supported on carbon-modified alumina microspheres to remove trace amounts of CO from crude hydrogen gas via methanation under gas-solid two-phase conditions, reducing CO levels in the crude hydrogen gas to below 1 ppm.

[0009] One of the objectives of this invention is to provide a method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation. The method for removing carbon monoxide from crude hydrogen gas involves contacting a catalyst supported on carbon-modified alumina microspheres with crude hydrogen gas to carry out a methanation reaction to remove carbon monoxide.

[0010] The catalyst supported on the carbon-modified alumina microspheres includes a carbon-modified alumina microsphere composite support and an active component supported on the composite support.

[0011] Based on the weight of the composite carrier as 100%,

[0012] The carbon content is 0.01–10 wt%; preferably 0.1–1 wt%; for example, it can be 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, or any parameter range between two values, preferably 0.1–1 wt%; more preferably 0.1–0.82 wt%.

[0013] Based on the catalyst by weight of 100%,

[0014] The content of the active component is 20-60 wt%, for example, it can be 20 wt%, 21 wt%, 23 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, or any parameter range between two values, preferably 35%-50% wt%.

[0015] Preferably,

[0016] The methanation reaction is carried out at a temperature of 140-200℃ and a reaction pressure of 0.1-7.0 MPa; and / or,

[0017] The volumetric hourly space velocity (VHSV) of crude hydrogen gas under standard conditions is less than 20,000 h⁻¹. -1 The preferred range is 1000-20000h. -1 ; and / or,

[0018] The concentration of CO in the crude hydrogen gas is less than 5000 ppm.

[0019] Preferably,

[0020] The alumina microspheres are monodisperse alumina microspheres, preferably alumina microspheres with an average diameter of 200-800 μm and a coefficient of variation of 3-8%.

[0021] In this invention, alumina microspheres can be prepared in-house or purchased from existing alumina microspheres that meet the requirements.

[0022] Preferably,

[0023] The active component is selected from at least one of Ni or Ru.

[0024] In this invention, the metal corresponding to the active component is in a reduced or oxidized state. In use, the oxidized catalyst can be reduced using conventional reduction methods.

[0025] Preferably,

[0026] The preparation method of the catalyst supported on the carbon-modified alumina microspheres includes the following steps:

[0027] (1) Alumina microspheres were added to a nitrogen-containing polymer solution, and then reacted by a solvothermal method. After post-treatment, a nitrogen-containing polymer-modified alumina microsphere composite carrier was obtained.

[0028] (2) The alumina microsphere composite carrier modified with nitrogen-containing polymer was calcined under an inert atmosphere to obtain a carbon-modified alumina microsphere composite carrier.

[0029] (3) The carbon-modified alumina microsphere composite support is immersed in the active component precursor solution, dried, and calcined to obtain the catalyst supported on carbon-modified alumina microspheres.

[0030] Preferably,

[0031] In step (1),

[0032] The nitrogen-containing polymer is selected from one or a combination of polyvinylimidazolium, polyvinylpyrrolidone, or polyvinylpyridine; and / or,

[0033] The concentration of the nitrogen-containing polymer solution is 0.1–1 wt%; and / or,

[0034] The solvent in the nitrogen-containing polymer solution is selected from one or a combination of methanol and ethanol.

[0035] Preferably,

[0036] In step (1),

[0037] The mass ratio of the alumina microspheres to the nitrogen-containing polymer solution is 1:1 to 10; and / or,

[0038] The solvothermal method involves a reaction temperature of 100–120°C and a reaction time of 4–10 h; and / or,

[0039] The alumina microspheres were prepared using a microchannel reactor.

[0040] The microchannel reactor can be any commonly used microchannel reactor in the prior art, and can be a single-channel reactor or a multi-channel reactor.

[0041] The multi-channel reactor can preferably be an eight-channel reactor. In this invention, the structure of the eight-channel reactor is preferably that of the eight-channel reactor disclosed in Chinese Patent CN113041974A, which is used for the large-scale preparation of alumina microspheres.

[0042] Alumina microspheres are obtained by using aluminum sol as the dispersed phase and organic solvent as the continuous phase through a microchannel reactor, followed by solidification, drying and calcination.

[0043] More

[0044] The solid content of aluminum sol is 5-10 wt%.

[0045] The continuous phase flow rate is 6-10 mL / min, and the dispersed phase flow rate is 1-4 mL / min;

[0046] The roasting temperature is 500-800℃, and the time is 3-6 hours.

[0047] In this invention, the organic solvent can be any conventional organic solvent used in microchannel reactors, with octanol being preferred.

[0048] Preferably,

[0049] In step (2),

[0050] The roasting temperature is 400–800℃; the roasting time is 2–10 hours.

[0051] Preferably,

[0052] In step (3),

[0053] The precursor solution of the active component is selected from the salt solution of the active component, preferably from the nitrate solution of the active component, and more preferably from at least one of the nickel nitrate solution or the ruthenium nitrate solution; and / or,

[0054] The metal ion concentration of the active component precursor solution is 0.1–15 wt%; and / or,

[0055] The mass ratio of the carbon-modified alumina microsphere composite carrier to the active component precursor solution is 1:1 to 10; and / or,

[0056] The carbon-modified alumina microsphere composite carrier is immersed in the active component precursor solution for 1–5 hours; and / or,

[0057] The roasting temperature is 300–600℃; the roasting time is 4–8 hours.

[0058] In the preparation method of the catalyst supported on carbon-modified alumina microspheres of the present invention, the post-processing of step (1) can be carried out by conventional processing methods, such as cooling and filtration.

[0059] The inert atmosphere in step (2) can be any conventional inert atmosphere, preferably a nitrogen atmosphere;

[0060] The drying in step (3) can be carried out under existing conventional drying conditions, preferably at 100-140℃ for 10-15 hours.

[0061] The second objective of this invention is to refine hydrogen gas using the low-temperature methanation method for removing carbon monoxide from crude hydrogen gas, as described in one objective of this invention.

[0062] Compared with the prior art, the present invention has at least the following advantages:

[0063] (1) The present invention uses a catalyst supported on carbon-modified alumina microspheres to remove trace amounts of CO through methanation under gas-solid two-phase conditions, which can remove trace amounts of CO in crude hydrogen gas to less than 1 ppm.

[0064] (2) The present invention uses a catalyst supported on carbon-modified alumina microspheres. In the catalyst, carbon is uniformly covered on the surface of the alumina microsphere carrier with abundant mesoporous structure, so that the surface of the alumina microsphere carrier is covered by carbon elements as much as possible, forming a carbon-modified alumina microsphere composite carrier.

[0065] (3) The present invention uses a catalyst supported on carbon-modified alumina microspheres. The acidity of the surface of the carbon-modified alumina microspheres in the catalyst is significantly reduced, which helps to avoid byproducts generated by acid catalysis, improves reaction selectivity, and thus improves the CO removal effect.

[0066] (4) The present invention uses a catalyst supported on carbon-modified alumina microspheres. The catalyst has a narrow particle size distribution, and macroscopically it can be considered that each catalyst particle has the same size. This is conducive to the uniform distribution of materials in the reactor, can avoid hot spots in the reactor, thereby avoiding reaction runaway and improving reaction selectivity.

[0067] (5) The present invention uses a catalyst supported on carbon-modified alumina microspheres, which has a higher surface area, higher utilization rate of active components, and higher catalytic activity.

[0068] (6) The present invention uses a catalyst supported on carbon-modified alumina microspheres. This catalyst can be applied to dynamic reactors such as moving beds and fluidized beds, which can minimize catalyst wear and improve reaction efficiency.

[0069] (7) The present invention uses a catalyst supported on carbon-modified alumina microspheres, which can effectively remove trace amounts of CO from crude hydrogen gas at low temperatures, with less energy consumption and lower production costs. Attached Figure Description

[0070] Figure 1 Microscopic images of the carbon-modified alumina microsphere composite carrier of the present invention;

[0071] Figure 2 This is a particle size distribution diagram of the carbon-modified alumina microsphere composite carrier of the present invention. Detailed Implementation

[0072] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0073] The average diameter of the alumina microspheres was calculated by measuring the diameter of each alumina microsphere based on microscope images.

[0074] The coefficient of variation of alumina microspheres is calculated according to the following formula:

[0075]

[0076] CV: Coefficient of variation, n: Alumina particle count, X: Alumina particle size.

[0077] Example 1

[0078] Step 1: Preparation of monodisperse alumina microspheres using an eight-channel microreactor

[0079] The dispersed phase was an aluminum sol (aluminum sol obtained by reacting aluminum hydroxide and excess sodium hydroxide) with a solid content of 7.5 wt%. The continuous phase and the liquid in the oil column were both organic solvents, specifically octanol. First, the flow rate of the continuous phase was adjusted to fill the continuous phase distribution layer and flow into the droplet formation layer, then flow out from the outlet. The continuous phase flow rate was eventually stabilized at 7 mL / min. Then, the dispersed phase flow rate was adjusted to 2 mL / min to fill the dispersed phase distribution layer and flow into the droplet formation layer, further generating droplets under the shearing action of the continuous phase. The droplets solidified in the oil column to obtain gel microspheres. After drying at 120℃ for 12 hours and calcining at 600℃ for 4 hours, alumina microspheres with an average diameter of 345 μm and a coefficient of variation of 6.5% were obtained.

[0080] Step 2: Preparation of carbon-modified alumina microspheres

[0081] Take 20g of the above alumina microspheres and immerse them in an ethanol solution of polyvinylimidazole with a concentration of 1.8wt%, with a mass ratio of alumina microspheres to polyvinylimidazole ethanol solution of 1:10; then transfer them to a hydrothermal reactor and react at 100℃ for 10h, cool and filter to obtain polymer-modified alumina microsphere composite carrier.

[0082] The polymer-modified alumina microsphere composite carrier obtained above was placed in a nitrogen atmosphere and calcined at 600°C for 5 hours to obtain a carbon-modified alumina microsphere composite carrier. The corresponding electron microscopy images and particle size distribution diagrams are shown below. Figure 1 , 2 As shown.

[0083] Step 3: Preparation of nickel catalyst supported on carbon-modified alumina microspheres

[0084] Take 200g of a nickel nitrate aqueous solution containing 15wt% Ni and put it into a beaker. Place 20g of carbon-modified alumina microspheres into the Ni aqueous solution. After 1 hour, take out the alumina microspheres, drain them, dry them at 120℃ for 12 hours, and calcine them at 400℃ for 6 hours under nitrogen protection to obtain the nickel catalyst supported on alumina microspheres.

[0085] The component contents of the catalysts prepared by the above method are shown in Table 1.

[0086] Example 2

[0087] Step 1: Preparation of monodisperse alumina microspheres using an eight-channel microreactor

[0088] The dispersed phase was an aluminum sol (aluminum sol obtained by reacting aluminum hydroxide and excess sodium hydroxide) with a solid content of 7.5 wt%. The continuous phase and the liquid in the oil column were both organic solvents, specifically octanol. First, the flow rate of the continuous phase was adjusted to fill the continuous phase distribution layer and flow into the droplet generation layer, then flow out from the outlet. The continuous phase flow rate was eventually stabilized at 9 mL / min. Then, the flow rate of the dispersed phase was adjusted to 3 mL / min to fill the dispersed phase distribution layer and flow into the droplet generation layer, further generating droplets under the shearing action of the continuous phase. The droplets solidified in the oil column to obtain gel microspheres. After drying at 120℃ for 12 hours and calcining at 600℃ for 4 hours, alumina microspheres with an average diameter of 480 μm and a coefficient of variation of 7.2% were obtained.

[0089] Step 2: Preparation of carbon-modified alumina microspheres

[0090] Take 20g of the above alumina microspheres and immerse them in an ethanol solution of 0.6wt% polyvinylimidazole, with a mass ratio of alumina microspheres to polyvinylimidazole ethanol solution of 1:2; then transfer them to a hydrothermal reactor and react at 100℃ for 10h, cool and filter to obtain polymer-modified alumina microsphere composite carrier.

[0091] The polymer-modified alumina microsphere composite carrier obtained above was placed in a nitrogen atmosphere and calcined at 800°C for 3 hours to obtain a carbon-modified alumina microsphere composite carrier.

[0092] Step 3: Preparation of nickel catalyst supported on carbon-modified alumina microspheres

[0093] Take 200g of a nickel nitrate aqueous solution containing 10wt% Ni and put it into a beaker. Place 15g of carbon-modified alumina microspheres into the Ni aqueous solution. After 1 hour, take out the alumina microspheres, drain them, dry them at 120℃ for 12 hours, and calcine them at 400℃ for 6 hours under nitrogen protection to obtain the nickel catalyst supported on alumina microspheres.

[0094] The component contents of the catalysts prepared by the above method are shown in Table 1.

[0095] Comparative Example 1

[0096] Step 1: Preparation of monodisperse alumina microspheres using an eight-channel microreactor

[0097] The dispersed phase was an aluminum sol (aluminum sol obtained by reacting aluminum hydroxide and excess sodium hydroxide) with a solid content of 7.5 wt%. The continuous phase and the liquid in the oil column were both organic solvents, specifically octanol. First, the flow rate of the continuous phase was adjusted to fill the continuous phase distribution layer and flow into the droplet formation layer, then flow out from the outlet. The continuous phase flow rate was eventually stabilized at 7 mL / min. Then, the dispersed phase flow rate was adjusted to 2 mL / min to fill the dispersed phase distribution layer and flow into the droplet formation layer, further generating droplets under the shearing action of the continuous phase. The droplets solidified in the oil column to obtain gel microspheres. After drying at 120℃ for 12 hours and calcining at 600℃ for 4 hours, alumina microspheres with an average diameter of 345 μm and a coefficient of variation of 6.5% were obtained.

[0098] Step 2: Preparation of nickel catalyst supported on alumina microspheres

[0099] Take 200g of a 15wt% Ni-nitric acid aqueous solution and place it in a beaker. Place 20g of carbon-modified alumina microspheres in the Ni aqueous solution. After 1 hour, remove the alumina microspheres, drain them, dry them at 120℃ for 12 hours, and calcine them at 400℃ for 6 hours under nitrogen protection to obtain the nickel catalyst supported on alumina microspheres.

[0100] The component contents of the catalysts prepared by the above method are shown in Table 1.

[0101] Table 1. Component content of the catalyst

[0102]

[0103] Example 3

[0104] The effect of the catalyst prepared in Example 1 above on the removal of carbon monoxide from crude hydrogen gas in the methanation reaction was investigated.

[0105] Six milliliters of catalyst were measured and loaded into a stainless steel fixed-bed reactor. High-purity nitrogen gas was introduced at a flow rate of 300 milliliters / min, and the temperature was raised to 160°C and maintained for 2 hours. Then, the reaction was switched to a feedstock containing 0.5 vol% CO, hydrogen gas. The gas composition after the reaction was analyzed by gas chromatography using an FID detector. The CO content was accurate to 1 ppm. The specific results are shown in Table 2.

[0106] Table 2 Evaluation results of the catalyst methanation reaction in Example 1

[0107]

[0108]

[0109] Example 4

[0110] The effect of the catalyst prepared in Example 2 above on the removal of carbon monoxide from crude hydrogen gas in the methanation reaction was investigated.

[0111] Six milliliters of catalyst were measured and loaded into a stainless steel fixed-bed reactor. High-purity nitrogen gas was introduced at a flow rate of 300 milliliters / min, and the temperature was raised to 160°C and maintained for 2 hours. Then, the reaction was switched to a feedstock containing 0.5 vol% CO, hydrogen gas. The gas composition after the reaction was analyzed by gas chromatography using an FID detector. The CO content was accurate to 1 ppm. The specific results are shown in Table 3.

[0112] Table 3 Evaluation results of catalyst methanation reaction in Example 2

[0113]

[0114] Comparative Example 2

[0115] The effect of the catalyst prepared in Comparative Example 1 on the removal of carbon monoxide from crude hydrogen gas in the methanation reaction was investigated.

[0116] Six milliliters of catalyst were loaded into a stainless steel fixed-bed reactor, and high-purity nitrogen gas was introduced at a flow rate of 300 milliliters / min. The reactor was heated to 160°C and maintained for 2 hours. Then, the reaction was switched to a feedstock containing 0.5 vol% CO, hydrogen gas. The gas composition after the reaction was analyzed by gas chromatography using an FID detector. The CO content was accurate to 1 ppm. The specific results are shown in Table 4.

[0117] Table 4 Evaluation results of the catalyst methanation reaction in Comparative Example 1

[0118]

[0119] When a catalyst removes carbon monoxide from crude hydrogen gas during methanation, a lower outlet CO content (ppm) indicates higher catalyst activity. As shown in Tables 1-3, the catalyst of Example 3 of this invention still exhibits an outlet CO content of less than 1 ppm after 60 hours of operation, while the catalyst of Comparative Example 1 shows that the outlet CO content begins to exceed 1 ppm after 32 hours of operation. Clearly, the catalyst of this invention exhibits better catalytic performance.

[0120] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

[0121] 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.

Claims

1. A method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation, characterized in that, The method for removing carbon monoxide from crude hydrogen gas involves contacting a catalyst supported on carbon-modified alumina microspheres with the crude hydrogen gas to perform a methanation reaction to remove carbon monoxide. The catalyst supported on the carbon-modified alumina microspheres includes a carbon-modified alumina microsphere composite support and an active component supported on the composite support. Based on the weight of the composite carrier as 100%, The carbon content is 0.01~10 wt%; Based on the catalyst by weight of 100%, The content of the active component is 20~60 wt%; The preparation method of the catalyst supported on the carbon-modified alumina microspheres includes the following steps: (1) Alumina microspheres are added to a nitrogen-containing polymer solution, and then reacted by a solvothermal method, followed by post-treatment to obtain a nitrogen-containing polymer-modified alumina microsphere composite carrier; the nitrogen-containing polymer is selected from one or a combination of polyvinylimidazolium, polyvinylpyrrolidone or polyvinylpyridine. (2) The alumina microsphere composite carrier modified with nitrogen-containing polymer was calcined under an inert atmosphere to obtain a carbon-modified alumina microsphere composite carrier. (3) The carbon-modified alumina microsphere composite support is immersed in the active component precursor solution, dried, and calcined to obtain the catalyst supported on carbon-modified alumina microspheres.

2. The method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation according to claim 1, characterized in that, Based on the weight of the composite carrier as 100%, The carbon content is 0.1~1wt%; Based on the catalyst by weight of 100%, The content of the active component is 35~50wt%.

3. The method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation according to claim 1, characterized in that, The methanation reaction is carried out at a temperature of 140-200°C; and / or, The reaction pressure is 0.1-7.0 MPa; and / or, The volumetric hourly space velocity (VHSV) of crude hydrogen gas under standard conditions is less than 20,000 h⁻¹. -1 ; and / or, The concentration of CO in the crude hydrogen gas is less than 5000 ppm.

4. The method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation according to claim 1, characterized in that, The alumina microspheres are monodisperse alumina microspheres.

5. The method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation according to claim 4, characterized in that, The alumina microspheres are selected from alumina microspheres with an average diameter of 200-800 μm and a coefficient of variation of 3-8%.

6. The method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation according to claim 1, characterized in that, The active component is selected from at least one of Ni or Ru.

7. The method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation according to claim 1, characterized in that, In step (1), The concentration of the nitrogen-containing polymer solution is 0.1~1 wt%; and / or, The solvent in the nitrogen-containing polymer solution is selected from one or a combination of methanol and ethanol.

8. The method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation according to claim 1, characterized in that, In step (1), The mass ratio of the alumina microspheres to the nitrogen-containing polymer solution is 1:1~10; and / or, The solvothermal method involves a reaction temperature of 100-120℃ and a reaction time of 4-10 hours; and / or, The alumina microspheres were prepared using a microchannel reactor.

9. The method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation according to claim 8, characterized in that, Using aluminum sol as the dispersed phase and an organic solvent as the continuous phase, a dispersed phase droplets were obtained through a microchannel reactor, and then solidified, dried and calcined sequentially to obtain alumina microspheres.

10. The method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation according to claim 9, characterized in that, The solid content of aluminum sol is 5-10 wt%; The continuous phase flow rate is 6-10 mL / min, and the dispersed phase flow rate is 1-4 mL / min; The roasting temperature is 500-800℃, and the time is 3-6 hours.

11. The method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation according to claim 5, characterized in that, In step (2), The roasting temperature is 400~800℃; the roasting time is 2~10h.

12. The method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation according to claim 1, characterized in that, In step (3), The active component precursor solution is selected from the active component salt solution; and / or, The metal ion concentration of the active component precursor solution is 0.1~15wt%; and / or, The mass ratio of the carbon-modified alumina microsphere composite carrier to the active component precursor solution is 1:1~10; and / or, The carbon-modified alumina microsphere composite carrier is immersed in the active component precursor solution for 1–5 h; and / or, The roasting temperature is 300~600℃; the roasting time is 4~8h.

13. The method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation according to claim 12, characterized in that, The precursor solution of the active component is selected from the nitrate solution of the active component.

14. The method for removing carbon monoxide from crude hydrogen gas by low-temperature methanation according to claim 13, characterized in that, The active component precursor solution is selected from at least one of nickel nitrate solution or ruthenium nitrate solution.

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