A bow-shaped stacked zirconium dioxide nanosheet supported nickel-ruthenium bimetallic catalyst, a preparation method and application thereof

Abstract

The application discloses a bow-shaped stacked zirconium dioxide nanosheet supported nickel-ruthenium bimetallic catalyst and a preparation method and application thereof, and relates to the field of catalyst material synthesis. The bow-shaped stacked zirconium dioxide nanosheet is prepared by a solvothermal method to serve as a carrier, and is impregnated with nickel and ruthenium bimetallic active components, and then is calcined and reduced to obtain the bow-shaped zirconium dioxide nanosheet supported nickel-ruthenium bimetallic catalyst (Ni-Ru / ZrO2). The catalyst preparation process is simple, the noble metal Ru is used in a very small amount, can be used for deep removal of carbon monoxide (CO) in hydrogen-rich gas, the CO concentration at the outlet of a reactor can be reduced to below 10 ppm, the reaction selectivity is greater than 85%, and the catalyst has good stability, activity and selectivity.

Description

Technical Field

[0001] This invention belongs to the field of heterogeneous catalyst technology, and specifically relates to a nickel-ruthenium bimetallic catalyst supported on zirconium dioxide nanosheets stacked in a bow-knot shape, its preparation method and application. Background Technology

[0002] Proton exchange membrane fuel cells (PEMFCs), as a clean and efficient energy conversion technology, boast advantages such as high energy conversion efficiency, zero emissions, and low-temperature start-up, making them a research hotspot in fields such as new energy vehicles and portable electronic devices. The hydrogen fuel for PEMFCs primarily originates from the catalytic reforming of hydrocarbons. However, carbon monoxide (CO) is generated during catalytic reforming, which poisons the platinum (Pt) anode material in PEMFCs, leading to a decline in fuel cell performance. Therefore, the reformed hydrogen-rich fuel gas used in PEMFCs must undergo deep CO removal to below 10 ppm. Currently, the main chemical methods for deep CO removal from reformed hydrogen-rich gas include CO selective methanation (CO-SMET) and CO preferential oxidation (CO-PROX). CO-PROX requires a certain amount of external oxygen (or air) to participate in the reaction, increasing the complexity and cost of the process; while the CO-SMET process is simple, requires no additional reactants, and directly utilizes H2 and CO from the reformed hydrogen-rich gas, showing broad application prospects. CO hydrogenation to methane is an industrially mature process, but hydrogen-rich gases contain a large amount of CO2. The main challenge in selectively and deeply removing CO to extremely low concentrations and avoiding CO2 competition for methanation lies in the development of highly active, selective, and stable catalysts. In particular, CO-SMET, as a structure-sensitive reaction, is influenced by the catalyst's morphology and other microstructures. Metal oxide nanosheets, as an emerging two-dimensional material, have been widely used in heterogeneous catalysis due to their ordered Lewis acid-base sites, enhanced mass and heat transfer, and rich oxygen vacancies. Zirconium dioxide (ZrO2) is considered a promising support material for CO-SMET reactions due to its high chemical inertness, thermal stability, surface oxygen defects, and acid / basic properties. Li et al. (International Journal of Hydrogen Energy, 2016, 41: 17907-17921) used Ni-supported ZrO2 nanosheets for dry reforming of methane and demonstrated excellent catalytic performance. Hu et al. (International Journal of Hydrogen Energy, 2018, 43: 21345-21354) successfully loaded Ni nanoparticles on TiO2(001) nanosheets and applied them to carbon dioxide reforming (CRM) of methane. They found that Ni / TiO2(001) had better catalytic activity and stability than Ni / P25 in CRM.Sun et al. (Journal of Energy Chemistry, 2019, 29:3-7) supported metallic Ni on Al2O3 nanosheets and used it for CO2 methanation. They found that compared with traditional Ni / Al2O3 catalysts, the Ni / Al2O3 nanosheet catalyst exhibited enhanced CO2 conversion due to the smaller grain size of Ni particles and the presence of more suitable basic sites. Quan et al. (International Journal of Hydrogen Energy, 2021, 46:14395-14406) prepared Ni / ZrO2 catalysts with different morphologies by impregnation and subjected them to CO2 methanation. The Ni / ZrO2 catalyst supported on ZrO2 nanosheets, rich in oxygen vacancies, promoted the adsorption and dissociation of CO2 molecules, resulting in better catalytic performance.

[0003] Currently, non-precious metal Ni-based catalysts and precious metal Ru-based catalysts are the main components in CO-SMET reactions. Ni-based catalysts have considerable activity and low cost, but they are relatively prone to carbon deposition and sintering at high temperatures. Ru-based catalysts exhibit excellent low-temperature catalytic activity and good resistance to carbon deposition in CO-SMET reactions, but Ru is expensive. Xiao Gang et al. (Authorization Announcement No.: CN101607198B) supported 0.2-2 wt% Ru on a ZrO2-CeO2 composite oxide support, and the resulting Ru / ZrO2-CeO2 catalyst showed good activity in the range of 220-300℃, but could only reduce the CO outlet concentration to 25 ppm. Compared with monometallic supported catalysts, bimetallic supported catalysts show more advantages. Liu et al. (Petrochemical Technology, 2009, 38(7):711-715) coated a 4Ni-2Ru / ZrO2 bimetallic catalyst onto the walls of a microchannel and found that the volume fraction of CO at the outlet could be reduced to 1×10⁻⁶ within a temperature range of 260-300℃. -4The following are examples. Bhavani et al. (Korean Journal of Chemical Engineering, 2018, 56: 269-274) added Ce to a Ni-Co / ZrO2 bimetallic catalyst via co-precipitation and found that the Ni-Co / 2wt%CeZrO2 catalyst with 2wt% Ce addition exhibited good CO methanation activity. Zhang Jie et al. (Authorization Announcement No.: CN112642439B) applied a Ru-Ni / ZrO2 bimetallic active site catalyst to a low-temperature slurry bed methanation reaction. Under the conditions of reaction temperature 250℃, pressure 3.0MPa, H2 / CO ratio 3.0, and space velocity 6000mL / g / h, the CO conversion rate of this catalyst was between 84-93%, and the catalyst showed good stability at 20h and 200h.

[0004] Currently, metal-supported catalysts using ZrO2 nanosheets or ZrO2 composites as supports still have the following problems: poor low-temperature activity (initial reaction temperature window above 220℃), low reaction selectivity due to excessively high reaction temperature, CO content at reactor outlet exceeding 10ppm which fails to meet the requirements of PEMFC for hydrogen-rich gas fuel quality, and large amount of precious metal Ru (greater than 1wt%). Summary of the Invention

[0005] In order to overcome the shortcomings of the prior art, the primary objective of this invention is to provide a nickel-ruthenium bimetallic catalyst supported on zirconium dioxide nanosheets stacked in a bow-knot shape.

[0006] Another object of the present invention is to provide a method for preparing the above-mentioned bow-shaped stacked zirconium dioxide nanosheets supported on a nickel-ruthenium bimetallic catalyst.

[0007] Another object of the present invention is to provide the application of the above-mentioned bow-shaped stacked zirconium dioxide nanosheets supported on nickel-ruthenium bimetallic catalyst in the deep removal of CO in hydrogen-rich gas.

[0008] The objective of this invention can be achieved through the following solutions:

[0009] A nickel-ruthenium bimetallic catalyst supported on bow-knot-shaped stacked zirconium dioxide nanosheets is obtained by using bow-knot-shaped stacked zirconium dioxide nanosheets as a support and nickel and ruthenium as active components through impregnation, calcination and reduction processes.

[0010] Preferably, the catalyst contains 1-10 wt% nickel and 0.01-0.2 wt% ruthenium.

[0011] More preferably, the ruthenium loading in the catalyst is 0.05-0.125 wt%.

[0012] The preferred loading is 5 wt% nickel and 0.1 wt% ruthenium.

[0013] The preparation method of the above-mentioned bow-shaped stacked zirconium dioxide nanosheets supporting nickel-ruthenium bimetallic catalyst specifically includes the following steps:

[0014] (1) Add polyether (F127) to tetrahydrofuran, acetic acid and nitric acid and stir. Then add zirconium acetylacetonate and stir to mix evenly to obtain a transparent pale yellow solution. Then heat the transparent pale yellow solution to evaporate the tetrahydrofuran and obtain a yellow solution.

[0015] (2) Add the yellow solution obtained in step (1) to ethanol, and add glycerol dropwise while stirring; then transfer the resulting mixture to a reaction vessel for solvothermal reaction and obtain a precipitate. Filter and dry the precipitate, and calcine it in a muffle furnace to obtain a bow-shaped stacked zirconium dioxide nanosheet carrier.

[0016] (3) The bow-shaped stacked zirconium dioxide nanosheet support obtained in step (2) was immersed in an ethanol solution of nickel salt, and then immersed in an ethanol solution of ruthenium salt. After drying, calcining in air, and reduction in a hydrogen atmosphere, a bow-shaped stacked zirconium dioxide nanosheet supported nickel-ruthenium bimetallic catalyst was obtained, labeled as Ni-Ru / ZrO2.

[0017] In step (1), the molar ratio of polyether (F127), tetrahydrofuran, acetic acid, nitric acid and zirconium acetylacetonate in the transparent pale yellow solution is (0.009-0.013):(36-38):(3.9-4.5):(5-9):1; preferably, the molar ratio of polyether (F127), tetrahydrofuran, acetic acid, nitric acid and zirconium acetylacetonate in the transparent pale yellow solution is 0.011:37:4.2:7:1.

[0018] The heating temperature in step (1) is 30-60℃ and the heating time is 18-30h; preferably, the heating temperature is 45℃ and the heating time is 24h.

[0019] The volume ratio of the yellow solution, ethanol and glycerol in step (2) is (0.17-0.67):1:(0.5-1); preferably, the volume ratio of the yellow solution, ethanol and glycerol is 0.33:1:0.67.

[0020] The stirring time in step (2) is 5-20 min, the solvothermal reaction temperature is 90-120℃, and the solvothermal reaction time is 9-11 h; preferably, the stirring time is 10 min, the solvothermal reaction temperature is 100℃, and the solvothermal reaction time is 10 h.

[0021] The drying temperature in step (2) is 50-100℃ and the drying time is 6-18h, and the calcination temperature is 300-400℃ and the calcination time is 3-9h; preferably, the drying temperature is 90℃ and the drying time is 12h, and the calcination temperature is 350℃ and the calcination time is 6h.

[0022] The mass of the bow-shaped stacked zirconium dioxide nanosheet carrier in step (3) is 0.1-0.5g; preferably, the mass of the bow-shaped stacked zirconium dioxide nanosheet carrier is 0.3g.

[0023] The nickel salt in step (3) is one of nickel nitrate, nickel acetate, nickel chloride and nickel oxalate, and the concentration of the ethanol solution of the nickel salt is 0.2-0.4 mol / L; preferably, the nickel salt is nickel nitrate and the concentration of the ethanol solution of the nickel salt is 0.3 mol / L.

[0024] The ruthenium salt in step (3) is ruthenium acetate or ruthenium trichloride, and the concentration of the ruthenium salt ethanol solution is 0.005-0.006 mol / L; preferably, the ruthenium salt is ruthenium acetate, and the concentration of the ruthenium salt ethanol solution is 0.0056 mol / L.

[0025] The immersion temperature in step (3) is room temperature, and the immersion time is 10-20 hours; preferably, the immersion time is 12 hours.

[0026] The drying temperature in step (3) is 60-120℃ and the drying time is 6-12h, and the calcination temperature is 400-600℃ and the calcination time is 3-7h; preferably, the drying temperature is 100℃ and the drying time is 10h, and the calcination temperature is 500℃ and the calcination time is 5h.

[0027] The reduction temperature in step (3) is 300-400℃ and the reduction time is 1-3h; preferably, the reduction temperature is 350℃ and the reduction time is 1.5h.

[0028] The above-mentioned bow-shaped stacked zirconium dioxide nanosheets supporting a nickel-ruthenium bimetallic (Ni-Ru / ZrO2) catalyst are used for the deep removal of CO from hydrogen-rich gas, wherein the concentration of carbon monoxide in the hydrogen-rich gas is 1 vol.%.

[0029] The space velocity of the hydrogen-rich gas is 4000-8000 mL / g / h, preferably 6000 mL / g / h, and the reaction temperature for deep CO removal by the catalyst in the hydrogen-rich gas is 210-290℃.

[0030] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0031] This invention provides a method for preparing and applying a Ni-Ru / ZrO2 supported bimetallic catalyst, using bow-knot-shaped stacked zirconium dioxide nanosheets as a support and non-noble metal Ni and noble metal Ru as active components. The ZrO2 support exhibits a bow-knot-shaped stacked nanosheet morphology; its layered sheet structure facilitates the dispersion of active component particles and inhibits the aggregation of surface active component particles. The abundant oxygen defect sites on the ZrO2 support surface promote oxygen migration during the reaction, contributing to improved efficiency of the CO methanation reaction. The addition of noble metal Ru enhances the reducing power of Ni species in Ni-Ru / ZrO2, thereby improving its CO methanation reaction activity. Furthermore, the catalyst prepared by this invention, with a noble metal Ru loading as low as 0.1 wt%, can reduce the CO outlet concentration of hydrogen-rich gas containing 1 vol.% CO to below 10 ppm within a temperature window of 210-290 °C, while maintaining a selectivity of over 50%. Attached Figure Description

[0032] Figure 1 The image shows the XRD pattern of the ZrO2 support prepared according to this invention.

[0033] Figure 2 This is a scanning electron microscope image of the ZrO2 support prepared in this invention.

[0034] Figure 3 Scanning electron microscope image of the ZrO2-8h support prepared for Comparative Example 2.

[0035] Figure 4 The graphs show the CO concentration versus reaction temperature in the selective methanation of CO on catalysts in Comparative Examples 1-2 and Examples 1-5.

[0036] Figure 5 The graphs show the CH4 concentration versus reaction temperature in the CO selective methanation reaction on the catalysts of Comparative Examples 1-2 and Examples 1-5.

[0037] Figure 6 The figure shows the stability test results of the sample prepared in Example 1 after 120 h of CO selective methanation reaction. Detailed Implementation

[0038] The present invention will now be described in further detail with reference to embodiments and accompanying drawings, but the implementation of the present invention is not limited thereto. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Instruments used without specified manufacturers are all commercially available conventional products.

[0039] Unless otherwise specified, all reagents used in the comparative examples and embodiments are commercially available.

[0040] The following is a test method for the performance of CO selective methanation catalyst: The catalyst prepared in the comparative example or the example is pressed into tablets and granulated. 0.2 g of 40-60 mesh catalyst is placed in a quartz reaction tube with an inner diameter of 6 mm. The hydrogen-rich gas composition is 79 vol.% H2, 20 vol.% CO2, and 1 vol.% CO. The space velocity is 6000 mL / g / h, and the reaction temperature is 150-320℃. The reaction product is dried and then detected online by gas chromatography.

[0041] Comparative Example 1

[0042] Polyether (F127) was added to tetrahydrofuran, acetic acid, and nitric acid and stirred. Then, zirconium acetylacetonate was added and stirred until homogeneous to obtain a transparent pale yellow solution. The molar ratio of polyether (F127), tetrahydrofuran, acetic acid, nitric acid, and zirconium acetylacetonate in the transparent pale yellow solution was 0.011:37:4.2:7:1. The transparent pale yellow solution was heated at 45°C for 24 h to evaporate the tetrahydrofuran and obtain a yellow solution. 10 mL of the yellow solution was added to 30 mL of ethanol, and 20 mL of glycerol was added dropwise while stirring. After stirring for 10 min, the mixture was transferred to a reaction vessel for a solvothermal reaction at 100°C for 10 h. The reaction was then cooled to room temperature, the precipitate was filtered, washed three times with ethanol, dried in a 90°C oven for 12 h, and finally calcined in a muffle furnace at 350°C for 6 h to obtain the bow-shaped stacked zirconium dioxide nanosheet carrier of the present invention.

[0043] Figure 1 The XRD pattern of the ZrO2 support prepared according to the present invention shows that the ZrO2 support prepared according to the present invention exhibits amorphous characteristics.

[0044] Figure 2 The image shows a scanning electron microscope (SEM) image of the ZrO2 support prepared in this invention. It can be seen that the prepared ZrO2 support exhibits a butterfly-shaped stacked nanosheet morphology.

[0045] Weigh more than 0.3 g of the prepared bow-shaped stacked ZrO2 support and place it in 0.745 mL of 0.3 mol / L nickel nitrate ethanol solution. After impregnation at room temperature for 12 h, dry it in an oven at 100 °C for 10 h, calcine it in a muffle furnace at 500 °C for 5 h, and then reduce it at 350 °C in a mixed gas of 50 vol% H2 and 50 vol% N2 for 1.5 h to obtain a Ni / ZrO2 catalyst with a Ni loading of 5 wt%. The sample is designated as 5Ni / ZrO2.

[0046] The activity of the 5Ni / ZrO2 catalyst was tested, and the results are shown in the table below. Figure 4 and Figure 5As shown in the figure, the 5Ni / ZrO2 catalyst can reduce 1 vol% CO in hydrogen-rich gas to below 10 ppm within a temperature window of 240-280℃, while maintaining a selectivity of over 50%.

[0047] Comparative Example 2

[0048] The ZrO2 support was prepared using the same method as Comparative Example 1, but the solvothermal reaction time was 8 h, and this support was designated as ZrO2-8h.

[0049] Weigh more than 0.3 g of the prepared ZrO2-8h support and place it in 0.745 mL of 0.3 mol / L nickel nitrate ethanol solution. Impregnate for 12 h at room temperature, dry in an oven at 100 °C for 10 h, calcine in a muffle furnace at 500 °C for 5 h, and then reduce in a mixed gas of 50 vol% H2 and 50 vol% N2 at 350 °C for 1.5 h to obtain a Ni / ZrO2-8h catalyst with a Ni loading of 5 wt%. The sample is designated as 5Ni / ZrO2-8h.

[0050] The activity of the 5Ni / ZrO2-8h catalyst was evaluated, and the results are shown in the table below. Figure 4 , Figure 5 As shown in the figure, the 5Ni / ZrO2-8h catalyst can only reduce the CO concentration of 1 vol% in hydrogen-rich gas to below 10 ppm within a temperature window of 260-290℃.

[0051] Figure 3 The image shows a scanning electron microscope (SEM) image of the ZrO2-8h support prepared in this comparative example. It can be seen that the prepared ZrO2-8h support exhibits a stacked nanosheet morphology.

[0052] Example 1

[0053] The ZrO2 support was prepared using the same method as in Comparative Example 1.

[0054] 0.3 g of ZrO2 support was first impregnated in 0.745 mL of a 0.3 mol / L nickel nitrate ethanol solution for 12 h, then impregnated in 1.15 mL of a 0.0056 mol / L ruthenium acetate ethanol solution for 12 h. The solution was then dried in an oven at 100 °C for 10 h, calcined in a muffle furnace at 500 °C for 5 h, and then reduced at 350 °C in a mixture of 50 vol% H2 and 50 vol% N2 for 1.5 h to obtain a Ni-Ru / ZrO2 catalyst with a Ni loading of 5 wt% and a Ru loading of 0.1 wt%, denoted as 5Ni-0.1Ru / ZrO2. The catalyst activity was evaluated, and the results are shown below. Figure 4 , Figure 5 .

[0055] Example 2

[0056] The ZrO2 support was prepared using the same method as in Comparative Example 1.

[0057] 0.3 g of ZrO2 support was first impregnated in 0.745 mL of 0.3 mol / L nickel nitrate ethanol solution for 12 h, then impregnated in 0.57 mL of 0.0056 mol / L ruthenium acetate ethanol solution for 12 h. The solution was then dried in an oven at 100 °C for 10 h, calcined in a muffle furnace at 500 °C for 5 h, and then reduced at 350 °C in a mixture of 50 vol% H2 and 50 vol% N2 for 1.5 h to obtain a Ni-Ru / ZrO2 catalyst with a Ni loading of 5 wt% and a Ru loading of 0.05 wt%, denoted as 5Ni-0.05Ru / ZrO2. The catalyst activity was evaluated, and the results are shown below. Figure 4 , Figure 5 .

[0058] Example 3

[0059] The ZrO2 support was prepared using the same method as in Comparative Example 1.

[0060] 0.3 g of ZrO2 support was first impregnated in 0.745 mL of a 0.3 mol / L nickel nitrate ethanol solution for 12 h, then impregnated in 0.86 mL of a 0.0056 mol / L ruthenium acetate ethanol solution for 12 h. The solution was then dried in an oven at 100 °C for 10 h, calcined in a muffle furnace at 500 °C for 5 h, and then reduced at 350 °C in a mixture of 50 vol% H2 and 50 vol% N2 for 1.5 h to obtain a Ni-Ru / ZrO2 catalyst with a Ni loading of 5 wt% and a Ru loading of 0.075 wt%, denoted as 5Ni-0.075Ru / ZrO2. The catalyst activity was evaluated, and the results are shown below. Figure 4 , Figure 5 .

[0061] Example 4

[0062] The ZrO2 support was prepared using the same method as in Comparative Example 1.

[0063] 0.3 g of ZrO2 support was first impregnated in 0.745 mL of a 0.3 mol / L nickel nitrate ethanol solution for 12 h, then impregnated in 1.45 mL of a 0.0056 mol / L ruthenium acetate ethanol solution for 12 h. The solution was then dried in an oven at 100 °C for 10 h, calcined in a muffle furnace at 500 °C for 5 h, and then reduced at 350 °C in a mixture of 50 vol% H2 and 50 vol% N2 for 1.5 h to obtain a Ni-Ru / ZrO2 catalyst with a Ni loading of 5 wt% and a Ru loading of 0.125 wt%, denoted as 5Ni-0.125Ru / ZrO2. The catalyst activity was evaluated, and the results are shown below. Figure 4 , Figure 5 .

[0064] Example 5

[0065] The ZrO2 support was prepared using the same method as in Comparative Example 1.

[0066] 0.3 g of ZrO2 support was first impregnated in 0.745 mL of 0.3 mol / L nickel nitrate ethanol solution for 12 h, then impregnated in 2.3 mL of 0.0056 mol / L ruthenium acetate ethanol solution for 12 h. The solution was then dried in an oven at 100 °C for 10 h, calcined in a muffle furnace at 500 °C for 5 h, and then reduced at 350 °C in a mixture of 50 vol% H2 and 50 vol% N2 for 1.5 h to obtain a Ni-Ru / ZrO2 catalyst with a Ni loading of 5 wt% and a Ru loading of 0.2 wt%, designated as 5Ni-0.2Ru / ZrO2. The catalyst activity was evaluated, and the results are shown below. Figure 4 , Figure 5 .

[0067] like Figure 4 and Figure 5 As shown, the catalyst sample 5Ni-0.1Ru / ZrO2 with a Ni loading of 5wt% and a Ru loading of 0.1wt% exhibits the best performance, capable of reducing 1 vol% CO in hydrogen-rich gas to below 10 ppm within a temperature window of 210-290℃ while maintaining a selectivity of over 50%.

[0068] Example 6

[0069] 0.2 g of the 5Ni-0.1Ru / ZrO2 sample obtained in Example 1 was placed in a fixed-bed reactor and subjected to a CO-selective methanation reaction at a reaction temperature of 210 °C for 120 h. The test results are shown in [Figure 1]. Figure 6 .

[0070] like Figure 6 As shown, during the 120-hour CO selective methanation reaction time, 5Ni-0.1Ru / ZrO2 maintained good stability, with CO concentration removed to below 10 ppm and reaction selectivity greater than 85%.

[0071] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a nickel-ruthenium bimetallic catalyst supported on bow-shaped stacked zirconium dioxide nanosheets, characterized in that, Includes the following steps: (1) Add polyether to tetrahydrofuran, acetic acid and nitric acid and stir. Then add zirconium acetylacetonate and stir to mix evenly to obtain a transparent pale yellow solution. Then heat the transparent pale yellow solution to evaporate the tetrahydrofuran and obtain a yellow solution. (2) The yellow solution obtained in step (1) is added to ethanol, and glycerol is added dropwise while stirring; the resulting mixture is then transferred to a reaction vessel for solvothermal reaction and a precipitate is obtained. The precipitate is filtered and dried, and then calcined in a muffle furnace to obtain a bow-shaped stacked zirconium dioxide nanosheet carrier; the solvothermal reaction temperature is 90-120℃. (3) The bow-shaped stacked zirconium dioxide nanosheet support obtained in step (2) is immersed in an ethanol solution of nickel salt, and then immersed in an ethanol solution of ruthenium salt. After drying, calcining in air, and reduction in a hydrogen atmosphere, a bow-shaped stacked zirconium dioxide nanosheet supported nickel-ruthenium bimetallic catalyst is obtained, labeled as Ni-Ru / ZrO2. The catalyst uses bow-shaped stacked zirconium dioxide nanosheets as the support and nickel and ruthenium as the active components. The loading of nickel in the catalyst is 1-10 wt%, and the loading of ruthenium is 0.01-0.2 wt%.

2. The preparation method according to claim 1, characterized in that: The ruthenium loading in the catalyst is 0.05-0.125 wt%.

3. The preparation method according to claim 1, characterized in that: The molar ratio of polyether, tetrahydrofuran, acetic acid, nitric acid and zirconium acetylacetonate in the transparent pale yellow solution in step (1) is (0.009-0.013):(36-38):(3.9-4.5):(5-9):1; The heating temperature in step (1) is 30-60℃, and the heating time is 18-30h.

4. The preparation method according to claim 1, characterized in that: The volume ratio of the yellow solution, ethanol, and glycerol in step (2) is (0.17-0.67):1:(0.5-1); The stirring time in step (2) is 5-20 min, and the solvothermal reaction time is 9-11 h; The drying temperature in step (2) is 50-100℃ and the drying time is 6-18h. The calcination temperature is 300-400℃ and the calcination time is 3-9h.

5. The preparation method according to claim 1, characterized in that: The nickel salt in step (3) is one of nickel nitrate, nickel acetate, nickel chloride, and nickel oxalate, and the concentration of the ethanol solution of the nickel salt is 0.2-0.4 mol / L; The ruthenium salt in step (3) is ruthenium acetate or ruthenium trichloride, and the concentration of the ruthenium salt in the ethanol solution is 0.005-0.006 mol / L; The immersion temperature in step (3) is room temperature, and the immersion time is 10-20 hours. The drying temperature in step (3) is 60-120℃ and the drying time is 6-12h. The calcination temperature is 400-600℃ and the calcination time is 3-7h.

6. The preparation method according to claim 1, characterized in that: The reduction temperature in step (3) is 300-400℃ and the reduction time is 1-3h.

7. The application of the bow-shaped stacked zirconium dioxide nanosheets supported on a nickel-ruthenium bimetallic catalyst prepared by the preparation method according to any one of claims 1-6 in the deep removal of CO from hydrogen-rich gas, characterized in that, The concentration of carbon monoxide in the hydrogen-rich gas is 0.5-1 vol.%, the space velocity of the hydrogen-rich gas is 4000-8000 mL / g / h, and the reaction temperature of the catalyst for deep CO removal in the hydrogen-rich gas is 210-290℃.

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