Monolithic carbon monoxide catalyst as well as preparation method and application thereof

Abstract

The invention belongs to the field of catalysts, and particularly relates to a monolithic carbon monoxide catalyst as well as a preparation method and application thereof. The monolithic carbon monoxide catalyst comprises a carrier and metal catalytic particles loaded on the surface of the carrier, and the loading capacity of the metal catalytic particles is 90kg / m < 3 >-150kg / m < 3 >. The integral carbon monoxide catalyst is relatively high in sulfur resistance and water resistance, so that the catalyst is high in catalytic stability in sintering flue gas purification. The loading capacity of the metal catalytic particles in the integral carbon monoxide catalyst is 90-150kg / m < 3 >, so that the integral carbon monoxide catalyst has high adsorption capacity on carbon monoxide and is not easy to agglomerate in the catalysis process. Aiming at complex sintering flue gas conditions, synergistic combination of vanadium group elements, chromium group elements, precious metal elements and the like is achieved by adding the auxiliaries, and meanwhile precious metal is promoted to be highly dispersed to the nanometer size, so that the precious metal nanometer catalyst is formed. The catalyst produced by the method not only has high loading strength and excellent catalytic efficiency, but also can keep excellent catalytic performance in a sintering flue gas environment in which various complex components such as water, sulfur, nitrate, ammonium and dust exist. The water-resistant sulfur-resistant rubber has the characteristics of excellent water resistance and sulfur resistance.

Description

[0001] This invention claims the priority of the patent application with the application number 202410238967.7 (the patent application title is "Integral Carbon Monoxide Catalyst and Its Preparation Method and Application") submitted by the applicant to the Patent Office of the National Intellectual Property Administration on March 4, 2024. Technical Field

[0002] This invention belongs to the field of catalysts, and specifically relates to an integral carbon monoxide catalyst and its preparation method and application. Background Art

[0003] CO is one of the most widely distributed and abundant pollutants in the atmosphere, and has important hazards to the environment and human health. To evaluate air quality, the Air Quality Index (AQI) was introduced in 2012, and six major pollutants such as fine particulate matter, inhalable particulate matter, sulfur dioxide, nitrogen dioxide, ozone, and carbon monoxide are regarded as important reference indicators. The two main pollution sources in industrial activities are the steel industry and mobile sources. Nowadays, there are relatively mature CO removal technologies and rich engineering practice experiences in dealing with mobile source pollution, and good results have also been achieved; however, as the main source of CO emissions, the steel industry does not have a relatively mature catalytic oxidation CO removal technology. Currently, the two main pollution sources in industrial activities are the steel industry and mobile sources. In dealing with mobile source pollution, there are already mature CO removal technologies and rich engineering practice experiences, and remarkable results have been achieved. However, as one of the main sources of CO emissions, the steel industry lacks a mature catalytic oxidation CO removal technology.

[0004] In the iron and steel industry, the sintering process and the coking process are the two main links that generate CO, and the sintering process has the largest emissions. Actual tests show that the CO content in sintering flue gas can be as high as 6,000 - 10,000 ppm, far exceeding the emissions of SO2 and NOx. Therefore, purifying CO in sintering flue gas is the most effective way to reduce CO emissions in the iron and steel industry. Currently, the end-treatment technologies for treating CO in sintering flue gas in iron and steel enterprises mainly include direct combustion method, cryogenic separation method, solution absorption method, adsorption method, oxidation method, etc. Except for the oxidation method, other technologies have some problems, such as high ignition temperature, difficult to directly burn, unable to effectively separate CO and N2, and high treatment cost and energy consumption. The oxidation method is based on the principle of promoting the reaction of CO with O2 in the flue gas to convert it into CO2. It has the advantages of high purification efficiency, low operating temperature, safe use, and easy operation, so it has received wide acclaim. The catalysts widely used in this stage for purifying CO are mainly noble metal catalysts and non-noble metal catalysts. CO catalysts containing noble metals have certain water resistance, excellent catalytic activity and stability, but they are expensive; non-noble metal CO catalysts are mainly Hopcalite agents, which are composed of transition metals and are a multi-metal oxide system, having the advantages of high purification efficiency, long service life, wide application scenarios, safe use, convenient operation, and low cost. However, after the sintering flue gas is desulfurized, there will still be a small amount of SO2 residue, and this residual SO2 will cause the catalyst to be sulfur poisoned, resulting in a decrease in purification efficiency, and its regeneration requires a high-temperature environment, greatly increasing the cost.

[0005] At the same time, because the flue gas generated during the sintering production process mainly contains various pollutants such as dust, SO2, NO x , CO, dioxins, etc. Among them, the dust concentration is about 10 g / (N·m 3 ), the SO2 concentration is 1,000 - 3,000 mg / (N·m 3 ), the NOx concentration is 200 - 400 mg / (N·m 3 ), the CO concentration is 5,000 - 10,000 ppm, and the dioxins are about 1 - 3 ng-TEQ / (N·m 3 ); the oxygen content of the flue gas is about 15% - 18%, the moisture content is about 7% - 13%, and the flue gas temperature is about 120°C - 180°C; and due to the influence of production raw materials and operating conditions, factors such as large fluctuations in flue gas volume, flue gas temperature, and pollutant concentration, the existing CO catalysts cannot maintain high catalytic efficiency under such complex conditions, and often under the action of various pollutants in the flue gas, such as SO2, NO x and dust, etc., the catalyst will gradually be poisoned, and the catalytic efficiency will decrease over time until it drops to 0. Summary of the Invention

[0006] To solve the above problems, the present invention provides a monolithic carbon monoxide catalyst, its preparation method and application. The monolithic carbon monoxide catalyst has advantages such as sulfur resistance and water resistance. The method adjusts the active components in the monolithic carbon monoxide catalyst. By adding auxiliary agents such as acid solution (or alkali solution), binder, thickener, dispersant, water retention agent, etc., the synergistic effect of each active component in the monolithic carbon monoxide catalyst product can be strengthened. At the same time, the active components, especially noble metals, can be uniformly dispersed in the selected carrier or solution, enabling them to exert surface effects, increasing the specific surface area and surface energy of the metal catalytic particles in the monolithic carbon monoxide catalyst, and improving the activity and catalytic efficiency of the catalyst. The prepared monolithic carbon monoxide catalyst has stable catalytic properties and an extended service life.

[0007] The present invention is achieved through the following technical solutions:

[0008] One of the objectives of the present invention is to provide a monolithic carbon monoxide catalyst, which includes a carrier and metal catalytic particles loaded on the surface of the carrier;

[0009] The loading amount of the metal catalytic particles is 90 kg / m 3 ~150 kg / m 3 ;

[0010] The particle size range of the monolithic carbon monoxide catalyst is 50 nm to 200 nm;

[0011] The metal catalytic particles include one or more of titanium particles, cerium particles, cobalt particles, nickel particles, ruthenium particles, rhodium particles, palladium particles, iridium particles, platinum particles, molybdenum particles;

[0012] The particle size range of the metal catalytic particles is: 1 nm to 100 nm;

[0013] The carrier includes one or more of cordierite, honeycomb body, hierarchical pore carbon, foam metal.

[0014] The monolithic carbon monoxide catalyst provided by the present invention has high sulfur resistance and water resistance, resulting in high catalytic stability in sintering flue gas purification. The loading amount of the metal catalytic particles in the monolithic carbon monoxide catalyst is 90 kg / m 3 ~150 kg / m 3 , has a high adsorption capacity for carbon monoxide, and is not prone to agglomeration during the catalytic process. The monolithic carbon monoxide catalyst of the present invention can maintain stable high catalytic efficiency under the complex conditions of sintering flue gas.

[0015] The second objective of the present invention is to provide a preparation method of the monolithic carbon monoxide catalyst of the present invention, and the preparation method includes the following steps:

[0016] Prepare a first intermediate product solution from titanium oxide and cerium oxide;

[0017] Prepare a second intermediate product solution from an ammonium source, the first intermediate product solution, and an auxiliary agent;

[0018] Prepare a third intermediate product from a metal nitrate solution and the second intermediate product solution;

[0019] Prepare a fourth intermediate product solution from a cobalt source and the third intermediate product;

[0020] After making a supported slurry from a binder, a dispersant, a thickener, a water retention agent, and the fourth intermediate product solution, load the supported slurry onto a carrier to obtain a monolithic carbon monoxide catalyst.

[0021] A method for preparing a monolithic carbon monoxide catalyst provided by the present invention, the method sequentially prepares a first intermediate product, a second intermediate product, a third intermediate product, and a fourth intermediate product, and finally makes the fourth intermediate product into a supported slurry and mixes it with a carrier to obtain a monolithic carbon monoxide catalyst. The first intermediate product prepared first by the method has a large specific surface area; the second intermediate product prepared by using the first intermediate product has a product with a Keggin structure, where the Keggin structure refers to a special polynuclear polyacid structure in a variety of chemical compounds. This structure was first proposed by the French chemist Dorothy Crowfoot Hodgkin in the 1930s. Its role is to facilitate the connection of a variety of organic molecules and other macromolecules into a macromolecule, providing a structural basis for the subsequent preparation of the catalyst; after the metal nitrate solution and the second intermediate product solution are mixed, they are first dried and calcined to obtain the third intermediate product, reducing the intermolecular distance between the various components in the third intermediate product, and the intermolecular distance formed by subsequent preparation into a solution will be smaller, controlling the size of the active components at the nanometer level, which is beneficial to the catalytic effect of the catalyst obtained by subsequent loading; further, the third intermediate product prepared by using the second intermediate product is a catalyst with metal loading; further, the third intermediate product and a cobalt source are ball-milled and then calcined to obtain a fourth intermediate product with the function of catalyzing carbon monoxide; the fourth intermediate product is made into a supported slurry and loaded onto a carrier to obtain a monolithic carbon monoxide catalyst. The monolithic carbon monoxide catalyst prepared by the preparation method can maintain a stable high catalytic efficiency under the complex conditions of sintering flue gas, and at the same time, because it contains a carrier, it is not easy to agglomerate during the catalytic process.

[0022] The third object of the present invention is to provide the application of the monolithic carbon monoxide catalyst provided by the first object of the present invention or the monolithic carbon monoxide catalyst prepared by the preparation method provided by the second object of the present invention in the catalytic oxidation of carbon monoxide in flue gas. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a schematic flow chart of a preparation method of a monolithic carbon monoxide catalyst in an embodiment of the present invention;

[0024] Figure 2 It is a schematic diagram of an experimental device for carbon monoxide adsorption of the catalyst involved in the embodiment and comparative example of the present invention;

[0025] Figure 3 It is a schematic diagram showing the change of the catalytic efficiency of the catalyst provided in the embodiment and comparative example of the present invention for CO with time. DETAILED DESCRIPTION OF THE INVENTION

[0026] In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0027] On the contrary, the present invention covers any alternatives, modifications, equivalent methods and solutions made within the spirit and scope of the present invention defined by the claims. Further, in order to enable the public to better understand the present invention, some specific details are described in detail in the following detailed description of the present invention. Those skilled in the art can fully understand the present invention without the description of these details.

[0028] The following examples illustrate the present invention. In the examples, unless otherwise specified, the parts are calculated by weight parts, the percentages are calculated by weight percentages, and the temperature is in degrees Celsius. The relationship between the parts calculated by weight and the parts calculated by volume is the same as the relationship between grams and cubic centimeters.

[0029]

Monolithic Carbon Monoxide Catalyst

[0030] One object of the embodiment of the present invention is to provide a monolithic carbon monoxide catalyst, which includes a carrier and metal catalytic particles loaded on the surface of the carrier;

[0031] The loading amount of the metal catalytic particles is 90 kg / m 3 ~150 kg / m 3 .

[0032] An integral carbon monoxide catalyst provided by an embodiment of the present invention has high sulfur resistance and water resistance, making its catalytic stability high in sintering flue gas purification. The loading amount of metal catalytic particles in the integral carbon monoxide catalyst is 90 kg / m 3 ~150 kg / m 3 , and it has a high adsorption capacity for carbon monoxide. Since the carrier is combined with metal catalytic particles, agglomeration is not likely to occur during the catalytic process of the integral carbon monoxide catalyst.

[0033] In the embodiment, the loading amount of the metal catalytic particles can be 90 kg / m 3 , 100 kg / m 3 , 110 kg / m 3 , 120 kg / m 3 , 130 kg / m 3 , 140 kg / m 3 , 150 kg / m 3 and other typical but non-limiting loading amounts or ranges between any two loading amounts. In this loading amount range, the integral carbon monoxide catalyst has a high adsorption capacity for carbon monoxide.

[0034] In some embodiments, the particle size range of the integral carbon monoxide catalyst is 50 nm to 200 nm. Exemplarily, it can be 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm and other typical but non-limiting particle sizes or ranges between any two particle sizes. In this particle size range, the integral carbon monoxide catalyst can catalytically purify CO in sintering flue gas against poisoning; moreover, due to the use of a carrier, the nanoscale integral carbon monoxide catalyst has a high adsorption capacity for carbon monoxide and is not likely to agglomerate during the catalytic process.

[0035] In some embodiments, the metal catalytic particles include one or more of titanium particles, cerium particles, cobalt particles, nickel particles, ruthenium particles, rhodium particles, palladium particles, iridium particles, platinum particles, and molybdenum particles. These metals can be used to catalyze carbon monoxide.

[0036] In some embodiments, the particle size range of the metal catalytic particles is from 1 nm to 100 nm. Exemplarily, it can be typical but non-limiting particle sizes such as 1 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, or the range between any two particle sizes. In this particle size range, the size of the metal catalytic particles can be controlled at the nanometer level, enabling them to be highly uniformly dispersed on the carrier. Furthermore, the metal catalytic particles can be well loaded on the carrier, and the resulting monolithic carbon monoxide can maintain a stable high catalytic efficiency under the complex conditions of sintering flue gas.

[0037] In some embodiments, the carrier includes one or more of cordierite, honeycomb, hierarchical porous carbon, and foam metal. These carriers have a rich pore structure, which can increase the loading amount of the metal catalytic particles.

[0038]

Preparation Method of Monolithic Carbon Monoxide Catalyst

[0039] Another object of the embodiments of the present invention is to provide a preparation method of the monolithic carbon monoxide catalyst of the present invention. As Figure 1 shown, the preparation method includes the following steps:

[0040] S1. Prepare a first intermediate product solution from titanium oxide and cerium oxide.

[0041] S2. Prepare a second intermediate product solution from an ammonium source, the first intermediate product solution, and an auxiliary agent.

[0042] S3. Prepare a third intermediate product from a metal nitrate solution and the second intermediate product solution.

[0043] S4. Prepare a fourth intermediate product solution from a cobalt source and the third intermediate product.

[0044] S5. After making a loading slurry from a binder, a dispersant, a thickener, a water retention agent, and the fourth intermediate product solution, load the loading slurry on the carrier to obtain a monolithic carbon monoxide catalyst.

[0045] A preparation method of an integral carbon monoxide catalyst provided by an embodiment of the present invention sequentially prepares a first intermediate product, a second intermediate product, a third intermediate product, and a fourth intermediate product, and finally makes the fourth intermediate product into a supported slurry and mixes it with a carrier to obtain the integral carbon monoxide catalyst. The first intermediate product prepared first by the method has a large specific surface area; the second intermediate product prepared by using the first intermediate product has a product with a Keggin structure, where the Keggin structure refers to a special polynuclear polyacid structure in various chemical compounds. This structure was first proposed by the French chemist Dorothy Crowfoot Hodgkin in the 1930s. The role of the Keggin structure is to facilitate the connection of various organic molecules and other macromolecules into a macromolecule, providing a structural basis for the subsequent preparation of the catalyst; after the metal nitrate solution is mixed with the second intermediate product solution, it is first dried and calcined to obtain the third intermediate product, reducing the intermolecular distance between the components in the third intermediate product, and the intermolecular distance formed by subsequent preparation into a solution will be smaller, which is beneficial to the catalytic effect of the catalyst obtained by subsequent loading; the third intermediate product further prepared by using the second intermediate product is a catalyst with metal loading; further, the third intermediate product is ball-milled with a cobalt source and then calcined to obtain a fourth intermediate product with the function of catalyzing carbon monoxide; the fourth intermediate product is made into a supported slurry, and after mixing with the carrier, it is dried and calcined to obtain the integral carbon monoxide catalyst. The integral carbon monoxide catalyst prepared by the preparation method contains a sequential chemical bonding structure of noble metal-non-noble metal-carrier (Ce and Ti), can maintain a stable high catalytic efficiency under the complex conditions of sintering flue gas, and is not prone to agglomeration during the catalytic process due to the presence of the carrier.

[0046]

S1

[0047] In some embodiments, in the above step S1, the step of preparing the first intermediate product solution includes: performing a first ball-milling treatment on titanium oxide and cerium oxide and then performing a first calcination treatment to obtain the first intermediate product; mixing the first intermediate product solution with water to obtain the first intermediate product solution.

[0048] In some embodiments, the mass ratio of titanium oxide to cerium oxide is (3-6):1. Exemplarily, it can be typical but non-limiting mass ratios such as 3:1, 4:1, 5:1, 6:1, etc. or the range between any two mass ratios. In this case, the integral carbon monoxide catalyst prepared has a high adsorption capacity for carbon monoxide. Because the carrier is combined with the metal catalytic particles, it is not prone to agglomeration during the catalytic process of the integral carbon monoxide catalyst.

[0049] In some embodiments, in the first ball milling treatment, the ball-to-material mass ratio is (3.5 - 10):1; the rotation speed is 400 rpm to 600 rpm, and the time is 1 h to 1.5 h. Further, in the first ball milling treatment, the particle size of the grinding balls is not higher than 1 mm. Further, in the first ball milling treatment, the particle size of the grinding balls is not higher than 1 mm. Further, in the first ball milling treatment, the grinding balls include at least one of zirconia balls, alumina balls, and agate balls. Further, in the first ball milling treatment, the ball milling temperature is 25°C to 30°C. In this case, the particle size of the product obtained after ball milling is nanoscale, and after subsequent first calcination treatment, a dry nanoscale first intermediate product (1 nm - 100 nm) can be obtained.

[0050] In the embodiments, the ball-to-material mass ratio is (3.5 - 10):1. Exemplarily, it can be typical but non-limiting mass ratios such as 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, etc. or the range between any two mass ratios. Within this mass ratio range, combined with the rotation speed and ball milling time, the desired particle size of the product after the first ball milling can be obtained.

[0051] In the embodiments, the particle size of the grinding balls is not higher than 1 mm. Exemplarily, it can be typical but non-limiting particle sizes such as 1 mm, 10 mm, 15 mm, 20 mm, 500 μm, 100 μm, etc. or the range between any two particle sizes. In this case, the particle size of the product obtained after ball milling is nanoscale, and after subsequent first calcination treatment, a dry nanoscale first intermediate product (1 nm - 100 nm) can be obtained.

[0052] In some embodiments, in the above step S1, the particle size range of the product after the first ball milling is: 1 nm - 100 nm. Exemplarily, it can be typical but non-limiting particle sizes such as 1 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, etc. or the range between any two particle sizes.

[0053] In some embodiments, the temperature of the first calcination treatment is 450°C to 550°C, and the time is 1 h to 2 h.

[0054] In some embodiments, the particle size range of the first intermediate product is 1 nm - 100 nm. Exemplarily, it can be typical but non-limiting particle sizes such as 1 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, etc. or the range between any two particle sizes.

[0055]

S2

[0056] In some embodiments, in the above step S2, the step of preparing the second intermediate product solution includes: obtaining an ammonium source and a pH regulator, mixing them with the first intermediate product solution, followed by first drying and calcination to obtain the second intermediate product; mixing and stirring the second intermediate product and water at a constant temperature of 50°C to 80°C for 0.5 h to 2 h to obtain the second intermediate product solution.

[0057] In some embodiments, the ammonium source includes one or more of ammonium molybdate, ammonium phosphate, ammonium metavanadate, and ammonium tungstate.

[0058] In some embodiments, the pH regulator is an acid solution or a base solution. The additive is used to adjust the pH value of the system to be in the range of 1.2 to 3.6. Exemplarily, it can be typical but non-limiting pH values such as 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, etc. or the range between any two pH values. Within these pH value ranges, the stability of the solution can be ensured, and at the same time, other side reactions of the ammonium source can be inhibited.

[0059] In some specific embodiments, the acid solution includes one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, acetic acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution.

[0060] In some specific embodiments, the base solution includes one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and ammonia water.

[0061] In some embodiments, in the additive, the molar concentration of the solute is 0.001 mol / L to 10 mol / L. Exemplarily, it can be typical but non-limiting molar concentrations such as 0.001 mol / L, 0.01 mol / L, 0.1 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, 5 mol / L, 6 mol / L, 7 mol / L, 8 mol / L, 9 mol / L, 10 mol / L, etc. or the range between any two molar concentrations.

[0062] In some embodiments, the mass ratio of the first intermediate product to the ammonium source is (6 to 18):1. Exemplarily, it can be typical but non-limiting mass ratios such as 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, etc. or the range between any two mass ratios.

[0063] In some embodiments, the step of mixing the ammonium source and the additive with the first intermediate product solution includes: stirring at a constant temperature of 50°C to 80°C for 1 h to 4 h, and adding the additive while stirring to maintain the pH value of the reaction solution at 1.2 to 3.6.

[0064] In some embodiments, the temperature of the first drying is 110°C to 140°C, and the drying time is 8 h to 12 h.

[0065] In some embodiments, the temperature of the calcination is 400°C, and the calcination time is 2 h.

[0066]

S3

[0067] In some embodiments, in the above step S3, the steps of preparing the third intermediate product include: after mixing the metal nitrate solution and the second intermediate product solution, performing a second drying and a second calcination treatment to obtain the third intermediate product.

[0068] In some embodiments, in the metal nitrate solution, the metal elements include one or more of cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum.

[0069] In some embodiments, in the metal nitrate solution, the concentration of the solute is 8 g / L to 14 g / L. Exemplarily, it can be typical but non-limiting concentrations such as 8 g / L, 9 g / L, 10 g / L, 11 g / L, 12 g / L, 13 g / L, 14 g / L, or the range between any two concentrations.

[0070] In some embodiments, the step of mixing the metal nitrate solution and the second intermediate product solution includes: stirring for 1 h to 4 h under the condition of a constant temperature of 70°C to 90°C.

[0071] In some embodiments, the temperature of the second drying is 70°C to 90°C, and the drying time is 4 h to 10 h.

[0072] In some embodiments, the steps of the second calcination treatment include: grinding the dried reaction product solid into powder, and calcining for 2 h to 5 h under the condition of 400°C to 600°C to obtain the third intermediate product.

[0073] In some embodiments, the mass ratio of the second intermediate product to the metal nitrate solution is (1 to 3):2. Exemplarily, it can be typical but non-limiting mass ratios such as 1:2, 2:2, 3:2, or the range between any two mass ratios.

[0074] In some embodiments, in the third intermediate product, the loading amount of the metal particles is 0.1 wt% to 2 wt%. Exemplarily, it can be typical but non-limiting loading amounts such as 0.1 wt%, 0.2 wt%, 0.4 wt%, 0.6 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 2 wt%, or the range between any two loading amounts.

[0075]

S4

[0076] In some embodiments, in the above step S4, the step of preparing the fourth intermediate product solution includes: subjecting the cobalt source and the third intermediate product to a second ball milling treatment and then a third calcination treatment to obtain the fourth intermediate product; mixing the fourth intermediate product with water and stirring for 0.5 h to 1 h to obtain the fourth intermediate product solution.

[0077] In some embodiments, the cobalt source includes cobalt tetroxide.

[0078] In some specific embodiments, the preparation of cobalt tetroxide includes the steps of:

[0079] Respectively obtain the dosages of cobalt acetate, absolute ethanol, water, and sodium carbonate;

[0080] Under the condition of water bath heating, mix and stir absolute ethanol and cobalt acetate to obtain a cobalt acetate solution;

[0081] Under the condition of 60 °C, mix sodium carbonate and water and make up the volume to obtain a sodium carbonate solution with a concentration of 1 mol / L; at this concentration, when adjusting the pH of the cobalt acetate solution subsequently, the pH of the solution can be quickly and accurately controlled.

[0082] Under the condition of continuous stirring, slowly drop the sodium carbonate solution into the cobalt acetate solution and measure the pH value of the suspension. When the pH value reaches 10, stop dropping the sodium carbonate solution to obtain a suspension;

[0083] Continue to stir the suspension for 30 min, then stand and age for 30 min, and then filter and wash the suspension until it is neutral to obtain a paste;

[0084] After drying the paste, heat it to 450 °C at a heating rate of 3 °C / min in an air atmosphere and calcine for 3 h to 5 h to obtain cobalt tetroxide. In this case, heating to 450 °C can remove the organic matter therein. The prepared cobalt tetroxide has a purity of more than 99%, which is high-purity cobalt tetroxide and can improve the catalytic efficiency and catalytic stability of the monolithic carbon monoxide catalyst.

[0085] The calcination temperature is determined by the conversion temperature and conversion rate of cobalt oxide to cobalt tetroxide. At this temperature, the conversion of cobalt oxide to cobalt tetroxide can be promoted.

[0086] In some embodiments, the mass ratio of the cobalt source to the third intermediate product is 1:(6 - 10). Exemplarily, it can be typical but non-limiting mass ratios such as 1:6, 1:7, 1:8, 1:9, 1:10, etc. or the range between any two mass ratios.

[0087] In some embodiments, in the second ball milling process, the mass ratio of balls to materials is (3.5 - 10):1, the rotation speed is 400 rpm to 600 rpm, and the ball milling time is 1 h to 1.5 h. In some embodiments, in the second ball milling process, the particle size of the grinding balls is not higher than 1 mm. In some embodiments, in the second ball milling process, the particle size of the grinding balls is not higher than 1 mm. In some embodiments, in the second ball milling process, the grinding balls include at least one of zirconia balls, alumina balls, and agate balls. In some embodiments, in the second ball milling process, the ball milling temperature is 25°C to 30°C. In this case, the particle size of the product obtained after ball milling is nanoscale, and after subsequent third calcination treatment, a dry nanoscale fourth intermediate product (1 nm to 100 nm) can be obtained.

[0088] In the embodiments, the mass ratio of balls to materials is (3.5 - 10):1. Exemplarily, it can be typical but non-limiting mass ratios such as 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, etc., or the range between any two mass ratios. Within this mass ratio range, combined with the rotation speed and ball milling time, the desired particle size of the product after the second ball milling can be obtained.

[0089] In the embodiments, the particle size of the grinding balls is not higher than 1 mm. Exemplarily, it can be typical but non-limiting particle sizes such as 1 mm, 10 mm, 15 mm, 20 mm, 500 μm, 100 μm, etc., or the range between any two particle sizes. In this case, the particle size of the product obtained after ball milling is nanoscale, and after subsequent third calcination treatment, a dry nanoscale third intermediate product (1 nm to 100 nm) can be obtained.

[0090] In some embodiments, the particle size of the product after the second ball milling is: 1 nm to 100 nm. Exemplarily, it can be typical but non-limiting particle sizes such as 1 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, etc., or the range between any two particle sizes. The particle size of the ball milling product directly affects the particle size of the dried fourth intermediate product. Within this particle size range, the particle size of the fourth product obtained after drying is also nanoscale.

[0091] In some embodiments, the particle size range of the fourth intermediate product is from 1 nm to 100 nm. Exemplarily, it can be typical but non-limiting particle sizes such as 1 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm or the range between any two particle sizes. In this particle size range, the fourth intermediate product is made into a solution and then formed into a loading slurry, which is uniformly loaded on the carrier, and a nanoscale monolithic carbon monoxide catalyst can be obtained.

[0092]

S5

[0093] In some embodiments, in the above step S5, the binder includes one or more of calcium silicate, sodium silicate, calcium aluminate, phenolic resin, diatomaceous earth, aluminum sol, silica sol, kaolin, attapulgite, sodium silicate, bentonite, montmorillonite, and pseudo-boehmite. It is premixed with deionized water to form a binder solution with a mass fraction of 20% to 30%. At this concentration, the binder can have good dispersibility.

[0094] In some embodiments, in the above step S5, the dispersant includes one or more of polyacrylic acid, polypropylene, polystyrene, polyethylene wax, polyethylene ether, polyethylene ester, polyvinyl acetate, polyethylene, polyacrylamide, sodium polyacrylate, polyethylene glycol, and polyvinyl alcohol. It is premixed with deionized water to form a dispersant solution with a mass fraction of 5% to 10%. At this concentration, the dispersant can have good dispersibility.

[0095] In some embodiments, in the above step S5, the thickener includes one or more of hydroxymethyl cellulose, hydroxymethylpropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, cellulose ether, and starch. It is premixed with deionized water to form a thickener solution with a mass fraction of 5% to 10%. At this concentration, the thickener can have good dispersibility.

[0096] In some embodiments, in the above step S5, the water retention agent includes one or more of glycerol, lignin, sodium alginate, polyacrylamide, sodium polyacrylate, potassium polyacrylate, and ammonium polyacrylate.

[0097] In some embodiments, in the above step S5, the mass fractions of the components in the loading slurry include 5% to 50% of the fourth intermediate product, 0.2% to 15% of the dispersant, 0.1% to 15% of the thickener, and 1% to 15% of the binder. The loading slurry within this mass fraction range is more stable, and can improve the loading amount, loading uniformity, and mechanical stability of the catalyst active component, etc.

[0098] In some embodiments, before the carrier is mixed and loaded with the loading slurry in the above step S5, the carrier is pretreated, and the pretreatment includes the steps:

[0099] Place the carrier rinsed with distilled water in acetic acid or oxalic acid with a volume concentration of 5% - 25%, and seal and soak it for 2h - 3h under the constant temperature condition of 60°C - 90°C;

[0100] Take out the carrier and wash it ultrasonically with water until it is neutral;

[0101] Dry it for 5h - 8h under the constant temperature condition of 60°C - 90°C;

[0102] Calcine it in a muffle furnace at 350°C - 500°C for 1.5h - 3h, and cool it to room temperature to obtain the treated carrier.

[0103] In some embodiments, the step of mixing and loading the loading slurry with the carrier includes: using a vacuum coater to coat the loading slurry on the carrier.

[0104] In some embodiments, the drying temperature of the third drying is 90°C - 150°C, and the drying time is 8h - 20h. At this drying temperature and time, the moisture of the loading slurry is removed.

[0105] In some embodiments, in the third calcination treatment, the calcination temperature is 200°C - 350°C, and the calcination time is 1h - 10h. At this calcination temperature and time, with the assistance of a binder, etc., the fourth intermediate product as a metal catalyst is firmly loaded on the carrier to form a monolithic carbon monoxide catalyst.

[0106] The following is further illustrated in conjunction with embodiments.

[0107] Example 1

[0108] Example 1 provides a preparation method of a monolithic carbon monoxide catalyst, and the preparation method is as follows:

[0109] (1) Pretreat cordierite.

[0110] First rinse the cordierite with distilled water and then place it in acetic acid with a concentration of 11%. After covering and sealing, heat and soak it for 2.5h under the constant temperature condition of 70°C. Take it out and place it in an ultrasonic cleaner to wash it with water until it is neutral, then dry it at 70°C for 6h, and then calcine it in a muffle furnace at 400°C for 2h, and cool it to room temperature for use.

[0111] Unless otherwise specified, the following baking operations are all heated at a rate of 3°C / min.

[0112] (2) Prepare the first intermediate product: Place 50g of TiO2 and 10g of CeO2 in 500cm 3Sintered zirconia grinding jars with agate balls (20, 15, and 10 mm in diameter). The mass ratio of balls to material is 10:1, the rotation speed is 500 rpm, and the time is 1 h. Then the obtained powder is calcined at 500 °C for 2 h to obtain the first intermediate product.

[0113] (3) Preparation of the second intermediate product: Add 44.5 g of (NH4)6Mo7O 24 , 0.5 g of NH4H2PO4, and 60 g of the first intermediate product to 200 mL of distilled water, stir at a constant temperature of 60 °C for 2 h, and add a nitric acid solution to adjust the pH of the solution to 1.5. After stirring is completed, dry at 120 °C for 9 h and calcine at 400 °C for 2 h to obtain the second intermediate product.

[0114] (4) Preparation of the third intermediate product: Mix 60 g of the second intermediate product and 500 ml of deionized water, stir at a constant temperature of 70 °C for 1 h, then add 40 g of a 10 g / L platinum nitrate solution, stir at a constant temperature of 70 °C for 1 h, dry at 80 °C for 5 h, grind the obtained solid into powder, and calcine at 500 °C for 1.5 h to obtain the third intermediate product.

[0115] (5) Preparation of the fourth intermediate product: Place 6 g of cobalt tetroxide and 60 g of the third intermediate product in a grinding jar and mix and grind with agate balls (20, 15, and 10 mm in diameter). Calcinate the obtained 1 nm - 100 nm powder at 350 °C for 3 h to obtain the fourth intermediate product.

[0116] (6) Preparation of the monolithic carbon monoxide catalyst: Weigh 10 g of carboxymethyl cellulose and 90 g of deionized water to prepare a 10% concentration thickener solution.

[0117] Weigh 10 g of polypropylene powder and 90 g of deionized water to prepare a 10% concentration dispersant solution;

[0118] Weigh 50 g of the fourth intermediate product and 35 g of deionized water, mix and stir at room temperature for 1 h to obtain the fourth intermediate product solution;

[0119] Weigh 10 g of sodium silicate solution as a binder and 5 g of the dispersant solution, mix and stir at room temperature for 2 h, add the fourth intermediate product solution, stir at room temperature for 2 h, then weigh and add 0.5 g of polyacrylamide as a water retention agent, and then add 0.5 g of the thickener solution, and then stir at room temperature for 4 h to obtain the loading slurry;

[0120] Then use a vacuum coater to coat the loading slurry on the pretreated cordierite support, dry at 110 °C for 15 h, and calcine at 300 °C for 8 h to obtain the monolithic carbon monoxide catalyst.

[0121] Example 2

[0122] Example 2 provides a method for preparing an integral carbon monoxide catalyst. The steps are basically the same as those in Example 1, except that:

[0123] In step (3), the pH of the solution is adjusted to 1.2 with nitric acid solution.

[0124] In step (4), when preparing the third intermediate product, the mass of the platinum nitrate solution added is 45 g.

[0125] Example 3

[0126] Example 3 provides a method for preparing an integral carbon monoxide catalyst. The steps are basically the same as those in Example 1, except that:

[0127] In step (3), the pH of the solution is adjusted to 3.0 with nitric acid solution.

[0128] In step (4), when preparing the third intermediate product, the mass of the palladium nitrate solution added is 50 g, and the concentration of palladium nitrate is 10 g / L.

[0129] Example 4

[0130] Example 4 provides a method for preparing an integral carbon monoxide catalyst. The preparation method is basically the same as that in Example 3, except that:

[0131] In step (3), the pH of the solution is adjusted to 3.6 with nitric acid solution.

[0132] In step (4), when preparing the third intermediate product, the mass of the palladium nitrate solution added is 40 g.

[0133] Comparative Example 1

[0134] Comparative Example 1 provides a method for preparing a catalyst. The steps are basically the same as those in Example 1, except that: the fourth intermediate product is used as the final product catalyst, that is, the fourth intermediate product is not loaded on cordierite.

[0135] Comparative Example 2

[0136] Comparative Example 2 provides a method for preparing a catalyst. The steps are as follows:

[0137] (2-1) Mix 200 g of anatase TiO2 and 50 g of CeO2, place them in a grinding jar, process at a rate of 500 rpm for 1 h, and then calcine the powder at 500 °C for 2 h to obtain powder A.

[0138] (2-2) Mix 190 g of powder A, 24.2 g of (NH4)6Mo7O 24Mix with 1.2 g of NH4H2PO4, add 300 g of distilled water, stir for 0.5 h under the action of a mechanical rotor, and then adjust the pH of the solution by dropping nitric acid solution until pH = 1. Then continue to stir for 2 h to form solution B.

[0139] (2-3) Dry solution B at 80 °C for 6 h and calcine it at 350 °C for 2 h to obtain solid C.

[0140] (2-4) Dissolve 60 g of solid C in 500 ml of distilled water, then add 40 g of 10 g / L platinum nitrate solution, stir at 80 °C for 2 h, dry at 80 °C for 6 h, grind the solid into powder, and then calcine it at 350 °C for 2 h to obtain solid D.

[0141] (2-5) Place 6 g of cobalt tetroxide and 60 g of solid D in a grinding jar and mix and grind them. The obtained powder is calcined at 350 °C for 2 h to obtain catalytic particles E.

[0142] (2-6) Load catalytic particles E onto cordierite in the same way as in step (6) of Example 1 to obtain a catalyst.

[0143] Comparative Example 3

[0144] A preparation method of a catalyst proposed in this comparative example is basically the same as that of Comparative Example 2, except that: using catalyst particles E as the final product catalyst, that is, not loading catalyst particles E onto cordierite.

[0145] In order to verify the progressiveness of the embodiments of the present application, adsorption experiments of carbon monoxide were carried out on the catalysts prepared by the preparation methods of the catalysts involved in Examples 1 to 4 and Comparative Examples 1 to 3. The experimental contents include:

[0146] Place the catalysts prepared in Examples 1 to 4 and Comparative Examples 1 to 3 in the actual sintering flue gas of a steel mill with a flow rate of 10 m 3 / h. The space velocity (referring to the amount of gas processed by the catalyst per unit time per unit volume) is 6000 h -1 , and the experimental duration is 240 h. Carry out carbon monoxide adsorption experiments. The experimental device used is shown in Figure 2 . As Figure 2 shown, lead out a gas path from the desulfurized flue gas pipeline. Its power is provided by an air pump, its flow rate is controlled by a rotameter, and its temperature is controlled by a heating coil. Open the first ball valve and close the second ball valve. The lead-out gas enters the catalytic tower through the pipeline. The temperature of the catalytic tower is 200 °C to 220 °C. The catalytic tower is filled with the catalysts prepared in Examples 1 to 4 and Comparative Examples 1 to 3, and the carbon monoxide in the lead-out gas is catalytically oxidized to carbon dioxide to obtain the treated gas.

[0147] When conducting measurements, the gas treated by the integral carbon monoxide catalyst is introduced into the flue gas analyzer to measure the carbon monoxide content in the treated gas. After the reading of the flue gas analyzer stabilizes, record the carbon monoxide content and then evacuate.

[0148] Close the first ball valve and open the second ball valve to directly introduce the extracted gas into the flue gas analyzer to measure the carbon monoxide content of the extracted gas. After the reading of the flue gas analyzer stabilizes, record the carbon monoxide content. Finally, according to the carbon monoxide contents of the flue gas before treatment and the gas after treatment, substitute them into the following formula to calculate the purification efficiency of the catalyst for CO.

[0149]

[0150] In the formula, C is the purification efficiency %, ρ in is the content of CO in the flue gas before entering the catalyst in ppm, ρ out is the content of CO in the flue gas after entering the catalyst in ppm.

[0151] The average removal rate of CO refers to the removal rate after the purification efficiency stabilizes, which can best reflect the catalytic performance of the CO catalyst in actual applications. The deactivation rate is an important indicator for evaluating the stability of the catalyst, which can help to synergistically optimize the flue gas parameters and catalytic performance. The calculation formula of the deactivation rate is as follows:

[0152]

[0153] In the formula, M 失活率 is the deactivation rate % of the catalyst, C 初始净化效率 is the highest purification efficiency % of the catalyst at the beginning of operation, C 稳定后净化效率 is the purification efficiency % maintained by the catalyst after long-term operation.

[0154] The experimental results are shown in Table 1 below:

[0155] Table 1

[0156]

[0157] Note: In Table 1, ① represents "the average removal rate of CO by the catalyst (purification efficiency of the flue gas)"; ② represents "the deactivation rate of the catalyst (sulfur resistance and water resistance)"; ③ represents "whether the catalyst particles agglomerate".

[0158] As can be seen from Table 1 above:

[0159] (1) The adsorption rate (flue gas purification efficiency) of the monolithic carbon monoxide catalyst prepared in the embodiments of the present invention for CO is high (greater than 80%). Since in the preparation method of the catalyst in the embodiments of the present invention, the free metals that do not form the sequential chemical bonding structure of noble metal-non-noble metal-support (Ce and Ti) are not removed, these free metal ions will react with SO2 and SO3 in the sintering flue gas to form difficult-to-decompose sulfates, etc., resulting in the loss of a certain activity of the catalyst. However, after the free metal ions have completely reacted, the catalyst will no longer be deactivated further. Combining with the deactivation rate in Table 1, it can be seen that the sulfur resistance and water resistance of the monolithic carbon monoxide catalyst are better, and the purification efficiency is stable. And using cordierite as the support can significantly reduce the agglomeration phenomenon of the catalyst during the catalytic purification process. The loading amount of the metal catalytic particles affects the catalytic efficiency of the monolithic carbon monoxide catalyst.

[0160] (2) For the monolithic carbon monoxide catalyst prepared in the embodiments of the present invention, since the step of removing free metal ions is not carried out during the preparation process, during the catalytic reaction process, after all the free metal ions in the catalyst react with sulfur oxides (SO2 and SO3) in the flue gas to form difficult-to-decompose metal salts, they will no longer react with SO2 and SO3. The remaining sequential chemical bonding structure of noble metal-non-noble metal-support (Ce and Ti) will continuously and stably catalyze the oxidation of CO, and finally achieve the catalytic effect that the catalyst only oxidizes CO and cannot oxidize SO2 to cause the catalyst to be poisoned.

[0161] The above are only the preferred embodiments of the monolithic carbon monoxide catalyst and its preparation method of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A monolithic carbon monoxide catalyst, characterized in that: The monolithic carbon monoxide catalyst comprises a carrier and metal catalytic particles supported on the surface of the carrier; The loading amount of the metal catalytic particles is 90 kg / m 3 ~150kg / m 3 ; The metal catalytic particles include one or more of titanium particles, cerium particles, cobalt particles, nickel particles, ruthenium particles, rhodium particles, palladium particles, iridium particles, platinum particles, and molybdenum particles; The particle size range of the metal catalytic particles is: 1nm to 100nm; The carrier includes one or more of cordierite, honeycomb, and hierarchical porous carbon.

2. A method for preparing the integral carbon monoxide catalyst according to claim 1, characterized in that: The preparation method comprises the following steps: preparing titanium oxide and cerium oxide into a first intermediate product solution; preparing a second intermediate product solution by using an ammonium source, the first intermediate product solution and an auxiliary agent; preparing a third intermediate product from a metal nitrate solution and the second intermediate product solution; preparing a fourth intermediate product solution by using a cobalt source and the third intermediate product; After the binder, dispersant, thickener, water retaining agent and the fourth intermediate product solution are made into a loaded slurry, the loaded slurry is loaded on a carrier to obtain an integral carbon monoxide catalyst.

3. The method for preparing the integral carbon monoxide catalyst according to claim 2, characterized in that: The step of preparing the first intermediate product solution includes: subjecting titanium oxide and cerium oxide to a first ball milling process and then to a first calcination process to obtain a first intermediate product; mixing the first intermediate product solution with water to obtain the first intermediate product solution; And / or, the step of preparing the second intermediate product solution comprises: obtaining an ammonium source and an auxiliary agent, mixing them with the first intermediate product solution, and performing a first drying and roasting to obtain a second intermediate product; mixing the second intermediate product and water at a constant temperature of 50° C. to 80° C. and stirring for 0.5 h to 2 h to obtain the second intermediate product solution; And / or, the step of preparing the third intermediate product comprises: mixing the metal nitrate solution with the second intermediate product solution, and then performing a second drying and a second calcination treatment to obtain the third intermediate product; And / or, the step of preparing the fourth intermediate product solution comprises: subjecting the cobalt source and the third intermediate product to a second ball milling treatment and then to a third calcination treatment to obtain a fourth intermediate product; mixing the fourth intermediate product with water and stirring for 0.5 h to 1 h to obtain the fourth intermediate product solution; And / or, the step of loading the loading slurry on the carrier includes: after the loading slurry is mixed with the carrier and loaded, a third drying and a third calcination treatment are performed to obtain the integral carbon monoxide catalyst.

4. The method for preparing the integral carbon monoxide catalyst according to claim 3, characterized in that: The mass ratio of the titanium oxide to the cerium oxide is (3-6):1; And / or, the particle size range of the product after the first ball milling is: 1nm to 100nm; and / or, the particle size range of the first intermediate product is 1 nm to 100 nm; and / or, in the auxiliary agent, the molar concentration of the solute is 0.001 mol / L to 10 mol / L; And / or, the mass ratio of the first intermediate product to the ammonium source is (6-18):1; and / or, in the metal nitrate solution, the concentration of the solute is 8 g / L to 14 g / L; and / or, the mass ratio of the cobalt source to the third intermediate product is 1:(6-10); and / or, the mass ratio of the second intermediate product to the metal nitrate solution is (1-3):2; and / or, in the third intermediate product, the loading amount of the metal particles is 0.1 wt% to 2 wt%; And / or, the particle size range of the product after the second ball milling treatment is: 1nm ~ 100nm.

5. The method for preparing an integral carbon monoxide catalyst according to claim 3, wherein the mass fractions of the components in the loaded slurry include 5% to 50% of the fourth intermediate product, 0.2% to 15% of the dispersant, 0.1% to 15% of the thickener and 1% to 15% of the binder.

6. The method for preparing a monolithic carbon monoxide catalyst according to any one of claims 3 to 5, characterized in that: In the first ball milling process, the ball-to-material mass ratio is (3.5-10):1; the rotation speed is 400 rpm-600 rpm, and the time is 1 h-1.5 h; And / or, the temperature of the first calcination treatment is 450°C to 550°C, and the time is 1h to 2h; And / or, in the second ball milling process, the mass ratio of the ball material is (3.5-10):1, the rotation speed is 400 rpm-600 rpm, and the ball milling time is 1 h-1.5 h; And / or, the calcination temperature of the second calcination treatment is 400°C to 600°C, and the calcination time is 2h to 5h; And / or, in the third calcination treatment, the calcination temperature is 200° C. to 350° C., and the calcination time is 1 hour to 10 hours.

7. The method for preparing the integral carbon monoxide catalyst according to claim 6, characterized in that: The step of mixing the ammonium source, the auxiliary agent and the first intermediate product solution comprises: stirring at a constant temperature of 50° C. to 80° C. for 1 h to 4 h, and adding the auxiliary agent while stirring to maintain the pH value of the reaction solution at 1.2 to 3.6; And / or, the second calcination treatment step includes: grinding the dried reaction product solid into powder, and calcining at 500° C. to 600° C. for 1 h to 2 h to obtain the third intermediate product.

8. The method for preparing the integral carbon monoxide catalyst according to claim 6, characterized in that: The ammonium source includes at least one of ammonium molybdate, ammonium phosphate, ammonium metavanadate, and ammonium tungstate; And / or, the auxiliary agent is an acid solution or an alkaline solution; and / or, the metal element in the metal nitrate solution includes one or more of cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum; And / or, the cobalt source comprises cobalt tetroxide; And / or, the binder includes one or more of calcium silicate, sodium silicate, calcium aluminate, phenolic resin, diatomaceous earth, aluminum sol, silica sol, kaolin, attapulgite, sodium silicate, bentonite, montmorillonite, and pseudo-boehmite; and / or, the dispersant comprises one or more of polyacrylic acid, polypropylene, polystyrene, polyethylene wax, polyethylene ether, polyvinyl ester, polyvinyl acetate, polyethylene, polyacrylamide, sodium polyacrylate, polyethylene glycol, and polyvinyl alcohol; and / or, the thickener comprises one or more of hydroxymethyl cellulose, hydroxymethyl propyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, cellulose ether, and starch; And / or, the water retaining agent includes one or more of glycerol, lignin, sodium alginate, polyacrylamide, sodium polyacrylate, potassium polyacrylate, and ammonium polyacrylate.

9. The method for preparing the integral carbon monoxide catalyst according to claim 8, characterized in that: The acid solution includes at least one of citric acid solution, tartaric acid solution, hydrochloric acid solution, acetic acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution; And / or, the alkaline solution includes one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and ammonia water.

10. Use of an integral carbon monoxide catalyst prepared by the preparation method according to any one of claims 2 to 9 in catalysis of carbon monoxide in flue gas.

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