A sulfur-resistant and moisture-resistant CO oxidation regular structure catalyst, a preparation method and application thereof

Abstract

The application provides a sulfur-resistant and moisture-resistant CO oxidation regular structure catalyst and a preparation method and application thereof, and is suitable for the field of catalyst technology. The preparation method comprises the following steps: placing glass fiber corrugated board in a mixed gas to obtain surface-hydroxylated glass fiber corrugated board; obtaining glass fiber corrugated board loaded with single-layer silicon oxide; generating a porous silicon oxide layer on the surface of the glass fiber corrugated board loaded with single-layer silicon oxide to obtain glass fiber corrugated board loaded with double-layer silicon oxide; placing the glass fiber corrugated board loaded with double-layer silicon oxide in an impregnation liquid for impregnation, and then performing drying, calcination and reduction to obtain the sulfur-resistant and moisture-resistant CO oxidation regular structure catalyst. The preparation method uses the glass fiber corrugated board as a carrier, uses TEOS as a silicon source, and uses a triblock copolymer P123 as a template agent. Through a gas phase deposition process, the double-layer silicon oxide is continuously covered on the surface of the glass fiber corrugated board carrier. Then, through impregnation and calcination, the iron oxide and platinum catalytic components are loaded on the surface of the double-layer silicon oxide layer. The regular catalyst does not need to be formed and can be directly filled and applied.

Description

Technical Field

[0001] This application relates to the field of catalyst technology, specifically to a sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst, its preparation method, and its application. Background Technology

[0002] The steel industry is a crucial sector for my country's goal of achieving peak carbon emissions and carbon neutrality, resulting in green and low-carbon development. Sintering flue gas emitted during steel production contains a large amount of pollutants, with CO concentrations reaching 4,000-10,000 ppm, making it one of the most significant air pollutants in steel production areas. In 2024, five departments, including the National Development and Reform Commission, issued the "Special Action Plan for Energy Conservation and Carbon Reduction in the Steel Industry," requiring accelerated energy-saving and carbon-reduction transformation and equipment upgrades in the steel industry. CO purification and emission reduction in sintering flue gas is a critical area that urgently needs breakthroughs.

[0003] Currently, methods for reducing CO in sintering flue gas include steam injection into the sintering material surface, flue gas recirculation, oxygen-enriched combustion, and sintering process control. However, while these methods ensure the quality of sintered products, they are difficult to efficiently eliminate CO. Catalytic oxidation, on the other hand, catalytically oxidizes CO into non-toxic and harmless CO2 gas. By installing a CO catalytic reaction device between the desulfurization and denitrification processes, the chemical heat energy released by the CO oxidation reaction can be effectively utilized. The heat released from the complete oxidation of CO in the flue gas can raise the flue gas temperature by 30-40°C, which can replace traditional blast furnace gas supplementary heating, significantly reducing fuel consumption and carbon emissions. It has the advantages of low energy consumption and high efficiency.

[0004] Since sintering flue gas emitted during the steel industry production process contains small amounts of SO2 and water vapor, CO oxidation catalysts are easily deactivated during operation. Therefore, developing sulfur- and moisture-resistant CO oxidation catalysts is crucial for eliminating CO pollutants from sintering flue gas and comprehensively utilizing the heat of reaction. Existing technologies have numerous reports on sulfur- and moisture-resistant CO oxidation catalysts.

[0005] Patent CN116020459A discloses a sulfur-resistant and water-resistant CO catalyst, its preparation method, and its application. This method uses ZrO2-WO3 or ZrO2-WO3-R as a support and PdO2 as the catalyst substrate. x PtO x Alternatively, RuO2 can be used as the active component. The catalyst is formed by batch calcination, and after continuous testing for 100 hours in the presence of 100ppm SO2 and 10vol.% H2O, the CO conversion rate can be maintained above 90%.

[0006] Patent CN119588375A discloses a sulfur-resistant noble metal-based CO oxidation catalyst, its preparation method, and its application. The method involves immersing a support in an aqueous solution containing a noble metal precursor and an auxiliary precursor, followed by drying and calcination to obtain a catalyst matrix. The catalyst matrix is ​​then pre-reduced in a hydrogen-containing atmosphere to obtain a catalyst intermediate. The catalyst intermediate is then induced and activated in an atmosphere containing CO and H₂S. The support is composed of titanium oxide, cerium oxide, alumina, and zirconium oxide, while the auxiliary precursor contains metal elements such as Fe, Co, and Ni. This catalyst enables highly selective oxidation of H₂S species, inhibits the adsorption of sulfur species and sulfate formation, and achieves a high-conversion oxidation reaction of CO in the presence of H₂S.

[0007] Patent CN119857491A discloses a sulfur-resistant CO oxidation catalyst, its preparation method, and its application. The method includes: (1) contacting a platinum source with a substrate to be plated in the presence of a carrier gas to carry out a first contact reaction, obtaining material I; (2) passivating material I with a modifier in the presence of a carrier gas to obtain a passivated material; (3) carrying out a second contact reaction with a second metal source to obtain material II; (4) carrying out a third contact reaction with a hydrazine reducing agent and calcining the product obtained after the third contact reaction to obtain a sulfur-resistant CO oxidation catalyst. The sulfur-resistant CO oxidation catalyst prepared by the method provided by this invention has high metal additive dispersion, high catalytic conversion rate, low activation temperature, and excellent catalytic stability in a sulfur-containing atmosphere.

[0008] Patent CN119281336A discloses a high-entropy intermetallic compound catalyst resistant to sulfur and CO, its preparation method, and its application. The catalyst is a Ni-Co-Cu-Fe-In-M high-entropy intermetallic compound catalyst obtained by supporting a Ni-Co-Cu-Fe-In-M hexa-metallic compound on a mixed aluminum-magnesium metal oxide. Among them, Ni, Co, Cu, and Fe are active metals, In is an inert metal, and M is a sulfur-resistant metal, which is one of Zn, Mo, and Ce. This catalyst, by utilizing the synergistic effect between multiple elements in the high-entropy intermetallic compound catalyst, exhibits excellent CO resistance, overcoming the technical bottleneck of insufficient CO resistance and sulfur resistance of existing catalysts.

[0009] Patent CN114904517A discloses a method for preparing a sulfur-resistant hydrophobic CO oxidation catalyst. The method includes: preparing hydrophobic TiO2 powder using deionized water, ethanol, expanded graphite, TiO2, and fatty acid glycerides; preparing a first solution using a Pt salt solution, NH3·H2O to adjust the solution, and an alkali (earth) metal salt; introducing the hydrophobic TiO2 powder into the first solution to obtain a second solution; and treating the second solution to obtain the sulfur-resistant hydrophobic CO oxidation catalyst powder. The sulfur-resistant hydrophobic CO oxidation catalyst prepared using the method described in this application uses inexpensive and readily available raw materials, and the process is simple.

[0010] Patent CN119897100A discloses a catalyst resistant to CO oxidation by multiple impurity elements and its preparation method and application. The catalyst consists of a TiO2 support and active component elements and auxiliary elements supported on the surface of the TiO2 support. The active component elements are selected from at least one of Pt, Pd, and Ru; the auxiliary elements are selected from at least one of Sn, V, Mo, Nb, Zr, Cr, and Mn; the mass content of the active component elements is 1~20wt%, and the mass content of the auxiliary elements is 0.05~1.5wt%; the crystal form of the TiO2 support is selected from anatase or rutile; the active component elements exist in the form of highly dispersed single atoms, clusters, or nanoparticles in a high valence state; the catalyst has excellent CO oxidation activity and resistance to poisoning by multiple impurity elements.

[0011] In summary, the patents disclosed above all disclose powdered CO oxidation catalysts and their preparation methods. When applied, they need to be shaped, and the shaping process requires the addition of binders and other additives. The introduction of these additives will change the catalytic performance of the powdered catalyst and may even reduce its sulfur resistance and moisture resistance. Summary of the Invention

[0012] To address one of the aforementioned technical deficiencies, this application provides a sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst, its preparation method, and its application.

[0013] According to the first aspect of this application, a method for preparing a sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst is provided, comprising the following steps:

[0014] S1. Place the fiberglass corrugated material in a mixed gas and treat it at 100~200℃ for 1~3 hours to obtain surface-hydroxylated fiberglass corrugated material; the mixed gas includes water vapor and an inert gas;

[0015] S2. Using air as the carrier gas, tetraethyl orthosilicate (TEOS, Si(OC2H5)4) is carried into the mixed gas by bubbling. Then, it is passed into a tube furnace containing surface-hydroxylated glass fiber corrugated material. The furnace temperature is controlled at 400~500℃. TEOS undergoes thermal decomposition, and the thermal decomposition products are deposited on the surface-hydroxylated glass fiber corrugated material to form a dense silicon oxide layer, thus obtaining glass fiber corrugated material loaded with a single layer of silicon oxide.

[0016] S3. Using oxygen as the carrier gas, droplets formed from the mixed solution are carried into the mixed gas by a bubbling method, and then passed into a tube furnace containing fiberglass corrugated fiberglass loaded with a single layer of silica. The furnace temperature is controlled at 350~450℃. The droplets formed from the mixed solution undergo thermal decomposition, and the thermal decomposition products are deposited on the surface of the dense silica layer to form a porous silica layer, thus obtaining fiberglass corrugated fiberglass loaded with a double layer of silica. The mixed solution includes TEOS and polyoxyethylene-polyoxypropylene-polyoxyethylene (P123).

[0017] S4. The obtained glass fiber corrugated fiber loaded with double layer of silica is immersed in an impregnation solution and then dried; the impregnation solution includes an ethanol solution containing ferric nitrate and an ethanol solution containing chloroplatinic acid.

[0018] S5. The dried glass fiber corrugated material loaded with double-layer silica was placed in a tube furnace for calcination. The calcined product was uniformly loaded on the surface of the porous silica layer. Then, hydrogen was introduced into the tube furnace and reduced at 200~300℃ for 4h to obtain a sulfur-resistant and moisture-resistant CO oxidation regular structure catalyst.

[0019] Preferably, in step S1, the volume ratio of water vapor to inert gas is 1:5 to 1:10, and the flow rate of the mixed gas is 20 to 50 mL / min; the inert gas is nitrogen or argon.

[0020] Preferably, in step S2, the air flow rate is 30-80 mL / min, and when TEOS is carried into the mixed gas by bubbling, the bubbling temperature is 20-40°C; when the thermal decomposition products are deposited on the surface of the hydroxylated glass fiber corrugated to form a dense silicon oxide layer, the deposition time is 2-4 hours; and the thickness of the dense silicon oxide layer is 50-200 nm.

[0021] Preferably, in step S3, the mass ratio of TEOS to P123 in the mixed solution is 5:1 to 10:1, and the mass fraction of TEOS in the mixed solution is 10% to 20%; the flow rate of oxygen is 20 to 60 mL / min; when the thermal decomposition products are deposited on the surface of the dense silicon oxide layer to form a porous silicon oxide layer, the deposition time is 3 to 6 hours; the thickness of the porous silicon oxide layer is 200 to 500 nm, and the pore size is 5 to 20 nm.

[0022] Preferably, in step S4, the concentration of ferric nitrate in the impregnation solution is 0.05~0.2 mol / L, the concentration of chloroplatinic acid is 0.005~0.02 mol / L, and the molar ratio of ferric nitrate to chloroplatinic acid is 5~20:1; the impregnation is ultrasonic impregnation, and the impregnation time is 30~60 min; the drying temperature is 100~120℃.

[0023] Preferably, in step S5, the calcination is carried out in an air atmosphere, and the calcination temperature is 350~450℃, and the calcination time is 2~4h; the purity of the hydrogen is ≥99.9%, and the hydrogen flow rate is 50~100mL / min; the Pt loading in the sulfur-resistant and moisture-resistant CO oxidation regular structure catalyst is 0.1%~1% based on the total mass of the catalyst.

[0024] Preferably, the regular structure of the sulfur-resistant and moisture-resistant CO oxidation ordered catalyst is a cylinder, a cube, or a polygonal prism.

[0025] Preferably, the fiberglass corrugated material is a glass fiber reinforced composite material, and the thickness of the fiberglass corrugated material is 0.5~2mm, the height of the fiberglass corrugated material is 5~10mm, and the spacing of the fiberglass corrugated material is 10~20mm.

[0026] According to a second aspect of this application, a sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst is provided, which is prepared according to the preparation method of the sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst described in any of the preceding claims.

[0027] According to a third aspect of this application, an application is provided for a sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst, wherein the catalyst is the aforementioned sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst, used for the oxidation of CO in sintering flue gas.

[0028] The beneficial effects of this application are as follows:

[0029] This application provides a method for preparing a sulfur-resistant and moisture-resistant CO oxidation ordered catalyst. Using corrugated fiberglass as a support, TEOS as a silicon source, and triblock copolymer P123 as a template agent, a double-layer silica continuous coating is achieved on the surface of the corrugated fiberglass support via vapor deposition. Then, iron oxide and platinum catalytic active components are loaded onto the surface of the double silica layer through impregnation and calcination. This ordered catalyst does not require molding and can be directly loaded for application. Specifically, the double silica layer loaded on the corrugated fiberglass surface protects the support from corrosion by moisture and SO2 in flue gas during long-term use, while the porous outer silica layer increases the specific surface area of ​​the support, resulting in a highly dispersed state of the catalytic active components Pt and Fe2O3. Furthermore, the high-temperature treated silica layer has a hydrophobic surface, preventing water molecules from agglomerating on the catalyst surface and causing poisoning, thus achieving sulfur-resistant and moisture-resistant catalytic function. Simultaneously, using corrugated fiberglass as a support allows the molded catalyst to have a large gas flux and low gas passage resistance. Furthermore, through the synergistic effect among its components, this catalyst effectively improves its catalytic activity and resistance to sulfur and moisture.

[0030] Other features and advantages of this application will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the application. The objectives and other advantages of this application may be realized and obtained by means of what is pointed out in the written description, claims, and drawings. Attached Figure Description

[0031] The accompanying drawings, which are included to provide a further understanding of this application and form part of this application, illustrate exemplary embodiments and are used to explain this application, but do not constitute an undue limitation of this application. In the drawings:

[0032] Figure 1 XRD pattern of the sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst provided in this application;

[0033] Figure 2 A diagram showing the complete CO conversion temperature of the sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst provided in this application;

[0034] Figure 3 A schematic diagram of the catalytic effect evaluation device provided in this application;

[0035] In the diagram, 10 is a mixer, 20 is a gas supply assembly, 30 is a fixed-bed reactor, 40 is a pipeline electric heater, 50 is a flue gas analyzer, 201 is a CO cylinder, 202 is an SO2 cylinder, 203 is an N2 cylinder, 204 is a fan, and 205 is a humidifier. Detailed Implementation

[0036] To make the technical solutions and advantages of the embodiments of this application clearer, the exemplary embodiments of this application will be described in further detail below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, and not an exhaustive list of all embodiments. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of this application can be combined with each other.

[0037] Unless otherwise specified, the reagents and materials used in the examples are commercially available; the test methods used in the following examples are conventional methods in the art.

[0038] The amount of raw materials added and the reaction conditions in Examples 1 to 3 are shown in Table 1 below.

[0039] The preparation method of the sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst in Examples 1 to 3 of this application includes the following steps:

[0040] S1. Place the fiberglass corrugated material in a mixed gas and treat it at 100~200℃ for 1~3h to hydroxylate the surface of the fiberglass corrugated material, resulting in surface-hydroxylated fiberglass corrugated material. This facilitates chemical bonding with the subsequently thermally decomposed silicon oxide, forming a stable and non-detachable load layer. The mixed gas includes water vapor and an inert gas, with a volume ratio of water vapor to inert gas of 1:5~1:10 and a flow rate of 20~50mL / min. The fiberglass corrugated material is a glass fiber reinforced composite material, with a thickness of 0.5~2mm, a height of 5~10mm, and a spacing of 10~20mm.

[0041] S2. Using air as the carrier gas, TEOS is carried into the mixed gas by a bubbling method (bubbling temperature 20~40℃), and then passed into a tube furnace containing surface-hydroxylated glass fiber corrugated material. The furnace temperature is controlled at 400~500℃. TEOS undergoes thermal decomposition in the gas phase, and the thermal decomposition product SiO2 is densely deposited (deposition time 2~4h) on the surface-hydroxylated glass fiber corrugated material to form a dense silicon oxide layer, thus obtaining glass fiber corrugated material loaded with a single layer of silicon oxide. The air flow rate is 30~80mL / min; the thickness of the dense silicon oxide layer is 50~200nm.

[0042] S3. Using oxygen as the carrier gas, droplets formed from the mixed solution are carried into the mixed gas using a bubbling method. The gas is then passed into a tube furnace containing fiberglass corrugated fiberglass loaded with a single layer of silica. The furnace temperature is controlled at 350-450°C. The droplets formed from the mixed solution in the gas phase undergo thermal decomposition, and the decomposition product, SiO2, is deposited (deposition time 3-6 hours) on the surface of the dense silica layer to form a porous silica layer, resulting in fiberglass corrugated fiberglass loaded with a double layer of silica. The mixed solution includes TEOS and P123, with a TEOS to P123 mass ratio of 5:1-10:1. The mass fraction of TEOS in the mixed solution is 10%-20%, and the oxygen flow rate is 20-60 mL / min. The thickness of the porous silica layer is 200-500 nm, and the pore size is 5-20 nm.

[0043] S4. Place the obtained glass fiber corrugated fiber loaded with double-layer silica in an impregnation solution and ultrasonically impregnate for 30-60 minutes. After removal, dry at 100-120°C. The impregnation solution includes an ethanol solution containing ferric nitrate and an ethanol solution containing chloroplatinic acid, wherein the concentration of ferric nitrate is 0.05-0.2 mol / L, the concentration of chloroplatinic acid is 0.005-0.02 mol / L, and the molar ratio of ferric nitrate to chloroplatinic acid is 5-20:1.

[0044] S5. Place the dried fiberglass corrugated material loaded with double-layer silica in a tube furnace and calcine it at 350~450℃ for 2~4h in an air atmosphere to decompose ferric nitrate and chloroplatinic acid into ferric oxide and platinum oxide respectively, and uniformly load them onto the surface of the porous silica layer on the outer layer of the fiberglass corrugated material.

[0045] Subsequently, hydrogen gas with a purity ≥99.9% was introduced into the tubular furnace at a flow rate of 50~100 mL / min, and the reduction was carried out at 200~300℃ for 4 h. Platinum oxide was reduced by hydrogen gas to form metallic Pt active sites, thus obtaining a sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst. The Pt loading in the sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst was 0.1%~1% (based on the total mass of the catalyst).

[0046] This application provides a method for preparing a sulfur-resistant and moisture-resistant CO oxidation ordered catalyst. Using corrugated fiberglass as a support, TEOS as a silicon source, and triblock copolymer P123 as a template agent, a double-layer silica continuous coating is achieved on the surface of the corrugated fiberglass support via vapor deposition. Then, iron oxide and platinum catalytic active components are loaded onto the surface of the double silica layer through impregnation and calcination. This ordered catalyst does not require molding and can be directly loaded for application. Specifically, the double silica layer loaded on the corrugated fiberglass surface protects the support from corrosion by moisture and SO2 in flue gas during long-term use, while the porous outer silica layer increases the specific surface area of ​​the support, resulting in a highly dispersed state of the catalytic active components Pt and Fe2O3. Furthermore, the high-temperature treated silica layer has a hydrophobic surface, preventing water molecules from agglomerating on the catalyst surface and causing poisoning, thus achieving sulfur-resistant and moisture-resistant catalytic function. Simultaneously, using corrugated fiberglass as a support allows the molded catalyst to have a large gas flux and low gas passage resistance. Furthermore, through the synergistic effect among its components, this catalyst effectively improves its catalytic activity and resistance to sulfur and moisture.

[0047] Furthermore, the inert gas is nitrogen or argon.

[0048] Furthermore, the regular shape of the sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst is a cylinder, a cube, or a polygonal prism. The regular shape of the catalyst is the shape of the glass fiber corrugation, wherein the corrugation direction of the polygonal prism glass fiber corrugation is parallel to the reaction fluid channel, reducing fluid resistance, improving the contact efficiency between CO and the catalytic components, and reducing the accumulation of impurities on the support surface.

[0049]

[0050] The reaction principle and related reaction equations of the above preparation method are as follows:

[0051] In step S1, the main component of the glass fiber corrugated surface is silicon dioxide (SiO2), which reacts with water vapor to generate surface hydroxyl groups. This is due to the breakage of silicon-oxygen bonds and the combination of hydroxyl groups, resulting in an increase in the surface hydroxyl group density.

[0052] SiO2(surface) + H2O (g) → SiO2-OH(surface) + Si-OH(surface);

[0053] In step S2, TEOS undergoes thermal decomposition in air to generate SiO2 (a dense layer):

[0054] Si(OC2H5)4(g) + O2(g) → SiO2(s) + 4C2H4O(g) (400~500℃);

[0055] In step S3, TEOS undergoes thermal decomposition to generate a SiO2 framework:

[0056] Si(OC2H5)4(g) + O2(g) → SiO2(s) + 4C2H4O(g) (350~450℃);

[0057] P123 oxidative decomposition (removal of template agent, formation of channels):

[0058] (C2H4O) m -(C3H6O) n -(C2H4O) m +(3m+4.5n)O2→(2m+3n)CO2+(3m+3n)H2O (350~450℃);

[0059] In step S5, ferric nitrate decomposes into ferric oxide:

[0060] 4Fe(NO3)3→2Fe2O3(s)+12NO2(g)+3O2(g) (350~450℃);

[0061] Chloroplatinic acid decomposes into platinum oxide (intermediate state):

[0062] H2PtCl6·6H2O→PtO2(s)+6HCl(g)+4H2O(g) (350~450℃);

[0063] Hydrogen reduces platinum oxide to form metallic Pt:

[0064] PtO2(s)+2H2(g)→Pt(s)+2H2O(g) (200~300℃);

[0065] Under these reducing conditions, Fe2O3 cannot be reduced by H2, and the stable Fe-O bond in Fe2O3 is difficult to break at 200~300℃, so the reaction hardly occurs, thus realizing the coating of catalytically active components Pt and Fe2O3 on the surface of silicon oxide.

[0066] The above reactions include support surface modification, silica deposition, template removal, and formation of catalytically active components, ultimately constructing a well-structured CO oxidation catalyst with sulfur and moisture resistance.

[0067] To demonstrate the beneficial effects of the sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst prepared by the preparation method of this application, the sulfur-resistant and moisture-resistant CO oxidation ordered structure catalysts Cat-1 to Cat-3 prepared in Examples 1 to 3 were tested.

[0068] This application used X-ray diffraction to characterize the phase structures of the sulfur-resistant and moisture-resistant CO oxidation ordered catalysts Cat-1~Cat-3 prepared in Examples 1 to 3, and obtained the corresponding XRD patterns, as shown below. Figure 1 As shown. By Figure 1 It can be seen that the sulfur-resistant and moisture-resistant CO oxidation ordered structure catalysts prepared in Examples 1 to 3 all showed characteristic peaks of Fe2O3 at 33.1° and 35.6° (JCPDS No. 39-1346), and characteristic peaks of Pt at 39.8° (JCPDS No. 04-0802), proving that the Fe2O3 and Pt active components were successfully loaded on the surface of the catalyst and were uniformly dispersed.

[0069] This application tested the CO complete conversion temperature of the sulfur-resistant and moisture-resistant CO oxidation ordered structure catalysts Cat-1~Cat-3 prepared in Examples 1 to 3, such as... Figure 2 As shown. By Figure 2 It can be seen that the complete CO conversion temperatures of the sulfur-resistant and moisture-resistant CO oxidation ordered catalysts prepared in Examples 1 to 3 are 225℃, 230℃ and 228℃, respectively, which are lower than the complete CO conversion temperatures of existing powdered CO oxidation catalysts, further demonstrating the mass transfer advantages of ordered catalysts.

[0070] This application uses a catalytic performance evaluation device to test the catalytic performance of the sulfur-resistant and moisture-resistant CO oxidation ordered structure catalysts Cat-1 to Cat-3 prepared in Examples 1 to 3.

[0071] like Figure 3 As shown, the catalytic effect evaluation device includes:

[0072] Mixer 10;

[0073] The gas supply assembly 20 includes a CO cylinder 201, an SO2 cylinder 202, an N2 cylinder 203, a fan 204, and a humidifier 205. The CO cylinder 201 is connected to the first inlet of the mixer 10 via a first valve and a first flow meter. The SO2 cylinder 202 is connected to the second inlet of the mixer 10 via a second valve and a second flow meter. The N2 cylinder 203 is connected to the third inlet of the mixer 10 via a third valve and a third flow meter. The outlet of the fan 204 is connected to the inlet of the humidifier 205 via a fourth flow meter and a fourth valve. The outlet of the humidifier 205 is connected to the fourth inlet of the mixer 10.

[0074] The fixed-bed reactor 30 has its inlet connected to the outlet of the mixer 10 via a pipeline electric heater 40, and its outlet is connected to an exhaust pipe, with the exhaust port of the exhaust pipe connected to the outside.

[0075] The flue gas analyzer 50 has its inlet connected to its exhaust pipe via a fifth valve. In practice, after the flow rates of CO, SO2, and N2 stabilize, the fifth valve is opened, connecting the exhaust pipe to the flue gas analyzer 50.

[0076] Specifically, the first flow meter, the second flow meter, the third flow meter, and the fourth flow meter are all gas mass flow meters used to regulate the gas flow rate.

[0077] The catalytic performance testing method is as follows: the sulfur-resistant and moisture-resistant CO oxidation ordered structure catalyst prepared in this application is loaded into the fixed bed reactor 30. Turn on the blower 204 and adjust the air volume. Turn on the pipeline electric heater 40 to raise the temperature to about 200℃. Then open the valves of the CO, SO2, and N2 cylinders, adjust the CO flow rate to achieve a CO concentration of 3000ppm, and adjust the SO2 flow rate to achieve an SO2 concentration of 500ppm. The blower 204 introduces air, which is humidified by the humidifier 205 to increase the moisture content in the air. After the CO, SO2, and N2 flow rates stabilize, the exhaust pipe is connected to the flue gas analyzer 50. The CO, SO2, and N2 gases, along with the humidified air, are thoroughly mixed in the mixer 10 to obtain the feed gas. This feed gas is heated by the pipeline electric heater 40 and then enters the fixed-bed reactor 30, where it reacts under the action of the catalyst. Part of the reacted gas is analyzed by the flue gas analyzer 50 to detect changes in the CO component content and calculate the CO conversion rate, thereby evaluating the catalyst performance. The other part is discharged from the device. Furthermore, during the catalytic performance testing process, the water vapor content in the feed gas was 10% (volume percentage) during stable operation, and the catalyst space velocity was 10000 h⁻¹. -1 The inlet temperature of the mixed gas is 230℃, the bed temperature of the fixed bed reactor is 270℃, and the pressure drop of the catalyst bed is 300Pa.

[0078] Specifically, the formula for calculating CO conversion rate is as follows:

[0079] ;

[0080] In the formula, x represents the CO conversion rate, and CO in This indicates the concentration of CO in the feed gas. out This indicates the CO outlet concentration (i.e., the concentration of CO discharged from the fixed-bed reactor 30).

[0081]

[0082] As shown in Table 2, the sulfur-resistant and moisture-resistant CO oxidation ordered catalysts Cat-1 to Cat-3 prepared in this application achieve a CO conversion rate of 99.6% to 99.8% under conditions of CO concentration of 3000 ppm, SO2 concentration of 500 ppm, and water vapor content of 10%. In summary, the catalysts prepared in this application exhibit high catalytic activity and good catalytic efficiency, and possess excellent sulfur and moisture resistance. They can be directly applied to the treatment of CO in sintering flue gas in the steel industry, thus overcoming the performance degradation defect of powdered CO oxidation catalysts during molding.

[0083] Furthermore, this application also specifies that the catalysts in Examples 1 to 3 have a water vapor content of 10% (volume percentage) in the feed gas and a catalyst space velocity of 10000 h⁻¹. -1 Under the conditions of a mixed gas inlet temperature of 230℃, a fixed-bed reactor bed temperature of 270℃, and a catalyst bed pressure drop of 300Pa, the CO conversion rate was maintained at 99% after 100 hours of continuous testing.

[0084] In the description of this application, it should be understood that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0085] In this application, unless otherwise expressly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection, an electrical connection, or a connection that allows communication between them; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication between two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0086] Although preferred embodiments of this application have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments as well as all changes and modifications falling within the scope of this application.

[0087] Obviously, those skilled in the art can make various modifications and variations to this application without departing from the spirit and scope of this application. Therefore, if such modifications and variations fall within the scope of the claims of this application and their equivalents, this application also intends to include such modifications and variations.

Claims

1. A process for the preparation of a sulfur and moisture resistant CO oxidation shape selective catalyst, characterized in that, The method comprises the following steps: S1, placing the glass fiber corrugated board in a mixed gas, and treating at 100-200℃ for 1-3h to obtain a surface-hydroxylated glass fiber corrugated board; the mixed gas comprises water vapor and an inert gas; S2, carrying TEOS into the mixed gas by bubbling with air as the carrier gas, then introducing into a tubular furnace containing the surface-hydroxylated glass fiber corrugated board, and controlling the furnace temperature of the tubular furnace at 400-500℃, so that TEOS is thermally decomposed, and the thermal decomposition product is deposited on the surface of the surface-hydroxylated glass fiber corrugated board to form a dense silicon oxide layer, thereby obtaining a glass fiber corrugated board loaded with a single-layer silicon oxide; S3, carrying the droplets of the mixed solution into the mixed gas by bubbling with oxygen as the carrier gas, then introducing into a tubular furnace containing the glass fiber corrugated board loaded with a single-layer silicon oxide, and controlling the furnace temperature of the tubular furnace at 350-450℃, so that the droplets of the mixed solution are thermally decomposed, and the thermal decomposition product is deposited on the surface of the dense silicon oxide layer to form a porous silicon oxide layer, thereby obtaining a glass fiber corrugated board loaded with a double-layer silicon oxide; the mixed solution comprises TEOS and P123; S4, immersing the obtained glass fiber corrugated board loaded with a double-layer silicon oxide in an immersion liquid, and then drying; the immersion liquid comprises an ethanol solution containing ferric nitrate and an ethanol solution containing chloroplatinic acid; S5, calcining the dried glass fiber corrugated board loaded with a double-layer silicon oxide in a tubular furnace, so that the calcination product is uniformly loaded on the surface of the porous silicon oxide layer; then introducing hydrogen into the tubular furnace, and reducing at 200-300℃ for 4h to obtain a sulfur and moisture resistant CO oxidation regular structure catalyst.

2. The preparation method of the sulfur-resistant and moisture-resistant CO oxidation shape-selective catalyst according to claim 1, characterized in that, In S1, the volume ratio of water vapor to inert gas is 1:5-1:10, and the flow rate of the mixed gas is 20-50mL / min; The inert gas is nitrogen or argon.

3. The preparation method of the sulfur-resistant and moisture-resistant CO oxidation shape-selective catalyst according to claim 1, characterized in that, In S2, the flow rate of air is 30-80mL / min; when TEOS is carried into the mixed gas by bubbling, the bubbling temperature is 20-40℃; when the thermal decomposition product is deposited on the surface of the surface-hydroxylated glass fiber corrugated board to form a dense silicon oxide layer, the deposition time is 2-4h; The thickness of the dense silicon oxide layer is 50-200nm.

4. The preparation method of the sulfur-resistant and moisture-resistant CO oxidation shape-selective catalyst according to claim 1, characterized in that, In S3, the mass ratio of TEOS to P123 in the mixed solution is 5:1-10:1, and the mass fraction of TEOS in the mixed solution is 10%-20%; the flow rate of oxygen is 20-60mL / min; when the thermal decomposition product is deposited on the surface of the dense silicon oxide layer to form a porous silicon oxide layer, the deposition time is 3-6h; The thickness of the porous silicon oxide layer is 200-500nm, and the pore size is 5-20nm.

5. The preparation method of the sulfur-resistant and moisture-resistant CO oxidation shape-selective catalyst according to claim 1, characterized in that, In S4, the concentration of ferric nitrate in the immersion liquid is 0.05-0.2mol / L, the concentration of chloroplatinic acid is 0.005-0.02mol / L, and the molar ratio of ferric nitrate to chloroplatinic acid is 5-20:1; The immersion is ultrasonic immersion, and the immersion time is 30-60min; The drying temperature is 100-120℃.

6. The preparation method of the sulfur-resistant and moisture-resistant CO oxidation shape-selective catalyst according to claim 1, characterized in that, The calcining in the S5 is performed in an air atmosphere, and the calcining temperature is 350-450 DEG C, and the calcining time is 2-4h; The purity of the hydrogen is greater than or equal to 99.9%, and the hydrogen flow rate is 50-100 mL / min; The Pt loading in the anti-sulfur and moisture-resistant CO oxidation regular structure catalyst is 0.1%-1% based on the total mass of the catalyst.

7. The method of claim 1, wherein the method is characterized by: The regular structure of the anti-sulfur and moisture-resistant CO oxidation regular structure catalyst is a cylinder, a cube or a multi-prism.

8. The method of claim 1, wherein the preparation of the sulfur and moisture resistant CO oxidation catalyst with a regular structure is characterized by, The glass fiber corrugate is a glass fiber reinforced composite material, and the thickness of the glass fiber corrugate is 0.5-2 mm, the height of the glass fiber corrugate is 5-10 mm, and the spacing of the glass fiber corrugate is 10-20 mm.

9. A sulfur and moisture resistant, CO oxidation, regular structured catalyst, characterized in that, The anti-sulfur and moisture-resistant CO oxidation regular structure catalyst is prepared by the preparation method according to any one of claims 1-8.

10. Use of a sulfur and moisture resistant CO oxidation shapely structure catalyst, characterized in that, The catalyst is used for the oxidation of CO in sintering flue gas, and the catalyst is the anti-sulfur and moisture-resistant CO oxidation regular structure catalyst according to claim 9.

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