A water- and sulfur-resistant Pt-based catalyst and its preparation method

Abstract

This invention relates to the field of carbon monoxide catalyst technology, and more particularly to a water- and sulfur-resistant Pt-based catalyst and its preparation method. The catalyst is prepared by this method, which includes steps S1: preparing a CZ support; step S2: loading the active component Pt; step S3: doping with lanthanide oxides as an auxiliary agent to obtain a sulfur-resistant Pt-based catalyst; and step S4: hydrophobic modification to obtain a water- and sulfur-resistant Pt-based catalyst containing a hydrophobic layer. This invention can prepare a water- and sulfur-resistant Pt-based catalyst resistant to sulfur dioxide and water vapor. Furthermore, the active component Pt in this catalyst is uniformly and firmly bound to the CZ support, which solves the problem of Pt nanoparticle migration and agglomeration under the impact of high-temperature sintering flue gas in steel plants, leading to a decrease in catalytic activity.

Description

Technical Field

[0001] This invention relates to the field of carbon monoxide catalyst technology, and more particularly to a water- and sulfur-resistant Pt-based catalyst and its preparation method. Background Technology

[0002] As a major air pollutant, carbon monoxide emission control has become an important issue in the field of environmental protection. Especially in steel production, the carbon monoxide emitted contains a certain calorific value. Direct emission not only causes environmental pollution but also wastes energy. However, by using catalytic oxidation technology to catalytically oxidize carbon monoxide into carbon dioxide, carbon monoxide can be controlled, and the heat released by the reaction can be recovered and utilized, thus achieving the dual benefits of energy conservation and environmental protection.

[0003] Most existing carbon monoxide oxidation catalysts employ noble metal catalysts. While these catalysts can efficiently catalyze the oxidation of carbon monoxide over a wide temperature range, their active sites are prone to migration and aggregation under the complex and high-temperature conditions of steel plants, leading to a decrease in catalytic activity. Taking the common Pt / Al2O3 catalyst as an example, the impact of the high-temperature sintering flue gas in steel plants promotes the migration and aggregation of Pt nanoparticles in the catalyst, drastically reducing the number of originally highly dispersed Pt active sites and resulting in a decrease in catalytic activity.

[0004] Furthermore, the high-temperature sintering flue gas from steel plants has a complex composition, including not only carbon monoxide but also high concentrations of sulfur dioxide and a large amount of water vapor. These impurities can easily lead to a decrease in catalyst activity. For example, sulfur dioxide can react with the active sites of the catalyst to form sulfates, which cover the active centers and cause a decrease in catalyst activity; in the case of V2O5 / TiO2 catalysts, sulfur dioxide reacts with V... 5+ The reaction generates VOSO4, which not only clogs the catalyst pores but also reduces the catalyst's specific surface area, causing a sharp decline in catalytic activity. Water vapor not only dilutes the reactant concentration but may also participate in side reactions, generating hydroxyl species on some catalyst surfaces. This hinders the adsorption and activation of carbon monoxide by the catalyst, leading to a decrease in catalyst activity.

[0005] Therefore, it is necessary to provide a water- and sulfur-resistant Pt-based catalyst and its preparation method to solve the problems of decreased catalytic activity in existing carbon monoxide oxidation catalysts due to insensitivity to sulfur dioxide and water vapor, as well as the problem of decreased catalytic activity caused by the migration and aggregation of Pt nanoparticles under the impact of airflow from high-temperature sintering flue gas in steel plants. Summary of the Invention

[0006] The purpose of this invention is to provide a water- and sulfur-resistant Pt-based catalyst and its preparation method. The specific technical solution is as follows:

[0007] In a first aspect, the present invention provides a method for preparing a water- and sulfur-resistant Pt-based catalyst, comprising:

[0008] Step S1: Prepare the CZ vector;

[0009] Zirconium salt and cerium salt are added to water at a molar ratio of zirconium to cerium of 1:9~19. After the first stirring treatment, a mixed salt solution with a molar concentration of 0.3~0.6 mol / L is prepared.

[0010] Add alkali solution dropwise to the mixed salt solution and mix well until the pH is 9-10 to obtain a mixed solution containing precipitate;

[0011] After the precipitate-containing mixture is subjected to a second stirring treatment at 25-30°C, the solid phase is filtered out, and the solid phase is subjected to a first drying treatment and a first calcination treatment in sequence to obtain cubic CeO2-ZrO2, i.e., cubic CZ support; the stirring speed used in the second stirring treatment is 200-400 rpm, and the stirring time is 8-12 h.

[0012] Step S2: Loading the active component Pt;

[0013] Platinum salt is added to water and mixed to dissolve to obtain a platinum salt solution. Then, the CZ support that has been ground and sieved is added. After a third stirring treatment, the solution is subjected to a second drying treatment, a second calcination treatment and a third calcination treatment in sequence to obtain a Pt / CZ pre-prepared catalyst with the active component Pt uniformly loaded on the CZ support.

[0014] The platinum salt accounts for 0.5% to 2% of the mass of the CZ carrier; the second drying treatment uses vacuum drying at a temperature of 80 to 120°C for 3 to 6 hours; the second calcination treatment uses a calcination temperature of 320 to 380°C for 2 to 4 hours; and the third calcination treatment uses a calcination temperature of 500 to 650°C for 2 to 6 hours.

[0015] Step S3: Doping with lanthanide oxides as an auxiliary agent;

[0016] Lanthanum salt was added to water and stirred for the fourth time to obtain a lanthanum salt solution. The pH of the lanthanum salt solution was adjusted to 7-7.5 using a pH adjuster. The Pt / CZ pre-prepared catalyst was ground to the target particle size and added to the lanthanum salt solution. After stirring and mixing, it was subjected to evaporation, drying, and calcination in sequence to obtain a sulfur-resistant Pt-based catalyst.

[0017] The lanthanum salt accounts for 0.5% to 5% of the mass of the Pt / CZ pre-prepared catalyst.

[0018] Step S4: Hydrophobic modification;

[0019] The sulfur-resistant Pt-based catalyst was added to a silane hydrophobic agent solution, and after a fifth stirring treatment, it was subjected to a fourth drying treatment and a fifth calcination treatment to obtain a water-resistant and sulfur-resistant Pt-based catalyst containing a hydrophobic layer.

[0020] Optionally, the cerium salt includes cerium nitrate; the zirconium salt includes zirconium nitrate; and the alkaline solution includes either ammonia or an aqueous sodium hydroxide solution.

[0021] Optionally, the stirring speed used in the first stirring process is 400~1000 rpm, and the stirring time is 30~60 min;

[0022] The first drying process uses a drying temperature of 80~120℃ and a drying time of 8~12h;

[0023] The first calcination treatment uses a calcination temperature of 450~650℃ and a calcination time of 2~4h.

[0024] Optionally, in the platinum salt solution, the mass percentage of the platinum salt is 13% to 19%;

[0025] The platinum salt includes platinum nitrate.

[0026] Optionally, the grinding and sieving process involves grinding the CZ carrier into powder and then passing the powder through a 60-mesh sieve.

[0027] The third stirring process uses a stirring speed of 100-400 rpm and a stirring time of 30-60 min.

[0028] Optionally, in the lanthanum salt solution, the mass percentage of the lanthanum salt is 78.3%;

[0029] The lanthanum salt includes lanthanum nitrate;

[0030] The pH adjuster includes either an aqueous solution of sodium hydroxide or an ammonia solution.

[0031] Optionally, the target particle size is 2~5 nm;

[0032] The evaporation process uses an evaporation temperature of 60~100℃ until the food is completely dried.

[0033] The fourth stirring process uses a stirring speed of 150~300 rpm and a stirring time of 12~24 h;

[0034] The third drying process uses a drying temperature of 100~120℃ and a drying time of 2~4h.

[0035] The fourth calcination treatment uses a calcination temperature of 450~650℃ and a calcination time of 2~6h.

[0036] Optionally, the silane hydrophobic agent used in the silane hydrophobic agent solution has a volume percentage of 95%; the solvent used in the silane hydrophobic agent solution includes a 5% volume percentage ethanol solution; and the silane hydrophobic agent includes methyltrimethoxysilane.

[0037] Optionally, the fifth stirring process uses a stirring speed of 100~300 rpm and a stirring time of 1~3 h;

[0038] The fourth drying process uses a drying temperature of 60~80℃ and a drying time of 3~6h.

[0039] The fifth calcination treatment uses a calcination temperature of 120~180℃ and a calcination time of 1~3h.

[0040] In a second aspect, the present invention provides a water- and sulfur-resistant Pt-based catalyst, which is prepared by the method described above for preparing the water- and sulfur-resistant Pt-based catalyst.

[0041] The application of the technical solution of the present invention has at least the following beneficial effects:

[0042] This invention provides a method for preparing a water- and sulfur-resistant Pt-based catalyst, capable of producing a Pt-based catalyst resistant to sulfur dioxide and water vapor. Simultaneously, the active component Pt in this catalyst is uniformly and firmly bound to a CZ support, effectively addressing the problem of Pt nanoparticle migration and agglomeration leading to decreased catalytic activity under the impact of high-temperature sintering flue gas in steel plants. Specifically:

[0043] Regarding the uniform and firm binding of the active component Pt onto the CZ support, this invention first prepares a cubic phase CZ support in step S1, which contains uniformly dispersed oxygen vacancies on its surface and pore inner walls, so as to form bridging bonds with the active component Pt in step S2, thereby uniformly and firmly binding the active component Pt onto the CZ support. The principle of forming oxygen vacancies is as follows: In step S1, zirconium salt and cerium salt are first prepared into a mixed salt solution with the required molar concentration according to the required molar ratio. After adding alkali solution dropwise until the pH is 9-10, a precipitate-containing mixed solution is obtained. Then, after a second stirring treatment at 25-30℃, the diffusion rate of zirconium and cerium ions to the precipitate can be effectively controlled, thereby effectively controlling the growth rate of the precipitate nuclei. The first drying and calcination processes aim to promote the growth of precipitated nuclei into uniformly sized, highly pure, and evenly dispersed CZ support precursor particles. This ensures that after the first drying and calcination processes, a cubic CZ support with uniform particle size, high purity, and uniform Zr doping within the CeO2 lattice is obtained. If the temperature during the second stirring process is too low, insufficient growth kinetics of the precipitated nuclei can easily lead to the formation of amorphous or metastable CZ support precursor particles, which are also prone to hard agglomeration. This results in uneven particle size distribution and a decrease in specific surface area of ​​the CZ support after the first calcination process. Conversely, if the temperature during the second stirring process is too high, increased thermal motion accelerates the growth rate of the precipitated nuclei, leading to the formation of coarse particles. Furthermore, excessively high temperatures can cause localized dynamic dissolution of Zr from the precipitated nuclei. 4+ / Ce 3+ Concentration imbalance leads to uneven Zr doping in the CeO2 lattice after the first calcination treatment, preventing the formation of a stable cubic CZ support; furthermore, during the first calcination treatment, Zr... 4+ With Ce 4+ The radius difference causes localized stress when Zr doping enters the CeO2 lattice. To release this stress, some lattice oxygen detaches from its situ, forming oxygen vacancies. Additionally, a small portion of Ce... 4+ With Ce 3+ The valence state changes between them will also form oxygen vacancies. Therefore, a large number of oxygen vacancies can be formed on the cubic CZ support. As mentioned above, a cubic CZ support with uniform Zr doping in the CeO2 lattice can be obtained, which in turn makes the oxygen vacancies uniformly distributed on the CZ support.

[0044] Furthermore, the principle of bridging bonds formed by the active component Pt is as follows: First, the second drying process in step S2 is vacuum drying. By controlling an appropriate drying temperature and time, the active component Pt is uniformly diffused and adsorbed onto the oxygen vacancies on the CZ support. Vacuum drying also avoids the influence of air convection on the uniform diffusion of the active component Pt during the drying process. Second, the appropriate calcination temperature and time used in the second calcination process ensure that the platinum salt is completely decomposed into PtO2 with uniform particle size, which facilitates the catalytic sensitivity to carbon monoxide. If the calcination temperature used in the second calcination process is too high, it can easily lead to the decomposed PtO2 undergoing "Ostwald ripening". The mechanism of agglomeration into large particles (e.g., particle size ≥ 10 nm) greatly reduces the catalytic sensitivity to carbon monoxide. In addition, if the calcination temperature used in the second calcination treatment is too high, it will also cause gas generation during the decomposition of platinum salt into PtO2, thereby breaking the uniform dispersion of PtO2 and even causing agglomeration. Subsequently, the appropriate calcination temperature and calcination time used in the third calcination treatment ensure that PtO2 forms bridging bonds with lattice oxygen at oxygen vacancies (Pt-O-Ce or Pt-O-Zr), thereby ensuring that the active component Pt is uniformly and firmly bound on the CZ support, which greatly improves the catalyst's tolerance to the airflow impact of high-temperature sintering flue gas.

[0045] Regarding its tolerance to sulfur dioxide, the active component Pt, uniformly and firmly bound to the CZ support, possesses a positive charge and readily adsorbs hydroxyl groups from water in the lanthanum salt solution prepared in step S3. The lanthanum salt solution, with a pH of 7–7.5, exhibits slight alkalinity, which protonates the adsorbed hydroxyl groups, transferring the protonated hydrogen from the hydroxyl groups adsorbed by the active component Pt to the OH groups in the lanthanum salt solution. - This leads to the adsorption of negatively charged -O by the active component Pt. - The process involves creating a negatively charged region where positively charged lanthanum ions are stably adsorbed onto the surface of the active component Pt due to electrostatic attraction between the positive and negative charges. The Pt / CZ pre-prepared catalyst is ground to the target particle size before being added to the lanthanum salt solution. This increases the surface area for adsorption of lanthanum ions by the active component Pt in the Pt / CZ pre-prepared catalyst, ensuring sufficient adsorption of lanthanum ions by the active component Pt. Finally, through evaporation, a third drying treatment, and a fourth calcination treatment, lanthanum ions are oxidized to form La2O3. Sulfur dioxide tends to bind with La2O3 rather than diffuse to the active site Pt surface, preventing the formation of strongly covalently bonded Pt-S species by sulfur, thus blocking the active site and improving the tolerance of the active component Pt to sulfur dioxide.

[0046] Regarding the tolerance to water vapor, in step S4, a silane hydrophobic agent is added to modify the hydrophobicity of the anti-sulfur Pt-based catalyst, forming a water-resistant and anti-sulfur Pt-based catalyst with a hydrophobic layer, thereby improving the catalyst's tolerance to water vapor.

[0047] In addition to the objectives, features, and advantages described above, the present invention has other objectives, features, and advantages. The invention will now be described in further detail with reference to the figures. Attached Figure Description

[0048] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0049] Figure 1 The results show the catalytic CO reaction of the water- and sulfur-resistant Pt-based catalyst prepared in Example 1 of this invention within 500 hours. Detailed Implementation

[0050] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0051] Example 1:

[0052] A method for preparing a water- and sulfur-resistant Pt-based catalyst, comprising:

[0053] Step S1: Prepare the CZ vector;

[0054] Zirconium salt and cerium salt were added to water at a molar ratio of zirconium to cerium of 1:9. After the first stirring treatment, a mixed salt solution with a molar concentration of 0.5 mol / L was prepared.

[0055] Add alkali solution dropwise to the mixed salt solution and mix well until the pH is 9-10 (specifically 10) to obtain a mixed solution containing precipitate;

[0056] The precipitate-containing mixture was subjected to a second stirring treatment at 25-30°C (specifically 25°C), the solid phase was filtered out, and the solid phase was first washed with deionized water until neutral. Then, it was subjected to a first drying treatment and a first calcination treatment to obtain cubic CeO2-ZrO2, i.e., cubic CZ support. The stirring speed used in the second stirring treatment was 200-400 rpm (specifically 200 rpm), and the stirring time was 12 hours.

[0057] Step S2: Loading the active component Pt;

[0058] Platinum salt is added to water and mixed to dissolve to obtain a platinum salt solution. Then, the CZ support that has been ground and sieved is added. After a third stirring treatment, the solution is subjected to a second drying treatment, a second calcination treatment and a third calcination treatment in sequence to obtain a Pt / CZ pre-prepared catalyst with the active component Pt uniformly loaded on the CZ support.

[0059] The platinum salt accounts for 1% of the mass of the CZ carrier; the second drying treatment uses vacuum drying at a temperature of 80°C for 4 hours; after the second drying treatment, the temperature is increased to the calcination temperature used in the second calcination treatment at a rate of 2°C / min; the second calcination treatment uses a calcination temperature of 350°C for 2 hours; the third calcination treatment uses a calcination temperature of 500°C for 3 hours.

[0060] Step S3: Doping with lanthanide oxides as an auxiliary agent;

[0061] Lanthanum salt was added to water and stirred for the fourth time to obtain a lanthanum salt solution. The pH of the lanthanum salt solution was adjusted to 7-7.5 (specifically 7) using a pH adjuster. The Pt / CZ pre-prepared catalyst was ground to the target particle size (specifically 2-5 nm) and added to the lanthanum salt solution. After stirring and mixing, it was then subjected to evaporation, drying, and calcination treatments in sequence to obtain a sulfur-resistant Pt-based catalyst.

[0062] The lanthanum salt accounts for 1% of the mass of the Pt / CZ pre-prepared catalyst;

[0063] Step S4: Hydrophobic modification;

[0064] The sulfur-resistant Pt-based catalyst was added to a silane hydrophobic agent solution, and after a fifth stirring treatment, it was subjected to a fourth drying treatment and a fifth calcination treatment to obtain a water-resistant and sulfur-resistant Pt-based catalyst containing a hydrophobic layer.

[0065] The cerium salt is cerium nitrate with the molecular formula Ce(NO3)3·6H2O; the zirconium salt is zirconium nitrate with the molecular formula Zr(NO3)4·5H2O; the alkaline solution includes either ammonia or sodium hydroxide aqueous solution, such as ammonia.

[0066] The first stirring process uses a stirring speed of 400~1000rpm (specifically 500rpm) and a stirring time of 30min;

[0067] The first drying process uses a drying temperature of 100℃ and a drying time of 12 hours.

[0068] The first calcination treatment uses a calcination temperature of 500℃ and a calcination time of 3 hours. After the first drying treatment, the temperature is increased to the calcination temperature used in the first calcination treatment at a heating rate of 5℃ / min.

[0069] In the platinum salt solution, the mass percentage of the platinum salt is 13% to 19% (specifically 15%).

[0070] The platinum salt is platinum nitrate.

[0071] The grinding and sieving process involves grinding the CZ carrier into powder and then passing it through a 60-mesh sieve.

[0072] The third stirring process uses a stirring speed of 100~400 rpm (specifically 200 rpm) and a stirring time of 30 min.

[0073] In the lanthanum salt solution, the mass percentage of the lanthanum salt is 78.3%;

[0074] The lanthanum salt is lanthanum nitrate, with the molecular formula La(NO3)3·6H2O;

[0075] The pH adjuster includes either an aqueous solution of sodium hydroxide or ammonia, such as ammonia.

[0076] The evaporation process is carried out at a temperature of 80°C until the food is completely dried.

[0077] The fourth stirring process uses a stirring speed of 150~300 rpm (specifically 150 rpm) and a stirring time of 12~24h (specifically 24h).

[0078] The third drying process uses a drying temperature of 120℃ and a drying time of 4 hours.

[0079] The fourth calcination treatment used a calcination temperature of 500℃ and a calcination time of 2 hours.

[0080] The silane hydrophobic agent used in the silane hydrophobic agent solution has a volume percentage of 95%; the solvent used in the silane hydrophobic agent solution is a 5% volume percentage ethanol solution; and the silane hydrophobic agent is methyltrimethoxysilane.

[0081] The fifth stirring process uses a stirring speed of 100~300rpm (specifically 200rpm) and a stirring time of 1h;

[0082] The fourth drying process uses a drying temperature of 60℃ and a drying time of 3~6h (specifically 6h).

[0083] The fifth calcination treatment used a calcination temperature of 150℃ and a calcination time of 1 hour.

[0084] Example 2:

[0085] Unlike Example 1, in step S1, the zirconium salt and cerium salt are adjusted to a molar ratio of zirconium to cerium of 1:14.

[0086] Example 3:

[0087] Unlike Example 1, in step S1, the zirconium salt and cerium salt are adjusted to a molar ratio of zirconium to cerium of 1:19.

[0088] Example 4:

[0089] Unlike Example 1, in step S2, the platinum salt accounts for 0.5% of the mass of the CZ carrier.

[0090] Example 5:

[0091] Unlike Example 1, in step S2, the platinum salt accounts for 2% of the mass of the CZ carrier.

[0092] Example 6:

[0093] Unlike Example 1, in step S3, the lanthanum salt accounts for 0.5% of the mass of the Pt / CZ pre-prepared catalyst.

[0094] Example 7:

[0095] Unlike Example 1, in step S3, the lanthanum salt accounts for 3% of the mass of the Pt / CZ pre-prepared catalyst.

[0096] Example 8:

[0097] Unlike Example 1, in step S3, the lanthanum salt accounts for 5% of the mass of the Pt / CZ pre-prepared catalyst.

[0098] Comparative Example 1:

[0099] Unlike Example 1, steps S3 and S4 are omitted.

[0100] Comparative Example 2:

[0101] Unlike Example 1, step S4 is omitted.

[0102] Comparative Example 3:

[0103] Unlike Example 1, the second calcination treatment is omitted in step S2.

[0104] Comparative Example 4:

[0105] Unlike Example 1, in step S3, the pH adjuster is omitted, that is, the pH value of the lanthanum salt solution is not adjusted.

[0106] Samples of the catalysts prepared in Examples 1-8 and Comparative Examples 1-4 were taken and tested for their catalytic CO performance against high-temperature sintering flue gas from a steel plant for up to 20 hours. The test conditions were as follows: the temperature of the high-temperature sintering flue gas from the steel plant was 250°C, its composition was 6000 ppm CO, 100 ppm SO2, and 10% water vapor by volume, and the flue gas space velocity was 15000 h⁻¹. -1 The test results are shown in Table 1.

[0107] Table 1 Performance test results of catalytic CO

[0108]

[0109] As shown in Table 1, compared with Comparative Examples 1-4, the catalysts prepared by Examples 1-8 of this invention all exhibited significant and stable catalytic performance for CO catalysis under different test durations within 20 hours.

[0110] By comparing Comparative Example 1 with Example 1, it is known that by omitting steps S3 and S4 in Comparative Example 1, the prepared catalyst does not have water and sulfur resistance properties, which leads to a gradual decrease in the performance of catalytic CO as the test time is extended.

[0111] By comparing Comparative Example 2 with Example 1, it is known that omitting step S4 in Comparative Example 2 results in a catalyst that lacks water resistance, leading to a gradual decrease in the performance of CO catalysis as the testing time is extended.

[0112] By comparing Comparative Example 3 with Example 1, it is known that in Comparative Example 3, the second calcination treatment in step S2 was omitted, causing the platinum salt to decompose directly into PtO2 at an excessively high calcination temperature. The excessively high calcination temperature will cause gas to be generated during the decomposition of platinum salt into PtO2, thereby breaking the uniform dispersion of PtO2 and even causing agglomeration. This leads to a decrease in the performance of the prepared catalyst in catalyzing CO. Moreover, the performance in catalyzing CO shows a gradual decreasing trend when the test time is extended. This may be caused by further agglomeration of the active component Pt under the impact of the sintering flue gas flow.

[0113] By comparing Comparative Example 4 with Example 1, it is known that in Comparative Example 4, the use of pH adjuster was omitted in step S3, that is, the pH value of the lanthanum salt solution was not adjusted. This prevented the formation of a negatively charged region on the surface of the active component Pt to adsorb lanthanum ions, and thus prevented the oxidation to form La2O3. As a result, the catalyst did not have sulfur resistance performance, and the performance of catalytic CO showed a gradual decreasing trend as the test time was extended.

[0114] The catalyst prepared in Example 1 was sampled and its catalytic CO performance was tested on high-temperature sintering flue gas from a steel plant for up to 500 hours. The test conditions were the same as in Table 1. The test results are shown below. Figure 1 .Depend on Figure 1 It is known that the catalyst prepared by Example 1 of this invention exhibits significant and stable catalytic performance for CO catalysis under different test durations within 500 h.

[0115] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made using the present invention's specification under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A process for the preparation of a water and sulfur resistant Pt-based catalyst, characterized in that, The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst.

2. The method of preparing a water-resistant, sulfur-resistant Pt-based catalyst according to claim 1, wherein The application relates to a preparation method of a sulfur-resistant Pt-based catalyst.

3. The method of preparing a water-resistant, sulfur-resistant Pt-based catalyst according to claim 1, wherein The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst.

4. The method of making a water resistant, sulfur resistant Pt-based catalyst of claim 1, wherein, The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst.

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The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of a sulfur-resistant Pt-based catalyst. The application relates to a preparation method of 6. The method of making a water resistant, sulfur resistant Pt-based catalyst of claim 1, wherein, The mass percentage of the lanthanum salt in the lanthanum salt solution is 78.3%; The lanthanum salt comprises lanthanum nitrate; The pH regulator comprises any one of a sodium hydroxide aqueous solution and ammonia water.

7. The method of making a water resistant, sulfur resistant Pt-based catalyst of claim 1, wherein, The target particle size is 2-5 nm; The evaporation drying temperature used in the evaporation drying treatment is 60-100℃ until evaporation drying; The stirring speed used in the fourth stirring treatment is 150-300 rpm, and the stirring time is 12-24 h; The drying temperature used in the third drying treatment is 100-120℃, and the drying time is 2-4 h; The calcination temperature used in the fourth calcination treatment is 450-650℃, and the calcination time is 2-6 h.

8. The method of making a water resistant, sulfur resistant Pt-based catalyst of claim 1, wherein, The volume percentage of the silane hydrophobic agent used in the silane hydrophobic agent solution is 95%; the solvent used in the silane hydrophobic agent solution comprises an ethanol solution with a volume percentage of 5%; and the silane hydrophobic agent comprises methyltrimethoxysilane.

9. The method of making a water resistant, sulfur resistant Pt-based catalyst of claim 1, wherein, The stirring speed used in the fifth stirring treatment is 100-300 rpm, and the stirring time is 1-3 h; The drying temperature used in the fourth drying treatment is 60-80℃, and the drying time is 3-6 h; The calcination temperature used in the fifth calcination treatment is 120-180℃, and the calcination time is 1-3 h.

10. A water and sulfur resistant Pt-based catalyst, characterized by, The anti-water and anti-sulfur Pt-based catalyst is prepared by using the preparation method of any one of claims 1-9. The anti-water and anti-sulfur Pt-based catalyst is prepared by using the preparation method of any one of claims 1-9.

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