Catalyst for preparing propylene through propane dehydrogenation as well as preparation method and application of catalyst

Abstract

The invention discloses a catalyst for preparing propylene through propane dehydrogenation. The catalyst comprises a carrier, an active component, a first auxiliary agent and a second auxiliary agent. The invention also discloses a preparation method of the catalyst for preparing propylene through propane dehydrogenation, and the preparation method comprises the following steps: S1, dissolving the first auxiliary agent and the second auxiliary agent in an alcoholic solution with the concentration of 75-95% to obtain a mixed metal alcoholic solution; s2, carrying out pretreatment on a carrier, and carrying out vacuum drying on the carrier at 40-110 DEG C for 3-20 hours to obtain a pretreated carrier; s3, impregnating the pretreated carrier in the mixed metal alcohol solution obtained in the step S1, sealing, performing ultrasonic treatment, drying, and roasting to obtain a catalyst precursor loaded with the first auxiliary agent and the second auxiliary agent; and S4, dipping the catalyst precursor in an alcoholic solution of platinum, sealing, carrying out ultrasonic treatment, drying, and baking to obtain the catalyst. The catalyst provided by the invention can increase the propane dehydrogenation yield to 38%.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and in particular to a catalyst for the dehydrogenation of propane to propylene, its preparation method, and its application. Background Technology

[0002] With the large-scale extraction and utilization of shale gas, propane has become a low-cost chemical raw material. Converting propane into high-value-added propylene products is of great significance to economic development. This not only improves the utilization rate of propane raw materials but also meets the huge market demand for propylene products, greatly promoting the research and application of economical, environmentally friendly, and efficient new propylene development technologies.

[0003] In existing technologies, platinum-based propane dehydrogenation catalysts commonly used in propane dehydrogenation processes often suffer from problems such as easy sintering of platinum and carbon deposition, leading to rapid catalyst deactivation and irreversible sintering. This leaves significant room for improvement in existing platinum-based propane dehydrogenation catalysts. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a catalyst for propane dehydrogenation to propylene, its preparation method, and its application.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows: A catalyst for propane dehydrogenation to propylene includes: a support, an active component, a first promoter, and a second promoter; The active component is a noble metal salt, and the loading of the active component accounts for 0.05%-0.8% of the carrier mass. The mass ratio of the first auxiliary agent to the second auxiliary agent is 1:(0.5-10); The second auxiliary agent is one or more of rare earth metal salts, alkali metal salts, and alkaline earth metal salts.

[0006] The first auxiliary agent is a copper salt, wherein the copper salt is any one of copper chloride, copper nitrate, and copper sulfate; The alkali metal salt is any one of potassium nitrate, potassium chloride, sodium chloride, and lithium aluminum oxide; The alkaline earth metal salt is any one of magnesium nitrate, magnesium chloride, and calcium chloride. The rare earth metal salt is either lanthanum nitrate or cerium nitrate; The precious metal salt is a platinum salt.

[0007] The platinum salt is platinum nitrate, chloroplatinic acid, or ammonium chloroplatinate.

[0008] The second additive is a rare earth metal salt and an alkali metal salt in a mass ratio of (1-1.5):(2-1).

[0009] The second additive is a rare earth metal salt and an alkaline earth metal salt in a mass ratio of (1-1.5):1.

[0010] The second auxiliary agent is an alkali metal salt and an alkaline earth metal salt in a mass ratio of (2-1):1.

[0011] The second auxiliary agent is a rare earth metal salt, an alkali metal salt, and an alkaline earth metal salt in a mass ratio of (1-1.5):(2-1):1.

[0012] The carrier is Al2O3, zirconium oxide, silicon oxide, or molecular sieve.

[0013] This invention also provides a method for preparing a catalyst for propane dehydrogenation to propylene, comprising the following steps: S1. Pre-treat the carrier by vacuum drying it at 40-110℃ for 3-20 hours to obtain the pre-treated carrier. S2. Dissolve the first and second additives in an alcohol solution with a concentration of 75%-95% to obtain a mixed metal alcohol solution; S3. The pretreated support is immersed in the mixed metal alcohol solution obtained in step S2, and then sealed, sonicated, dried and calcined to obtain a catalyst precursor loaded with the first and second additives. S4. The catalyst precursor is then immersed in a platinum alcohol solution, sealed, sonicated, dried, and calcined to obtain the catalyst. In steps S3 and S4, the ultrasonic time is 3-40 min, the calcination temperature is 380-750℃, and the calcination time is 2-8 h. The platinum alcohol solution is obtained by dissolving 0.05%-0.8% platinum salt in an alcohol solution.

[0014] The alcohol solution is any one of methanol, ethanol, and propylene glycol.

[0015] The alcohol solution and the carrier have the same volume.

[0016] The present invention also provides the application of the above-described catalyst in propane dehydrogenation.

[0017] The beneficial effects of this invention are: 1. The catalyst of the present invention, under the synergistic effect of the first and second additives, can effectively control the size and surface area of ​​the active component of the catalyst, enhance the dispersibility of the active component, solve the problems of easy sintering of platinum-based active components and carbon deposition caused by acidity of catalyst support in the prior art, avoid catalyst deactivation from the source, and extend the service life of the catalyst. The catalyst can increase the dehydrogenation yield to 38% when used for propane dehydrogenation.

[0018] 2. The catalyst of the present invention uses copper as the first additive, which can effectively disperse the active component elements, prevent the clustering of active component elements, and allow the active components to be uniformly dispersed on the surface of the support, thereby increasing the activation area of ​​the active component elements and avoiding the deactivation of the catalyst caused by the sintering of the active component elements; the second additive in the catalyst of the present invention can effectively balance the acidic sites inherent in the catalyst support itself, thereby solving the problem of catalyst deactivation.

[0019] 3. Under the synergistic effect of the mass ratio of the first and second additives, as well as the composition and mass ratio of the second additive, the catalyst of the present invention can fully and uniformly disperse the active component elements on the surface of the support, avoid the clustering of active component elements, thereby increasing the activation area of ​​the active component elements, effectively controlling the size of the active component of the catalyst, and solving the problem of easy sintering of platinum-based active components in the prior art; it can also effectively balance the acidic sites inherent in the catalyst support itself, solve the problem of catalyst carbon deposition, avoid catalyst deactivation, and thus extend the service life of the catalyst.

[0020] 4. In this invention, the support used has a large number of acidic sites inside, which can directly affect the selectivity of the catalyst. The added second promoters can react with the acidic sites and effectively balance the acidic sites, thus avoiding the influence of the acidic sites on the selectivity of the catalyst and enhancing the selectivity of the catalyst for the dehydrogenation reaction.

[0021] 5. In this invention, since the active component needs to be loaded onto a blank support, the support needs to have a sufficiently large surface area and suitable pore volume and pore size to accommodate the element to be loaded.

[0022] 6. The catalyst preparation method of the present invention employs an ultrasonic impregnation method to first load a first auxiliary agent and a second auxiliary agent to obtain a catalyst precursor, and then ultrasonically impregnates and loads the active component platinum metal onto the catalyst precursor. Compared with other methods, ultrasonically impregnating and loading the first and second auxiliary agents first ensures that the support completely absorbs the impregnation solution of the first and second auxiliary agents, so that the first and second auxiliary agents are uniformly and firmly loaded on the surface of the support. Among them, the first auxiliary agent can disperse the active component elements, prevent the clustering of active component elements, and avoid sintering of active component elements; the second auxiliary agent can neutralize the acidic sites inherent in the support itself, effectively balancing the acidic sites inherent in the catalyst support itself, avoiding carbon deposition on the catalyst, thereby obtaining a catalyst with superior performance.

[0023] 7. In this invention, the method for pre-treating the carrier is as follows: the carrier is vacuum dried at 40-110℃ for 3-20 hours to obtain the pre-treated carrier. When the drying temperature is less than 40℃, the carrier will not dry completely, and the carrier spheres will easily crack during calcination. When the drying temperature is higher than 110℃, the technical elements impregnated on the carrier will easily be lost. The drying time depends on the sample amount to ensure that the spheres are fully dried.

[0024] 8. The ultrasonic impregnation of the present invention can effectively load the unimpregnated impregnation liquid into the carrier under the action of ultrasound, and balance the acidic sites in the already impregnated carrier, so that the impregnation aid is more evenly distributed on the carrier surface and the bond between the aid and the carrier is stronger.

[0025] 9. The ultrasonic time of this invention is 3-40 minutes. When the ultrasonic time is less than 3 minutes, it is not very meaningful for loading the first and second additives onto the carrier; when the ultrasonic time exceeds 40 minutes, the excessive ultrasonic time will cause the carrier to become fragile, thus leading to load failure.

[0026] 10. In the catalyst preparation method of the present invention, the calcination temperature is 380-750℃ and the time is 2-8h. If the temperature is below 380℃, the catalyst component, such as platinum, is not completely converted into elemental platinum. The catalyst needs to complete the catalysis through elemental platinum, so the temperature cannot be too low. If the temperature is too high, the catalyst pores will collapse and the additives will be difficult to adhere. Furthermore, the catalytic performance of propane is related to the number of platinum active sites. Therefore, smaller platinum particles, such as elemental platinum, have more active sites. The structural morphology of platinum particles has a significant impact on side reactions such as hydrogenolysis and isomerization of propane. Thus, when platinum is supported on the catalyst precursor, if the calcination temperature is below 350°C, this temperature is below the decomposition temperature of platinum salt into elemental platinum, making it difficult for elemental platinum to be supported on the support. Instead, it is supported on the support in the form of large-particle platinum salt, resulting in fewer active sites on the catalyst and easy aggregation of platinum salt. The resulting catalyst is prone to side reactions such as hydrogenolysis and isomerization of propane during propane dehydrogenation, leading to low catalytic efficiency and low economic value. On the other hand, when platinum is supported on the catalyst precursor, if the calcination temperature is above 750°C, the excessively high calcination temperature will cause the crystal form of the support to change easily, and the metal elements supported on the support, such as elemental platinum, the metal elements of the first and second promoters, will volatilize at high temperatures, resulting in extremely low catalyst efficiency.

[0027] 11. This invention uses aluminum oxide as a carrier. Aluminum oxide has a porous structure with a large specific surface area, pore volume and pore size, and a large number of acid centers on the surface. Alkali metals, alkaline earth metals and rare earth metals are introduced to balance its surface acidity, and the loaded metal platinum is the active component.

[0028] 12. The catalyst provided by this invention has a good ability to cope with carbon deposition and deactivation, and the obtained catalyst has good selectivity and high stability.

[0029] 13. In this invention, the alcohol solution can uniformly disperse the first auxiliary agent, the second auxiliary agent, and the active component to form a uniformly distributed impregnation solution. Attached Figure Description

[0030] Figure 1 This is a line graph showing the propane dehydrogenation selectivity of the present invention.

[0031] Figure 2 This is a line graph showing the propane dehydrogenation conversion rate of the present invention. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. It should be understood that these descriptions are merely exemplary and not intended to limit the scope of the invention. Furthermore, descriptions of well-known structures and technologies are omitted in the following description to avoid unnecessarily obscuring the concepts of the invention.

[0033] Example 1 This invention provides a catalyst for propane dehydrogenation, comprising: an Al2O3 support, an active component, a first promoter, and a second promoter; wherein the active component is made from platinum nitrate, and the platinum nitrate loading accounts for 0.05% of the support mass; The first auxiliary agent is copper nitrate; the second auxiliary agent is lanthanum nitrate, potassium nitrate and magnesium nitrate in a mass ratio of 1:2:1; the mass ratio of the first auxiliary agent to the second auxiliary agent is 1:0.5.

[0034] This invention also provides a method for preparing the above-mentioned catalyst, which employs a two-step impregnation method and a calcination method, and the catalyst is loaded and ultrasonically impregnated to obtain the catalyst, specifically including the following steps: Step 1: Dry the Al2O3 support under vacuum at 90℃ for 3 hours to obtain the pretreated support; Step 2: Dissolve the first auxiliary agent (copper nitrate) and the second auxiliary agent (lanthanum nitrate, potassium nitrate and magnesium nitrate in a mass ratio of 1:2:1) in 100 ml of 95% ethanol solution and stir until homogeneous to obtain a mixed metal alcohol solution. Step 3: Immerse the pretreated carrier in the above mixed metal alcohol solution, seal it, sonicate it for 10 min, dry it at 40°C for 3 h, and then place it in a muffle furnace and calcine it at 380°C for 2 h to obtain a catalyst precursor loaded with the first and second additives. Step 4: Dissolve 0.05% platinum nitrate in 100ml of 95% alcohol solution to obtain a platinum alcohol solution. Then, immerse the above catalyst precursor in the platinum alcohol solution, seal it, sonicate it for 10min, dry it at 40℃ for 3h, and then calcine it in a muffle furnace at 380℃ for 2h to obtain the catalyst.

[0035] Example 2 This invention provides a catalyst for propane dehydrogenation, comprising: an Al2O3 support, an active component, a first promoter, and a second promoter; wherein the active component is chloroplatinic acid, and the loading of chloroplatinic acid accounts for 0.5% of the support mass; The first auxiliary agent is copper chloride; the second auxiliary agent is cerium nitrate, potassium chloride and calcium chloride in a mass ratio of 1:1.5:1; the mass ratio of the first auxiliary agent to the second auxiliary agent is 1:5.

[0036] This invention also provides a method for preparing the above-mentioned catalyst, which employs a two-step impregnation method and a calcination method, and the catalyst is loaded and ultrasonically impregnated to obtain the catalyst, specifically including the following steps: Step 1: Dry the Al2O3 support under vacuum at 80℃ for 10 hours to obtain the pretreated support; Step 2: Dissolve the first auxiliary agent (copper chloride) and the second auxiliary agent (cerium nitrate, potassium chloride, and calcium chloride in a mass ratio of 1:1.5:1) in 100 ml of 95% 1,2-propanediol solution and stir until homogeneous to obtain a mixed metal alcohol solution. Step 3: Immerse the pretreated carrier in the above mixed metal alcohol solution, seal it, sonicate it for 35 min, dry it at 80°C for 10 h, and then calcine it in a muffle furnace at 550°C for 6 h to obtain a catalyst precursor loaded with the first and second additives. Step 4: Dissolve 0.3% chloroplatinic acid in 100 ml of 75% 1,2-propanediol solution to obtain a platinum alcohol solution. Then, impregnate the above catalyst precursor in the platinum alcohol solution, seal it, sonicate it for 35 min, dry it at 80 °C for 10 h, and then calcine it in a muffle furnace at 550 °C for 6 h to obtain the catalyst.

[0037] Example 3 This invention provides a catalyst for propane dehydrogenation, comprising: an Al2O3 support, an active component, a first promoter, and a second promoter; wherein the active component is ammonium chloroplatinate, and the loading of ammonium chloroplatinate accounts for 0.8% of the support mass; The first auxiliary agent is copper sulfate; the second auxiliary agent is cerium nitrate, lithium aluminum oxide and magnesium chloride in a mass ratio of 1.5:1:1; the mass ratio of the first auxiliary agent to the second auxiliary agent is 1:10. This invention also provides a method for preparing the above-mentioned catalyst, which employs a two-step impregnation method and a calcination method, and the catalyst is loaded and ultrasonically impregnated to obtain the catalyst, specifically including the following steps: Step 1: Dry the Al2O3 support under vacuum at 110℃ for 20 hours to obtain the pretreated support; Step 2: Dissolve the first auxiliary agent (copper sulfate) and the second auxiliary agent (cerium nitrate, lithium aluminum oxide, and magnesium chloride) in 100 ml of 95% methanol solution at a mass ratio of 1:10 to obtain a mixed metal alcohol solution. Step 3: The pretreated support is immersed in a mixed metal alcohol solution, sealed, sonicated for 40 min, dried at 110℃ for 20 h, and then calcined in a muffle furnace at 750℃ for 8 h to obtain a catalyst precursor loaded with the first and second additives. Step 4: Dissolve 0.8% (w / w) of ammonium platinum acid in 100 ml of 95% methanol solution to obtain a platinum alcohol solution. Then, immerse the above catalyst precursor in the platinum alcohol solution, seal it, sonicate it for 40 min, dry it at 110 °C for 20 h, and then calcine it in a muffle furnace at 750 °C for 8 h to obtain the catalyst.

[0038] Example 4 The second auxiliary agent for the catalyst in this embodiment is only cerium nitrate; the other components and the preparation method of the catalyst are described in Example 2.

[0039] Example 5 In this embodiment, the second auxiliary agent for the catalyst is only potassium nitrate; the other components and the catalyst preparation method are the same as in Example 2. Example 6 In this embodiment, the second auxiliary agent for the catalyst is only magnesium chloride; the other components and the catalyst preparation method are the same as in Example 2. Example 7 The second additive for the catalyst in this embodiment is cerium nitrate and potassium nitrate in a mass ratio of 1:2 or 1.5:1. The preparation methods of the remaining components and the catalyst are described in Example 2.

[0040] Example 8 The second additive for the catalyst in this embodiment is cerium nitrate and calcium chloride in a mass ratio of 1:1 or 1.5:1. The preparation methods of the remaining components and the catalyst are described in Example 2.

[0041] Example 9 The second auxiliary agent of the catalyst in this embodiment is potassium nitrate and magnesium chloride in a mass ratio of 2:1 or 1:1. The preparation methods of the remaining components and the catalyst are the same as in Example 2.

[0042] Example 10 The second auxiliary agent of the catalyst in this embodiment of the invention is cerium nitrate, potassium chloride and calcium chloride in a mass ratio of 1.2:1.5:1; the preparation methods of the remaining components and the catalyst are described in Example 2.

[0043] Example 11 In this embodiment of the invention, the ultrasonic time of the catalyst is 3 min, and the Al2O3 support is vacuum dried at 40°C; the preparation methods of the remaining components and the catalyst are described in Example 2.

[0044] Application Examples The catalysts prepared in Examples 1-3 and 1-11 were used for propane dehydrogenation. The specific steps included: the propane dehydrogenation conditions were as follows: 10-20g of catalyst was loaded into a tube furnace, and nitrogen gas with a hydrogen content of 5% was introduced to purge the catalyst at a flow rate of 50ml / min and a heating rate of 10℃ / min. The catalyst was reduced by raising the temperature from room temperature to 800℃. The catalyst sample loading amount is 4-10g. To ensure that the loading position is kept at a constant temperature, glass wool can be used to fix the position. After the sample is loaded, nitrogen gas is used to check for leaks to ensure that the reaction of the device is airtight. The heating program is set to bring the heater to the preset reduction temperature. Nitrogen gas is introduced as a protective gas during the heating process. After reaching the preset temperature, hydrogen gas is introduced at a hydrogen-to-nitrogen ratio of 1:9 as the reducing gas. Reduction is carried out for 2 hours. The hydrogen gas is then shut off, and nitrogen gas is introduced again to raise the temperature to the catalyst evaluation temperature. Once the heater reaches the reaction temperature, the nitrogen gas is shut off, and the propane inlet valve is opened. The valves and instruments are controlled to maintain the flow rate of the feed gas and the pressure in the reactor within a certain range, initiating the dehydrogenation reaction. Tail gas samples are taken at regular intervals for online analysis using gas chromatography. After completing the catalyst performance evaluation, the feed gas inlet valve, tail gas valve, feed gas flow meter, and pressure regulator are closed. The heater is shut off, and the reactor is allowed to cool naturally to room temperature. The power to the evaluation device control panel is then turned off.

[0045] The propane dehydrogenation reaction is carried out in a fixed-bed reactor. The reactor is connected to a gas chromatograph to analyze the content of the obtained gas in the gas in a timely manner and to calculate the reaction conversion rate, selectivity, etc. The normalization method is used for the calculation.

[0046] The catalysts prepared in Examples 1-3 and Examples 1-11 were compared in terms of propane conversion and propylene selectivity in propane dehydrogenation. Figure 1 and Figure 2 As shown.

[0047] As shown in the figure, the catalysts obtained in Examples 1-3 have better performance than those obtained in Examples 1-11. This indicates that the catalysts of the present invention can improve propane conversion and propylene selectivity.

[0048] The superior performance of the catalyst of this invention is primarily due to several factors. First, the use of copper as the first promoter effectively disperses the active components, preventing their clustering and ensuring uniform dispersion on the support surface. This increases the activation area of ​​the active components and prevents sintering, which can lead to catalyst deactivation. Second, the second promoter effectively balances the acidic sites inherent in the catalyst support, thus addressing the issue of catalyst deactivation due to carbon buildup. Finally, the synergistic effect of the mass ratio of the first and second promoters, the composition and mass ratio of the second promoter, and the catalyst preparation method of this invention ensures uniform dispersion of the active components on the support surface, preventing clustering and increasing the activation area. This effectively controls the size of the active components, solving the problem of easy sintering of platinum-based active components in existing technologies. Furthermore, the effective balancing of the acidic sites inherent in the catalyst support solves the problem of catalyst carbon buildup and prevents deactivation. Therefore, the catalyst of this invention can improve the dehydrogenation efficiency to 34% in propane dehydrogenation and is expected to extend the catalyst's lifespan.

[0049] It should be understood that the specific embodiments described above are merely illustrative or explanatory of the principles of the invention and do not constitute a limitation thereof. Therefore, any modifications, equivalent substitutions, improvements, etc., made without departing from the spirit and scope of the invention should be included within the protection scope of the invention. Furthermore, the appended claims are intended to cover all variations and modifications falling within the scope and boundaries of the appended claims, or equivalent forms of such scope and boundaries.

Claims

1. A catalyst for the dehydrogenation of propane to propylene, characterized in that, include: Carrier, active ingredient, first auxiliary agent and second auxiliary agent; The active component is a noble metal salt, and the loading of the active component accounts for 0.05%-0.8% of the carrier mass. The mass ratio of the first auxiliary agent to the second auxiliary agent is 1:(0.5-10); The second auxiliary agent is one or more of rare earth metal salts, alkali metal salts, and alkaline earth metal salts.

2. The catalyst for propane dehydrogenation to propylene according to claim 1, characterized in that, The first auxiliary agent is a copper salt, wherein the copper salt is any one of copper chloride, copper nitrate, and copper sulfate; The alkali metal salt is any one of potassium nitrate, potassium chloride, sodium chloride, and lithium aluminum oxide; The alkaline earth metal salt is any one of magnesium nitrate, magnesium chloride, and calcium chloride. The rare earth metal salt is either lanthanum nitrate or cerium nitrate; The precious metal salt is a platinum salt.

3. The catalyst for propane dehydrogenation to propylene according to claim 2, characterized in that, The platinum salt is platinum nitrate, chloroplatinic acid, or ammonium chloroplatinate.

4. The catalyst for propane dehydrogenation to propylene according to claim 1, characterized in that, The second additive is a rare earth metal salt and an alkali metal salt in a mass ratio of (1-1.5):(2-1).

5. The catalyst for propane dehydrogenation to propylene according to claim 1, characterized in that, The second additive is a rare earth metal salt and an alkaline earth metal salt in a mass ratio of (1-1.5):

1.

6. The catalyst for propane dehydrogenation to propylene according to claim 1, characterized in that, The second auxiliary agent is an alkali metal salt and an alkaline earth metal salt in a mass ratio of (2-1):

1.

7. The catalyst for propane dehydrogenation to propylene according to claim 1, characterized in that, The second auxiliary agent is a rare earth metal salt, an alkali metal salt, and an alkaline earth metal salt in a mass ratio of (1-1.5):(2-1):

1.

8. The catalyst for propane dehydrogenation to propylene according to claim 1, characterized in that, The carrier is Al2O3, zirconium oxide, silicon oxide, or molecular sieve.

9. A method for preparing a catalyst for propane dehydrogenation to propylene as described in any one of claims 1-8, characterized in that, Includes the following steps: S1. Pre-treat the carrier by vacuum drying it at 40-110℃ for 3-20 hours to obtain the pre-treated carrier. S2. Dissolve the first and second additives in an alcohol solution with a concentration of 75%-95% to obtain a mixed metal alcohol solution; S3. The pretreated support is immersed in the mixed metal alcohol solution obtained in step S2, and then sealed, sonicated, dried and calcined to obtain a catalyst precursor loaded with the first and second additives. S4. The catalyst precursor is then immersed in a platinum alcohol solution, sealed, sonicated, dried, and calcined to obtain the catalyst. In steps S3 and S4, the ultrasonic time is 3-40 min, the calcination temperature is 380-750℃, and the calcination time is 2-8 h. The platinum alcohol solution is obtained by dissolving 0.05%-0.8% platinum salt in an alcohol solution by mass percentage. The alcohol solution can be any one of methanol, ethanol, or propylene glycol. The alcohol solution and the carrier have the same volume.

10. The use of the catalysts of claims 1-8 and the catalysts obtained by the method of claim 9 in propane dehydrogenation.

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