Double-heterojunction catalytic material capable of being used for efficiently preparing propylene through propane dehydrogenation
By constructing a dual heterojunction structure of metal cobalt and nitrogen-doped carbon and precious metals on a carbon-based support, the problems of low selectivity and high cost in the prior art are solved, and a low-temperature and efficient propane dehydrogenation process is achieved. , significantly improves conversion rate and selectivity, and reduces process costs.
Patent Information
- Application Number
- CN202411137369.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-19
- Publication Date
- 2024-12-31
AI Technical Summary
In the existing propane dehydrogenation process, the metal chromium-based catalyst has low selectivity and fast catalyst deactivation, and the platinum-based catalyst is costly and requires high temperature operation, making it difficult to reduce the temperature and reduce the amount of precious metals when ensuring high conversion and selectivity. .
Build a dual heterojunction structure of metal cobalt and nitrogen-doped carbon and precious metals on carbon-based support, and achieve electron and substance transfer through rectifying contact and overflow effects to prepare a dual heterojunction heterojunction heterogeneous catalytic material of metal cobalt/metal-based , synthesis is achieved by high-temperature calcination and chemical reduction method to achieve low-temperature and high-efficiency propane dehydrogenation.
It significantly improves propane conversion and propylene selectivity, extends the activity stability of the catalyst, reduces process costs and temperature rise, has strong applicability, and is suitable for industrial production.
Smart Images
Figure CN119215947A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of direct dehydrogenation of propane to produce propylene, and specifically relates to the catalytic function of coordinated transfer of electrons and substances between double Schottky heterojunctions. Background Art
[0002] Propylene is an important chemical raw material. At present, the main method for industrial production of propylene is to rely on steam cracking of heavy hydrocarbons in petroleum, but the selectivity of propylene using this method is low. At the same time, the catalytic cracking of petroleum consumes a lot of energy and produces a lot of carbon dioxide emissions, which is not in line with the development theme of green sustainable chemistry today. The propane direct dehydrogenation process is considered to be the most promising propylene production process due to its good product uniformity, high economic benefits, and strong environmental protection. In recent years, a large amount of propane extracted from shale gas can provide abundant raw materials for the propane direct dehydrogenation process, further reducing the cost of the process and promoting the promotion of the process.
[0003] Commercial catalysts such as metal chromium and platinum have shown high catalytic activity in the process of propane dehydrogenation to propylene. However, the main disadvantage of metal chromium-based catalysts is the low selectivity for propylene and the high catalyst deactivation rate due to the large amount of carbon deposits on the catalyst surface. On the other hand, highly toxic chromium ions also seriously pollute the environment. For metal platinum-based catalysts, the selectivity of propane dehydrogenation to propylene is high. However, due to the thermodynamic limitations of propane dehydrogenation, a certain propane conversion rate can only be obtained at a higher reaction temperature (>600°C), and the preparation cost of the catalyst is high. Therefore, while ensuring high propane conversion rate and propylene selectivity, reducing the catalytic reaction temperature and reducing the amount of precious metals used in the catalyst are one of the current research focuses.
[0004] Based on the Schottky heterojunction catalytic material composed of metal and semiconductor, it can use the difference in work function between metal and semiconductor to achieve rectifying contact between heterojunctions, thereby adjusting the charge density of the target active center, thereby triggering the catalytic activity of propane dehydrogenation to produce propylene. At the same time, it can also use the overflow efficiency and charge density of precious metals to complete the material transfer between heterojunctions, inhibit the deposition of carbon deposits, and thus ensure the long-term catalytic activity of the catalyst.
[0005] Based on the above analysis results, the research focus of this patent is to use metal cobalt as the main catalyst on a carbon-based carrier, introduce trace amounts of precious metal (Pt, Pd, Ru, Rh, Ir, etc.) nanoparticles as the guest, construct independent double heterojunction structures of metal cobalt and carrier and precious metal and carrier on the carbon-based carrier, realize electron and material transfer between heterojunctions through rectifying contact and overflow effect, and complete the efficient propane dehydrogenation to propylene process at low temperature. This type of double heterojunction catalytic material has a simple synthesis method, a wide source of materials and strong applicability, mature industrial preparation conditions, and has high propane conversion rate and propylene selectivity and catalytic activity stability. The development of metal cobalt / metal-based double heterojunction multiphase catalytic materials can not only significantly promote the development of the propane dehydrogenation to propylene industry, but also provide guidance for the design of high-performance catalysts for other hydrocarbon conversions in industry. Summary of the invention
[0006] In view of the shortcomings of the prior art, the present invention provides a metal cobalt / metal-based double heterojunction heterogeneous catalytic material for preparing propylene by dehydrogenation of propane, and in particular relates to a double heterojunction structure of metal cobalt and nitrogen-doped carbon and noble metal (Pt, Pd, Ru, Rh, Ir, etc.) and nitrogen-doped carbon independently constructed on the same carrier, and the synergistic transfer of electrons and reaction intermediates between the double heterojunctions promotes the selectivity of propylene.
[0007] The preparation method of the double heterojunction catalytic material of the present invention comprises the following process steps:
[0008] A method for preparing a double heterojunction catalytic material for efficient propane dehydrogenation to propylene, wherein the characteristic process steps are as follows: preparing a single heterojunction nitrogen-doped carbon-loaded metal cobalt composite material by high-temperature calcination; and preparing a metal cobalt / metal-based double heterojunction multiphase catalytic material by chemical reduction.
[0009] The preparation method of nitrogen-doped carbon-loaded metal cobalt composite material has the following characteristic process steps: a carbon source (citric acid, glucose, phenolic resin, etc.), a nitrogen source (dicyandiamide, melamine, urea, etc.), and a cobalt source (cobalt flakes, cobalt carbonate, cobalt chloride, etc.) are used to obtain a nitrogen-doped carbon-loaded metal cobalt composite material through a one-step calcination method.
[0010] The metal cobalt / metal-based double heterojunction heterogeneous catalytic material disperses the nitrogen-doped carbon-loaded metal cobalt composite material into water by ultrasonic dispersion. A solution containing a noble metal (Pt, Pd, Ru, Rh, Ir, etc.) is dripped into water containing a nitrogen-doped carbon-loaded metal cobalt composite material and stirred at room temperature. The noble metal is then reduced using a reducing agent (sodium borohydride, hydrogen), and finally washed and dried. The resulting sample is a metal cobalt / metal-based double heterojunction heterogeneous catalytic material.
[0011] In the metal cobalt / metal-based double heterojunction heterogeneous catalytic material, the mass percentage of cobalt element is 0.0001-50wt%, the types of precious metals are Pt, Pd, Ru, Rh, Ir, and the mass percentage of precious metal elements is 0.0001-40wt%,
[0012] The metal cobalt / metal-based double heterojunction heterogeneous catalytic material can be prepared as a catalyst for preparing propylene by dehydrogenating propane, and exhibits high propane conversion rate and propylene selectivity as well as long-term catalytic activity stability.
[0013] The technical feature of the present invention is: synthesizing metal cobalt / metal-based double heterojunction multiphase catalytic materials by high-temperature calcination and chemical reduction (sodium borohydride, hydrogen). The method has abundant raw materials, low cost, simple production process, green and safe production process, and can achieve the goal of industrial scale production. BRIEF DESCRIPTION OF THE DRAWINGS
[0014] Figure 1 This is a transmission electron microscope photograph of the metal cobalt / metal-based double heterojunction multiphase catalytic material prepared in Example 1.
[0015] Figure 2 The high-resolution transmission electron microscope photograph a and the energy dispersive X-ray spectroscopy element mapping map b of the metal cobalt / metal-based double heterojunction heterogeneous catalytic material prepared in Example 1.
[0016] Figure 3 This is the X-ray diffraction pattern of the metal cobalt / metal-based double heterojunction multiphase catalytic material prepared in Example 1.
[0017] Figure 4 X-ray photoelectron spectra of the metal cobalt / metal-based double heterojunction multiphase catalytic material prepared in Example 1, the nitrogen-doped carbon-supported metal platinum composite material prepared in Comparative Example 1, and the nitrogen-doped carbon-supported metal cobalt composite material prepared in Comparative Example 2.
[0018] Figure 5 The H of the metal cobalt / metal-based double heterojunction heterogeneous catalytic material prepared in Example 1, the nitrogen-doped carbon-supported metal platinum composite material prepared in Comparative Example 1, and the nitrogen-doped carbon-supported metal cobalt composite material prepared in Comparative Example 2 is 2 Temperature programmed reduction spectrum.
[0019] Figure 6 The conversion rate of propane dehydrogenation obtained under the test conditions of Example 13 by filling the nitrogen-doped carbon-supported metal platinum composite material obtained in Comparative Example 1 in the manner of Example 12.
[0020] Figure 7The conversion rate of propane dehydrogenation was obtained by filling the nitrogen-doped carbon-loaded metal cobalt composite material obtained in Comparative Example 2 with the metal cobalt / metal-based double heterojunction multiphase catalytic material obtained in Example 1 in accordance with the filling method of Example 12 under the test conditions of Example 13.
[0021] Figure 8 The propylene selectivity for propane dehydrogenation obtained under the test conditions of Example 13 is obtained by filling the nitrogen-doped carbon-loaded metal cobalt composite material obtained in Comparative Example 2 with the metal cobalt / metal-based double heterojunction multiphase catalytic material obtained in Example 1 in accordance with the filling method of Example 12. DETAILED DESCRIPTION
[0022] The following specific embodiments illustrate the implementation of the present invention, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. Although the description of the present invention will be introduced in conjunction with the preferred embodiment, this does not mean that the features of this invention are limited to this implementation. On the contrary, the purpose of introducing the invention in conjunction with the implementation is to cover other options or modifications that may extend based on the claims of the present invention. In order to provide a deep understanding of the present invention, the following description will include many specific details. The present invention can also be implemented without using these details. In addition, in order to avoid confusion or blurring the focus of the present invention, some specific details will be omitted in the description. It should be noted that the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.
[0023] It should be noted that in this specification, similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, it does not need to be further defined and explained in the subsequent drawings.
[0024] The terms “first”, “second”, etc. are only used for distinguishing descriptions and should not be understood as indicating or implying relative importance.
[0025] In the description of this embodiment, it is also necessary to explain that, unless otherwise clearly specified and limited, the terms "set", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in this embodiment can be understood according to specific circumstances.
[0026] In order to make the objectives, technical solutions and advantages of the present invention more clear, the embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.
[0027] After mixing the cobalt source material, the carbon source material, and the nitrogen source material in a certain proportion, calcining at 800-1000°C, cooling naturally, and grinding into powder with a mortar to obtain a composite material of nitrogen-doped carbon loaded with metal cobalt. The noble metal precursor is loaded on the carrier material by chemical reduction to obtain a metal cobalt / metal-based double heterojunction multiphase catalytic material. The carbon source can be citric acid, glucose, phenolic resin, etc., preferably glucose, the nitrogen source can be dicyandiamide, melamine, urea, etc., preferably dicyandiamide, the cobalt source can be cobalt flakes, cobalt carbonate, cobalt chloride, etc., preferably cobalt flakes, and the noble metal precursor can be platinum tetrachloride, platinum nitrate, palladium tetrachloride, palladium nitrate, rhodium dichloride, ruthenium dichloride, iridium trichloride, etc., preferably platinum tetrachloride. Among them, the mass ratio of glucose as a carbon source to dicyandiamide as a nitrogen source is 1:1-100:1. The mass ratio of glucose as a carbon source to cobalt flakes as a cobalt source is 15:1-200:1.
[0028] Embodiment 1:
[0029] Mix 1g of glucose with 100g of dicyandiamide. The obtained white powder and 4g of cobalt flakes are calcined at 800°C and then cooled to ambient temperature. The result is a composite material of nitrogen-doped carbon-supported metal cobalt. Add a solution containing 30mg of platinum tetrachloride to a solution containing a nitrogen-doped carbon-supported metal cobalt composite material and stir at room temperature. Then reduce, wash and dry the product. Obtain a metal cobalt / metal-based double heterojunction multiphase catalytic material.
[0030] Embodiment 2:
[0031] Mix 1g of glucose with 100g of melamine. The obtained white powder and 4g of cobalt flakes are calcined at 800°C and then cooled to ambient temperature. The result is a composite material of nitrogen-doped carbon-supported metal cobalt. Add a solution containing 30mg of platinum tetrachloride to a solution containing a nitrogen-doped carbon-supported metal cobalt composite material and stir at room temperature. Then reduce, wash and dry the product. Obtain a metal cobalt / metal-based double heterojunction multiphase catalytic material.
[0032] Embodiment 3:
[0033] Mix 1g of glucose with 100g of urea. The obtained white powder and 4g of cobalt flakes are calcined at 800°C and then cooled to ambient temperature. The result is a composite material of nitrogen-doped carbon-supported metal cobalt. Add a solution containing 30mg of platinum tetrachloride to a solution containing a nitrogen-doped carbon-supported metal cobalt composite material and stir at room temperature. Then reduce, wash and dry the product. Obtain a metal cobalt / metal-based double heterojunction multiphase catalytic material.
[0034] Embodiment 4:
[0035] Mix 1g of citric acid with 100g of dicyandiamide. The resulting white powder and 4g of cobalt flakes are calcined at 800°C and then cooled to ambient temperature. The result is a composite material of nitrogen-doped carbon-supported metal cobalt. Add a solution containing 30mg of platinum tetrachloride to a solution containing a nitrogen-doped carbon-supported metal cobalt composite material and stir at room temperature. Then reduce, wash and dry the product. Obtain a metal cobalt / metal-based double heterojunction multiphase catalytic material.
[0036] Embodiment 5:
[0037] Mix 1g of phenolic resin with 100g of dicyandiamide. The obtained white powder and 4g of cobalt flakes are calcined at 800°C and then cooled to ambient temperature. The result is a composite material of nitrogen-doped carbon-supported metal cobalt. Add a solution containing 30mg of platinum tetrachloride to a solution containing a nitrogen-doped carbon-supported metal cobalt composite material and stir at room temperature. Then reduce, wash and dry the product. Obtain a metal cobalt / metal-based double heterojunction multiphase catalytic material.
[0038] Embodiment 6:
[0039] Mix 1g of glucose with 100g of dicyandiamide. The resulting white powder and 4g of cobalt flakes are calcined at 800°C and then cooled to ambient temperature. The result is a composite material of nitrogen-doped carbon-supported metal cobalt. Add a solution containing 30mg of platinum nitrate to a solution containing a nitrogen-doped carbon-supported metal cobalt composite material and stir at room temperature. Then reduce, wash and dry the product. Obtain a metal cobalt / metal-based double heterojunction multiphase catalytic material.
[0040] Embodiment 7:
[0041] Mix 1g of glucose with 100g of dicyandiamide. The resulting white powder and 4g of cobalt flakes are calcined at 800°C and then cooled to ambient temperature. The result is a composite material of nitrogen-doped carbon-supported metal cobalt. Add a solution containing 30mg of palladium tetrachloride to a solution containing a nitrogen-doped carbon-supported metal cobalt composite material and stir at room temperature. Then reduce, wash and dry the product. Obtain a metal cobalt / metal-based double heterojunction multiphase catalytic material.
[0042] Embodiment 8:
[0043] Mix 1g of glucose with 100g of dicyandiamide. The resulting white powder and 4g of cobalt flakes are calcined at 800°C and then cooled to ambient temperature. The result is a composite material of nitrogen-doped carbon-supported metal cobalt. Add a solution containing 30mg of palladium nitrate to a solution containing a nitrogen-doped carbon-supported metal cobalt composite material and stir at room temperature. Then reduce, wash and dry the product. Obtain a metal cobalt / metal-based double heterojunction multiphase catalytic material.
[0044] Embodiment 9:
[0045] Mix 1g of glucose with 100g of dicyandiamide. The resulting white powder and 4g of cobalt flakes are calcined at 800°C and then cooled to ambient temperature. The result is a composite material of nitrogen-doped carbon-supported metal cobalt. Add a solution containing 30mg of rhodium dichloride to a solution containing a nitrogen-doped carbon-supported metal cobalt composite material and stir at room temperature. Then reduce, wash and dry the product. Obtain a metal cobalt / metal-based double heterojunction multiphase catalytic material.
[0046] Embodiment 10:
[0047] Mix 1g of glucose with 100g of dicyandiamide. The resulting white powder and 4g of cobalt flakes are calcined at 800°C and then cooled to ambient temperature. The result is a composite material of nitrogen-doped carbon-supported metal cobalt. Add a solution containing 30mg of ruthenium dichloride to a solution containing a nitrogen-doped carbon-supported metal cobalt composite material and stir at room temperature. Then reduce, wash and dry the product. Obtain a metal cobalt / metal-based double heterojunction multiphase catalytic material.
[0048] Embodiment 11:
[0049] Mix 1g of glucose with 100g of dicyandiamide. The obtained white powder and 4g of cobalt flakes are calcined at 800°C and then cooled to ambient temperature. The result is a composite material of nitrogen-doped carbon-supported metal cobalt. Add a solution containing 30mg of iridium trichloride to a solution containing a nitrogen-doped carbon-supported metal cobalt composite material and stir at room temperature. Then reduce, wash and dry the product. Obtain a gold-metal cobalt / metal-based double heterojunction multiphase catalytic material.
[0050] Example 12: Catalyst filling
[0051] The catalyst was filled into a high temperature resistant quartz tube with a diameter of 1 cm for propane dehydrogenation test. The specific contents are as follows: first, 1-5 mg of quartz wool was placed at the bottom of the quartz tube, then 100-200 mg of the catalyst prepared in Example 1-11 was added, then 1-5 mg of quartz wool was continuously filled on the surface of the catalyst, and finally 0.5-2 g of quartz sand was filled on the surface of the upper quartz wool.
[0052] Example 13: Performance test of propane dehydrogenation to produce propylene
[0053] The catalyst prepared in Examples 1-11 of the present invention was tested for the dehydrogenation of propane to produce propylene in the filling manner of Example 12. The test temperature was 300-600°C, the test pressure was atmospheric pressure, the test time was 1-60h, and the flow rate of the raw material mixed gas was 30-100mL L -1The raw material mixed gas component ratio is propane: nitrogen: hydrogen = 1%-50%: 1%-50%: 1%-50% Comparative Example 1: Propane dehydrogenation test of nitrogen-doped carbon-supported metal platinum composite material to produce propylene
[0054] The commercial nitrogen-doped carbon-supported metal platinum composite material (metal platinum mass fraction of 20%) was filled in the manner of Example 12 and tested for the dehydrogenation of propane to produce propylene under the test conditions of Example 13. The comparative example used a commercial platinum-based catalyst that is currently more widely studied, and compared its performance with that of the example.
[0055] Comparative Example 2: Propane dehydrogenation test of nitrogen-doped carbon-supported metal cobalt composite material to produce propylene
[0056] The nitrogen-doped carbon-supported metal cobalt composite materials prepared in Examples 1-11 were filled in the same manner as in Example 12 and tested for the dehydrogenation of propane to produce propylene under the test conditions of Example 13. The comparative example used a single heterojunction nitrogen-doped carbon-supported metal cobalt composite catalytic material, which is currently widely studied, and compared its performance with that of the examples.
[0057] The following observations and evaluations are made on the preparation examples, especially the metal cobalt / metal-based double heterojunction multiphase catalytic material obtained mainly based on Example 1.
[0058] Figure 1 This is a transmission electron microscope photograph of the metal cobalt / metal-based double heterojunction multiphase catalytic material prepared in Example 1.
[0059] Figure 2 The high-resolution transmission electron microscope photograph a and the energy dispersive X-ray spectroscopy element mapping map b of the metal cobalt / metal-based double heterojunction heterogeneous catalytic material prepared in Example 1.
[0060] Figure 3 This is the X-ray diffraction pattern of the metal cobalt / metal-based double heterojunction multiphase catalytic material prepared in Example 1.
[0061] Figure 4 X-ray photoelectron spectra of the metal cobalt / metal-based double heterojunction multiphase catalytic material prepared in Example 1, the nitrogen-doped carbon-supported metal platinum composite material prepared in Comparative Example 1, and the nitrogen-doped carbon-supported metal cobalt composite material prepared in Comparative Example 2.
[0062] Figure 5 The H of the metal cobalt / metal-based double heterojunction heterogeneous catalytic material prepared in Example 1, the nitrogen-doped carbon-supported metal platinum composite material prepared in Comparative Example 1, and the nitrogen-doped carbon-supported metal cobalt composite material prepared in Comparative Example 2 is 2 Temperature programmed reduction spectrum.
[0063] Figure 6The conversion rate of propane dehydrogenation obtained under the test conditions of Example 13 by filling the nitrogen-doped carbon-supported metal platinum composite material obtained in Comparative Example 1 in the manner of Example 12.
[0064] Figure 7 The conversion rate of propane dehydrogenation was obtained by filling the nitrogen-doped carbon-loaded metal cobalt composite material obtained in Comparative Example 2 with the metal cobalt / metal-based double heterojunction multiphase catalytic material obtained in Example 1 in accordance with the filling method of Example 12 under the test conditions of Example 13.
[0065] Figure 8 The propylene selectivity for propane dehydrogenation obtained under the test conditions of Example 13 is obtained by filling the nitrogen-doped carbon-loaded metal cobalt composite material obtained in Comparative Example 2 with the metal cobalt / metal-based double heterojunction multiphase catalytic material obtained in Example 1 in accordance with the filling method of Example 12.
[0066] from Figure 4 From the data, we can know that in the metal cobalt / metal-based double heterojunction heterogeneous catalytic material, metal platinum gains electrons, while metal cobalt loses electrons.
[0067] from Figure 5 From the data, it can be seen that in the metal cobalt / metal-based double heterojunction multiphase catalytic material, metal platinum can promote the overflow of hydrogen atoms to the nearby metal cobalt, thereby forming metal cobalt nanoparticles enriched with reaction intermediates (hydrogen atoms).
[0068] from Figure 6-Figure 8 From the data, it can be known that the hydrogen-rich electron-poor metal cobalt nanoparticles formed in the double heterojunction catalytic material of the present invention can be used as a catalyst for the dehydrogenation of propane to produce propylene. This unique catalytic material can not only obtain a very high propane conversion rate and propylene selectivity, but also has long-term performance stability.
[0069] Although the present invention has been illustrated and described with reference to certain preferred embodiments of the present invention, it should be understood by those skilled in the art that the above is a further detailed description of the present invention in conjunction with specific embodiments, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions. Those skilled in the art may make various changes in form and details, including making several simple deductions or substitutions, without departing from the spirit and scope of the present invention.
Claims
1. A metal cobalt / metal-based double heterojunction multiphase catalytic material that can be used for efficient propane dehydrogenation to propylene, the structural characteristics of the catalytic material are as follows: metal cobalt nanoparticles are embedded in a nitrogen-doped carbon carrier, while precious metals are loaded on the outer surface of the nitrogen-doped carbon carrier. The nitrogen-doped carbon carrier separates the two metal components, thereby forming a mutually independent double heterojunction structure on the same carrier.
2. According to claim 1, the mutually independent double heterojunctions in the metal cobalt / metal-based double heterojunction multiphase catalytic material can realize the transfer of electrons from metal cobalt to precious metals through the drive of the work function difference of the metal components, thereby forming charge-rich precious metal nanoparticles and charge-poor metal cobalt nanoparticles.
3. According to claims 1-2, the mutually independent double heterojunctions in the metal cobalt / metal-based double heterojunction multiphase catalytic material can realize the transfer of reaction intermediate hydrogen atoms from the precious metal to the metal cobalt nanoparticles through the precious metal overflow effect, thereby forming hydrogen-enriched, electrically poor metal cobalt nanoparticles.
4. The metal cobalt / metal-based double heterojunction heterogeneous catalytic material according to claims 1-3. The mass percentage of cobalt element is 0.0001-50wt%, the types of precious metals are Pt, Pd, Ru, Rh, Ir, etc., and the mass percentage of precious metal elements is 0.0001-40wt%.
5. The metal cobalt / metal-based double heterojunction heterogeneous catalytic material according to claims 1-4 can be prepared as a catalyst for dehydrogenating propane to produce propylene, and exhibits high propane conversion and propylene selectivity as well as long-term catalytic activity stability.