阅读说明：本技术 二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的金属氧化物改性铂基催化剂及方法 (Metal oxide modified platinum-based catalyst for preparing propylene and synthesis gas by carbon dioxide oxidation propane hydrodehydrogenation and method ) 是由 刘忠文 任星 杨国庆 王磊 胡蓉蓉 宋永红 葛汉青 于 2021-07-29 设计创作，主要内容包括：本发明公开了一种二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的金属氧化物改性铂基催化剂及方法,该催化剂的载体是SiO-(2)或Al-(2)O-(3),活性成分为Pt和Sn,助剂为CeO-(2)、MnO-(2)、ZrO-(2)、ZnO、TiO-(2)等金属氧化物中任意一种或多种；以催化剂的质量为100％计,Pt的负载量为0.1％～1.0％,Sn的负载量为0.5％～5.0％,助剂中金属元素的负载量为0.1％～5.0％；该催化剂采用浸渍法制备而成,制备工艺简单,成本低,经济环保。本发明催化剂对二氧化碳氧化丙烷临氢脱氢制丙烯和合成气不仅具有较高的丙烷和二氧化碳转化率,丙烯收率以及稳定性,而且能够富产氢气和一氧化碳。(The invention discloses a metal oxide modified platinum-based catalyst and a method for preparing propylene and synthesis gas by oxidizing propane with carbon dioxide and dehydrogenating the propane in hydrogen 2 Or Al 2 O 3 Active components of Pt and Sn and assistant of CeO 2 、MnO 2 、ZrO 2 、ZnO、TiO 2 Any one or more of metal oxides; based on the mass of the catalyst as 100%, the load capacity of Pt is 0.1-1.0%, the load capacity of Sn is 0.5-5.0%, and the load capacity of metal elements in the auxiliary agent is 0.1-5.0%; the catalyst is prepared by adopting an impregnation method, and has the advantages of simple preparation process, low cost, economy and environmental protection. The catalyst has high conversion rate of propane and carbon dioxide, propylene yield and stability, and can produce hydrogen and carbon monoxide in a rich way.)

1. A metal oxide modified platinum-based catalyst for preparing propylene and synthesis gas by carbon dioxide oxidation propane hydrodehydrogenation is characterized in that: the carrier of the catalyst is SiO₂Or Al₂O₃Active components of Pt and Sn and assistant of CeO₂、MnO₂、ZrO₂、ZnO、TiO₂Any one or more metal oxides; based on the mass of the catalyst as 100%, the load capacity of Pt is 0.1-1.0%, the load capacity of Sn is 0.5-5.0%, and the load capacity of metal elements in the auxiliary agent is 0.1-5.0%; the catalyst is prepared by the following method:

dissolving a precursor of an active ingredient and a precursor of an auxiliary agent in absolute ethyl alcohol by adopting an impregnation method according to the composition of a catalyst, then mixing the obtained solution with carrier powder, standing for 6-12 h at room temperature, then drying for 4-10 h at 60-110 ℃, roasting for 3-6 h at 500-650 ℃, naturally cooling to room temperature, tabletting, granulating, and sieving by a 40-60-mesh sieve to obtain the catalyst;

the catalyst is used for catalyzing the carbon dioxide to oxidize propane and prepare propylene and synthesis gas through hydrogen dehydrogenation.

2. The metal oxide modified platinum-based catalyst for preparing propylene and synthesis gas by the hydrodeoxygenation of propane through carbon dioxide as claimed in claim 1, which is characterized in that: based on the mass of the catalyst as 100%, the load capacity of Pt is 0.3-0.6%, the load capacity of Sn is 0.5-2.5%, and the load capacity of metal elements in the auxiliary agent is 1.0-3.0%.

3. The metal oxide-modified platinum-based catalyst for producing propylene and synthesis gas by the hydrodeoxygenation of propane through carbon dioxide according to claim 1 or 2, characterized in that: the auxiliary agent is CeO₂、CeO₂-MnO₂、CeO₂-ZnO or ZrO₂-ZnO。

4. The metal oxide modified platinum-based catalyst for preparing propylene and synthesis gas by the hydrodeoxygenation of propane through carbon dioxide as claimed in claim 1, which is characterized in that: when the auxiliary agent is more than two metal oxides, the molar ratio of any one metal oxide in the auxiliary agent is not less than 10%.

5. The metal oxide modified platinum-based catalyst for preparing propylene and synthesis gas by the hydrodeoxygenation of propane through carbon dioxide as claimed in claim 1, which is characterized in that: the precursor of the active ingredient Pt is H₂PtCl₆·6H₂O, precursor of Sn as active component is SnCl₂·2H₂O。

6. The metal oxide-modified platinum-based catalyst for the simultaneous hydrodehydrogenation of propane oxide with carbon dioxide to produce propylene and synthesis gas as claimed in claim 1, wherein: auxiliary agent CeO₂、MnO₂、ZrO₂The precursor of ZnO is metal nitrate; auxiliary agent TiO₂The precursor of (a) is titanium tetraisopropoxide.

7. The method for preparing propylene and synthesis gas by using the catalyst of claim 1 to catalyze the hydro-dehydrogenation of propane oxide by carbon dioxide is characterized by comprising the following steps: filling a 40-60-mesh catalyst into a quartz tube of a micro fixed bed reactor, introducing a mixed gas of hydrogen and argon into the reactor, heating the temperature to 250-550 ℃ from room temperature, reducing the temperature for 0.5-3 h, switching to argon, continuously heating to 500-650 ℃, switching to a reaction gas, wherein the reaction gas is a mixed gas of carbon dioxide gas, hydrogen and propane in a volume ratio of 0.5-5.0: 0.5-3.0: 1.0, and reacting under the pressure of 0.05-0.15 MPa.

8. The method for producing propylene and synthesis gas by the hydrodeoxygenation of propane dioxide according to claim 7, wherein: filling a 40-60 mesh catalyst into a quartz tube of a micro fixed bed reactor, introducing a mixed gas of hydrogen and argon into the reactor, heating the temperature to 400-500 ℃ from room temperature, reducing the temperature for 1-2 h, switching to argon, continuously heating to 580-630 ℃, switching to a reaction gas, and reacting under the pressure of 0.1-0.15 MPa.

9. The process for the preparation of propene and synthesis gas by the hydrodeoxygenation of propane with carbon dioxide according to claim 7 or 8, characterized in that: the reaction gas is a mixed gas of carbon dioxide gas, hydrogen and propane in a volume ratio of 1-2: 1-1.5: 1.

Technical Field

The invention belongs to the technical field of catalysts, and particularly relates to a metal oxide modified platinum-based catalyst for simultaneously preparing propylene and synthesis gas by the hydrodeoxygenation of propane by carbon dioxide, and a method for simultaneously preparing propylene and synthesis gas by the hydrodeoxygenation of propane by carbon dioxide by adopting the catalyst.

Background

Propylene is an important basic chemical raw material and plays an important role in the modern petrochemical industry. For a long time, propylene is mainly produced by processes such as steam thermal cracking and catalytic thermal cracking of naphtha, but the processes have the problems of high equipment investment, low raw material processing capacity, high energy consumption, resource exhaustion and the like. In consideration of two important problems of large propylene demand gap and low comprehensive utilization rate of propane, the propane dehydrogenation is regarded as a key process for efficiently producing propylene at present.

Although direct dehydrogenation of propane has been industrialized, the above-mentioned routes have had problems such as low propylene yield and poor catalyst stability, etc., in view of the existing possibilities such as direct dehydrogenation (PDH) for producing propylene by dehydrogenation of propane, oxidative dehydrogenation of oxygen, oxidative dehydrogenation of a weak oxidizing agent such as carbon dioxide, etc. For the direct dehydrogenation of propane, the thermodynamic analysis result shows that the introduction of hydrogen into the reaction system is not favorable for the forward progress of the PDH reaction and further inhibits the generation of propylene. The result of the dynamics research shows that the propane dehydrogenation can effectively inhibit the carbon deposition reaction on the catalyst, thereby obviously reducing the carbon loss and obviously improving the yield of the propylene while improving the stability of the catalyst. Therefore, propane dehydrogenation has important research and application values from the industrial application and dynamics perspective.

Carbon dioxide oxidative propane dehydrogenation (CO)₂ODP) not only can overcome the problems of high PDH energy consumption, low raw material processing capacity and the like, but also can realize greenhouse gas CO₂The resource utilization of the catalyst is expected to become an energy-saving and environment-friendly green synthesis process, but the existing catalyst generally has the problems of low activity, rapid inactivation and the like.

Disclosure of Invention

The invention comprehensively analyzes the existing PDH and CO₂On the basis of the advantages and disadvantages of ODP, the simultaneous introduction of H into the direct propane dehydrogenation reaction system is proposed₂And CO₂On the one hand, by means of CO introduced into the reaction system₂The weak oxidant is used for relieving the thermodynamic equilibrium limit of direct dehydrogenation of propane, improving the conversion rate of propane and simultaneously introducing H into a reaction system₂Carbon deposit is inhibited, the service life of the catalyst is prolonged, and the propylene selectivity is improved; on the other hand, the aim of simultaneously preparing propylene and synthesis gas is achieved by utilizing a propane and carbon dioxide reforming reaction (CRP), a reverse water gas shift Reaction (RWGS) and a coupling effect of the CRP and the RWGS.

The invention also provides a metal oxide modified platinum-based catalyst with the functions of catalyzing PDH, CRP and RWGS, so as to meet the requirements of high activity and good stability for simultaneously preparing propylene and synthesis gas by the hydrodehydrogenation of propane oxide through carbon dioxide.

For the above purpose, the carrier of the platinum-based catalyst modified with a metal oxide used in the present invention is SiO₂Or Al₂O₃Active components of Pt and Sn and assistant of CeO₂、MnO₂、ZrO₂、ZnO、TiO₂Any one or more metal oxides; based on the mass of the catalyst as 100%, the load capacity of Pt is 0.1-1.0%, the load capacity of Sn is 0.5-5.0%, and the load capacity of metal elements in the auxiliary agent is 0.1-5.0%; the catalyst is prepared by the following method:

dissolving a precursor of an active ingredient and a precursor of an auxiliary agent in absolute ethyl alcohol by adopting an impregnation method according to the composition of the catalyst, then mixing the obtained solution with carrier powder, standing for 6-12 h at room temperature, then drying for 4-10 h at 60-110 ℃, roasting for 3-6 h at 500-650 ℃, naturally cooling to room temperature, tabletting, granulating, and sieving by a 40-60-mesh sieve to obtain the catalyst.

In the metal oxide modified platinum-based catalyst, the preferable load of Pt is 0.3-0.6%, the load of Sn is 0.5-2.5%, and the load of metal elements in the auxiliary agent is 1.0-3.0%, wherein the mass of the catalyst is 100%.

In the platinum-based catalyst modified with metal oxide, CeO is preferably used as the auxiliary agent₂、CeO₂-MnO₂、CeO₂-ZnO or ZrO₂-ZnO。

When the auxiliary agent is two or more metal oxides, the molar ratio of any one of the metal oxides in the auxiliary agent is preferably not less than 10%.

In the preparation method of the catalyst, the precursor of the active ingredient Pt is H₂PtCl₆·6H₂Precursors of O and Sn are SnCl₂·2H₂O; the auxiliary agent CeO₂、MnO₂、ZrO₂The precursor of ZnO is metal nitrate, TiO₂The precursor of (a) is titanium tetraisopropoxide.

The method for preparing the propylene and the synthesis gas by the catalytic oxydehydrogenation of the propane oxide by the carbon dioxide comprises the following steps: filling a 40-60-mesh catalyst into a quartz tube of a micro fixed bed reactor, introducing a mixed gas of hydrogen and argon into the reactor, heating the temperature to 250-550 ℃ from room temperature, reducing the temperature for 0.5-3 h, switching to argon, continuously heating to 500-650 ℃, switching to a reaction gas, wherein the reaction gas is a mixed gas of carbon dioxide gas, hydrogen and propane in a volume ratio of 0.5-5.0: 0.5-3.0: 1.0, and reacting under the pressure of 0.05-0.15 MPa.

In the method for preparing propylene and synthesis gas by catalytic carbon dioxide oxidation propane hydrodehydrogenation, preferably, a 40-60-mesh catalyst is filled in a quartz tube of a miniature fixed bed reactor, mixed gas of hydrogen and argon is introduced into the reactor, the temperature is raised to 400-500 ℃ from room temperature, the temperature is reduced for 1-2 h, then the argon is switched, the temperature is continuously raised to 580-630 ℃, then the argon is switched to reaction gas, and the reaction is carried out under the pressure of 0.1-0.15 MPa.

The reaction gas is preferably a mixed gas of carbon dioxide gas, hydrogen gas and propane in a volume ratio of 1-2: 1-1.5: 1.

The invention has the following beneficial effects:

1. the invention uses the platinum-based catalyst modified by the metal oxide prepared by the dipping method in the reaction of preparing propylene and synthesis gas by the dehydrogenation of propane oxide with hydrogen in the presence of carbon dioxide, wherein the auxiliary agent CeO₂、MnO₂、ZrO₂、ZnO、TiO₂The metal oxides have rich oxygen vacancies and excellent oxidation-reduction performance, can improve the dispersion degree of active components and promote the efficient conversion of propane on one hand, and can effectively activate CO on the other hand₂. In addition, the reaction processes of PDH, CRP and RWGS and the coupling effect of the three are regulated and controlled by strictly controlling the contents and the proportion of the added active components and the additives, so that the aim of efficiently producing propylene and synthesis gas simultaneously is fulfilled.

2. On one hand, the method of the invention utilizes the carbon dioxide weak oxidant introduced into the reaction system to relieve the thermodynamic equilibrium limitation of direct dehydrogenation of propane, improves the conversion rate of propane, and simultaneously introduces H into the reaction system₂Inhibiting carbon deposit and prolonging the service life of the catalyst.

Detailed Description

The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.

Comparative example 1

With Al₂O₃As a support, the Pt loading was 1%, 26.8mg H₂PtCl₆·6H₂O was dissolved in 1mL of anhydrous ethanol, and the resulting solution was mixed with 1.0g of Al₂O₃Mixing the powder, standing for 6h at room temperature, drying in a blast oven at 80 ℃ for 6h, roasting in a muffle furnace at 550 ℃ for 4h, naturally cooling to room temperature, tabletting, granulating, and sieving with a 40-60 mesh sieve to obtain the catalyst, which is recorded as 1% Pt/Al₂O₃。

Comparative example 2

With Al₂O₃As a support, Pt loading was 1% and Sn loading was 1.2%, 27.1mg H₂PtCl₆·6H₂O and 23.3mg SnCl₂·2H₂O was dissolved in 1mL of anhydrous ethanol, and the resulting solution was mixed with 1.0g of Al₂O₃Mixing the powder, standing for 6h at room temperature, drying for 6h in a blast oven at 80 ℃, roasting for 4h at 550 ℃ in a muffle furnace, naturally cooling to room temperature, tabletting, granulating, and sieving with a 40-60-mesh sieve to obtain the catalyst, wherein the catalyst is marked as 1% Pt-1.2% Sn/Al₂O₃。

Example 1

With Al₂O₃As carrier, Pt loading 0.5%, Sn loading 0.6%, CeO₂The loading of the middle Ce element is 3 percent, and 13.8mg of H₂PtCl₆·6H₂O、11.9mg SnCl₂·2H₂O and 96.9mg Ce (NO)₃)₃·6H₂O was dissolved in 1mL of anhydrous ethanol, and the resulting solution was mixed with 1.0g of Al₂O₃Mixing the powder, standing for 6h at room temperature, drying for 8h in a blast oven at 60 ℃, roasting for 4h at 550 ℃ in a muffle furnace, naturally cooling to room temperature, tabletting, granulating, and sieving with a 40-60-mesh sieve to obtain the catalyst, wherein the catalyst is recorded as 0.5% of Pt, 0.6% of Sn and 3% of Ce/Al₂O₃。

Example 2

With Al₂O₃As carrier, Pt loading 0.5%, Sn loading 0.4%, CeO₂The loading of the middle Ce element is 3 percent, and 13.8mg of H₂PtCl₆·6H₂O、7.9mg SnCl₂·2H₂O and 96.7mg Ce (NO)₃)₃·6H₂O was dissolved in 1mL of anhydrous ethanol, and the resulting solution was mixed with 1.0g of Al₂O₃Mixing the powder, standing for 6h at room temperature, drying for 8h in a blast oven at 60 ℃, roasting for 4h at 550 ℃ in a muffle furnace, naturally cooling to room temperature, tabletting, granulating, and sieving with a 40-60-mesh sieve to obtain the catalyst, wherein the catalyst is recorded as 0.5% of Pt, 0.4% of Sn and 3% of Ce/Al₂O₃。

Example 3

With Al₂O₃To be loadedPt loading 0.5%, Sn loading 0.6%, TiO₂The loading of the Ti element is 5 percent, 14.1mg of H₂PtCl₆·6H₂O、12.1mg SnCl₂·2H₂O and 316.2mg C₁₂H₂₈O₄Ti was dissolved in 1mL of anhydrous ethanol, and the resulting solution was mixed with 1.0g of Al₂O₃Mixing the powder, standing for 6h at room temperature, drying for 3h in a 110 ℃ blast oven, roasting for 4h at 550 ℃ in a muffle furnace, naturally cooling to room temperature, tabletting, granulating, and sieving with a 40-60 mesh sieve to obtain the catalyst, wherein the mark is 0.5% of Pt-0.6% of Sn-5% of Ti/Al₂O₃。

Example 4

With Al₂O₃As a carrier, Pt loading of 1%, Sn loading of 1.2%, MnO₂The loading of the medium Mn element is 3 percent, and 28.0mg of H₂PtCl₆·6H₂O、24.0mg SnCl₂·2H₂O and 144.5mg Mn (NO)₃)₂·4H₂O was dissolved in 1mL of anhydrous ethanol, and the resulting solution was mixed with 1.0g of Al₂O₃Mixing the powder, standing for 6h at room temperature, drying for 4h in a blast oven at 80 ℃, roasting for 4h at 550 ℃ in a muffle furnace, naturally cooling to room temperature, tabletting, granulating, and sieving with a 40-60-mesh sieve to obtain the catalyst, wherein the catalyst is recorded as 1% of Pt-1.2% of Sn-3% of Mn/Al₂O₃。

Example 5

With SiO₂As a carrier, Pt loading of 0.5%, Sn loading of 0.6%, MnO₂The loading of the medium Mn element is 5 percent, and 14.1mg of H₂PtCl₆·6H₂O、12.1mg SnCl₂·2H₂O and 243.2mg Mn (NO)₃)₂·4H₂O was dissolved in 1.2mL of anhydrous ethanol, and the resulting solution was mixed with 1.0g of SiO₂Mixing the powder, standing for 6h at room temperature, drying for 4h in a blast oven at 80 ℃, roasting for 4h at 550 ℃ in a muffle furnace, naturally cooling to room temperature, tabletting, granulating, and sieving with a 40-60-mesh sieve to obtain the catalyst, wherein the mark is 0.5% of Pt-0.6% of Sn-5% of Mn/SiO₂。

Example 6

With Al₂O₃As a carrier, Pt loading is 1 percent, Sn loading is 1.2 percent, Zn element loading in ZnO is 3 percent, 28.0mg of H₂PtCl₆·6H₂O、24.0mg SnCl₂·2H₂O and 143.9mg Zn (NO)₃)₂·6H₂O was dissolved in 1mL of anhydrous ethanol, and the resulting solution was mixed with 1.0g of Al₂O₃Mixing the powder, standing for 6h at room temperature, drying for 4h in a blast oven at 80 ℃, roasting for 4h at 550 ℃ in a muffle furnace, naturally cooling to room temperature, tabletting, granulating, and sieving with a 40-60-mesh sieve to obtain the catalyst, wherein the catalyst is recorded as 1% of Pt-1.2% of Sn-3% of Zn/Al₂O₃。

Example 7

With SiO₂As a support, Pt supported 0.5%, Sn supported 0.6%, ZrO₂The amount of Zr in the resulting mixture was 2.5% and the amount of Zn in the resulting mixture was 0.5% (Zr/Zn molar ratio: 0.8/0.2), 13.8mg of H was added₂PtCl₆·6H₂O、11.9mg SnCl₂·2H₂O、125.1mg Zr(NO₃)₄·5H₂O and 21.7mg Zn (NO)₃)₂·6H₂O was dissolved in 1.2mL of anhydrous ethanol, and the resulting solution was mixed with 1.0g of SiO₂Mixing the powders, standing for 6h at room temperature, drying for 3h in a 110 ℃ blast oven, roasting for 4h at 550 ℃ in a muffle furnace, naturally cooling to room temperature, tabletting, granulating, and sieving with a 40-60 mesh sieve to obtain the catalyst, wherein the mark is 0.5% of Pt, 0.6% of Sn, 2.5% of Zr and 0.5% of Zn/SiO₂。

Example 8

With Al₂O₃As carrier, Pt loading 0.5%, Sn loading 0.6%, CeO₂The loading amount of the medium Ce element is 4.7 percent, and MnO is added₂The supported amount of the medium Mn element was 0.3% (Ce/Mn molar ratio ═ 0.85/0.15), and 14.1mg of H was added₂PtCl₆·6H₂O、12.1mg SnCl₂·2H₂O、154.3mg Ce(NO₃)₃·6H₂O and 15.7mg Mn (NO)₃)₂·4H₂O was dissolved in 1mL of anhydrous ethanol, and the resulting solution was mixed with 1.0g of Al₂O₃Mixing the powders, standing at room temperature for 6 hr, and air-drying at 80 deg.CDrying in a box for 4h, roasting in a muffle furnace at 550 ℃ for 4h, naturally cooling to room temperature, tabletting, granulating, and sieving with a 40-60-mesh sieve to obtain the catalyst, wherein the mark is 0.5% of Pt, 0.6% of Sn, 4.7% of Ce, and 0.3% of Mn/Al₂O₃。

Example 9

With Al₂O₃As carrier, Pt loading 0.5%, Sn loading 0.6%, CeO₂The load of the middle Ce element is 2.4 percent and the TiO is₂The amount of Ti supported was 0.6% (Ce/Ti molar ratio: 0.6/0.4), and 13.8mg of H was added₂PtCl₆·6H₂O，11.9mg SnCl₂·2H₂O，78.9mg Ce(NO₃)₃·6H₂O and 34.5mg C₁₂H₂₈O₄Ti was dissolved in 1mL of anhydrous ethanol, and the resulting solution was mixed with 1.0g of Al₂O₃Mixing the powder, standing for 8h at room temperature, drying for 4h in a 110 ℃ blast oven, roasting for 4h at 550 ℃ in a muffle furnace, naturally cooling to room temperature, tabletting, granulating, and sieving with a 40-60-mesh sieve to obtain the catalyst, wherein the mark is 0.5% of Pt, 0.6% of Sn, 2.4% of Ce, 0.6% of Ti/Al₂O₃。

Example 10

With Al₂O₃As carrier, Pt loading 0.5%, Sn loading 0.6%, CeO₂The loading amount of the medium Ce element is 2.7 percent, and ZrO is₂The loading amount of the medium Zr element is 2 percent, and MnO is₂The supported amount of the medium Mn element was 0.3% (Ce/Zr/Mn molar ratio: 0.42/0.46/0.12), and 14.1mg of H was added₂PtCl₆·6H₂O、12.1mg SnCl₂·2H₂O、89.1mg Ce(NO₃)₃·6H₂O、100.5mg Zr(NO₃)₄·5H₂O and 14.6mg Mn (NO)₃)₂·4H₂O was dissolved in 1mL of anhydrous ethanol, and the resulting solution was mixed with 1.0g of Al₂O₃Mixing the powder, standing for 6h at room temperature, drying for 4h in a blast oven at 80 ℃, roasting for 4h at 550 ℃ in a muffle furnace, naturally cooling to room temperature, tabletting, granulating, and sieving with a 40-60-mesh sieve to obtain the catalyst, wherein the catalyst is recorded as 0.5% of Pt, 0.6% of Sn, 2.7% of Ce, 2% of Zr and 0.3% of Mn/Al₂O₃。

The catalysts prepared in comparative examples 1-2 and examples 1-10 are used for catalyzing the reaction of oxidizing propane by carbon dioxide and dehydrogenating the propane by hydrogen to prepare propylene and synthesis gas, and the specific test method is as follows:

putting 500mg of 40-60 mesh catalyst into a quartz tube of a fixed bed reactor, and introducing H into the reactor₂Mixed gas with Ar in a volume ratio of 1:9, and the flow rate is 50 mL/min^-1At 5 ℃ in min^-1The temperature rising rate is increased from room temperature to 500 ℃, and after the temperature is stable, the reduction is continued for 1 hour. Then the gas mixture is turned off, Ar is switched to 5 ℃ min^-1The temperature is raised to 600 ℃, after the temperature is stable, the reaction gas is switched to N₂As an internal standard gas, the reaction gas is CO₂、C₃H₈、H₂Mixed gas of (1: 1: 1) by volume ratio of CO₂、C₃H₈、H₂And N₂The flow rates of (A) are 16, 16 and 2 mL. min^-1The total flow rate of the reaction gas was 50 mL/min^-1And reacting under the condition that P is 0.1 MPa. The reactor effluent was analyzed on a gas chromatograph model PANNA a91 Plus, manufactured by chango instruments ltd. The main product of the reaction is CO₂、CO、CH₄、C₂H₆、C₂H₄、C₃H₈、C₃H₆、H₂. Using Ar as chromatographic column carrier gas, TCD for CO analysis₂、CO、H₂Content of (1), FID is CH analysis₄、C₂H₄、C₂H₆、C₃H₆、C₃H₈The content of (a). To make a quantitative comparison of the stability of the catalysts, the relative deactivation rate R (R ═ X) of the different catalysts was calculated₅-X₈₀)/X₅×100％，X₅And X₈₀Representing the propane conversion after 5min and 80min of reaction respectively), wherein a larger value of R indicates a faster deactivation of the catalyst, i.e. a less stable catalyst. The results are shown in Table 1.

TABLE 1

As can be seen from table 1, compared with comparative examples 1 and 2 of the conventional catalyst, the catalyst modified by metal oxide according to the present invention can significantly improve the conversion rate and stability of propane and carbon dioxide while maintaining high propylene selectivity for the reaction of producing propylene and synthesis gas by dehydrogenating propane oxide with hydrogen. More importantly, by introducing the metal oxide, the hydrogen production is significantly increased, and the yield of the synthesis gas is improved.