A tungsten oxide-supported platinum-manganese catalyst and its preparation method and application

Abstract

The invention discloses a tungsten oxide-supported platinum-manganese catalyst and a preparation method and application thereof. A tungsten oxide-supported platinum-manganese catalyst is prepared, which can efficiently catalyze the hydrogenolysis of polyols such as glycerol to generate propylene glycol. The experiment is carried out in a high-pressure reactor, has few by-products, is simple to operate, and is green and pollution-free. The prepared tungsten oxide-supported platinum-manganese catalyst has very good reaction activity and stability. After the catalyst has been subjected to three cycle experiments, the selectivity of 1,2-propylene glycol is about 70%.

Description

Technical Field

[0001] The invention relates to the field of fine chemicals, in particular to a tungsten oxide-supported platinum-manganese catalyst and a preparation method and application thereof. Background Art

[0002] Fossil energy is the main energy consumed globally, and global consumption is still dominated by traditional energy. With the rapid development of social economy, the supply of fossil energy is becoming increasingly tight, and the environmental pollution and climate change problems it brings need to be solved urgently. The transformation from heavily polluting fossil energy to clean, renewable, and green new energy that is conducive to the sustainable development of society is the main direction of energy development today. Biomass has great application prospects as a renewable energy source to replace petroleum products. If more biomass energy is used to replace or completely replace the use of fossil fuels, the carbon dioxide in the atmosphere will not increase, but will decrease, because more and more carbon is stored in green plants. Polyols include glycerol, erythritol, xylitol, sorbitol, etc. For example, glycerol is the main by-product of biodiesel production from soybean oil or animal fat oil, accounting for about 10wt% of biodiesel production. Due to the large surplus of glycerol, the price continues to fall, so it is of great industrial value to convert excess glycerol and other polyols into high-value-added fine chemicals.

[0003] 1,2-propylene glycol is a colorless, transparent, viscous liquid. Due to its low freezing point, it can be mixed with water or ethylene glycol in an appropriate proportion to reduce the freezing point of the mixed liquid to -60°C. It is a good antifreeze agent. Due to its non-toxicity, good viscosity and hygroscopicity, it is widely used as a solvent, hygroscopic agent, lubricant, etc. in the pharmaceutical, food, cosmetics, detergent, coating and other industries. In the pharmaceutical industry, 1,2-propylene glycol can be used as an excipient, solvent and adjuvant for various ointments, creams and pills; in the food industry, 1,2-propylene glycol can be used as an emulsifier, etc.

[0004] At present, the main method for producing 1,2-propylene glycol at home and abroad is the hydrolysis of propylene oxide, that is, propylene oxide is hydrolyzed in the presence of an acidic catalyst to synthesize 1,2-propylene glycol in one step. Companies using this technology include Lyondell, Dow, Basfshell, etc. However, propylene oxide itself has disadvantages such as low melting point, flammability, and toxicity. In addition, the production process also has disadvantages such as harsh production conditions, serious corrosion of production equipment, high cost, and severe environmental pollution. Summary of the invention

[0005] The purpose of the present invention is to solve the deficiencies in the prior art and to provide a tungsten oxide-supported platinum-manganese catalyst and a preparation method and application thereof.

[0006] To achieve the above object, the present invention is implemented according to the following technical solutions:

[0007] The first object of the present invention is to provide a method for preparing a tungsten oxide-supported platinum-manganese catalyst, comprising the following steps:

[0008] S1. Using tungsten oxide as a carrier, immerse an equal volume of a deionized water solution containing hexahydrate chloroplatinic acid as a solute, stir evenly until it becomes a slurry, and then let it stand overnight to obtain a slurry solid;

[0009] S2, putting the slurry solid into a drying oven, drying it, and then grinding it into solid powder;

[0010] S3, placing the solid powder in a tube furnace, introducing H2 / Ar mixed gas, and calcining at 300°C for 1-3h; then switching the H2 / Ar mixed gas to O2 / N2 mixed gas, and passivating at room temperature for 1h to obtain black solid powder Pt / WO3;

[0011] S4, immersing an equal volume of black solid powder Pt / WO3 into a deionized water solution containing manganese nitrate tetrahydrate solute, stirring evenly until it becomes a slurry, and then immersing overnight to obtain a blue slurry solid;

[0012] S5, putting the blue slurry solid into a drying oven, drying it, and then grinding it into a blue solid powder;

[0013] S6. The blue solid powder is placed in a tubular furnace and introduced with H2 / Ar mixed gas and calcined at 700°C for 1-5h; then the H2 / Ar mixed gas is switched to O2 / N2 mixed gas, and passivated at room temperature for 1h to obtain tungsten oxide-supported platinum manganese catalyst Mn / Pt / W.

[0014] Preferably, the stirring time in steps S1 and S4 is 10-60 min.

[0015] Preferably, in steps S2 and S5, the drying time in the drying oven is 6-18 hours, and the drying temperature is 110°C.

[0016] Preferably, the concentration of H2 in the H2 / Ar mixed gas is 5-40%.

[0017] Preferably, the concentration of O2 in the O2 / N2 mixed gas is 1%.

[0018] The second object of the present invention is to provide a tungsten oxide-supported platinum-manganese catalyst prepared by the above method, wherein the platinum loading amount of the tungsten oxide-supported platinum-manganese catalyst is 1-3wt%, and the manganese loading amount is 1-16wt%.

[0019] The third object of the present invention is to provide a use of the aforementioned tungsten oxide-supported platinum-manganese catalyst in catalyzing the hydrogenolysis of polyols to prepare 1,2-propylene glycol.

[0020] Preferably, the polyol is one of glycerol, erythritol, xylitol and sorbitol.

[0021] Compared with the prior art, the present invention innovatively proposes a tungsten oxide-supported platinum-manganese catalyst, which can efficiently catalyze the hydrogenolysis of polyols such as glycerol to produce propylene glycol. The experiment is carried out in a high-pressure reactor, with few by-products, simple operation, and green and pollution-free. The prepared tungsten oxide-supported platinum-manganese catalyst has very good reaction activity and stability. After three cycle experiments on the catalyst, the selectivity of 1,2-propylene glycol is about 70%. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments. The specific embodiments described herein are only used to explain the present invention and are not used to limit the invention.

[0023] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0024] Unless otherwise specified, the materials and reagents used in the examples can be obtained from commercial sources.

[0025] The detection and analysis of the products are carried out quantitatively by Shimadzu's gas chromatography, using a FID detector and an HP-INNOWAX chromatographic column. Under this condition, products such as 1,2-propylene glycol, n-propanol, 1,3-propylene glycol, and 3-methoxy-1,2-propylene glycol can be well separated and quantitatively detected. Example

[0026] Take 1g of tungsten oxide as a carrier, immerse an equal volume of it in a deionized water solution containing hexahydrate chloroplatinic acid (H2PtCl6•6H2O, Aladdin, ≥37.5% Pt), stir for 60min until it becomes a slurry, and then let it stand overnight to obtain a slurry solid; put the slurry solid into a 110℃ drying oven and dry it for 12h, then grind it into a solid powder; put the solid powder into a tube furnace and pass it through a 10% H2 / Ar (v / v) mixed gas, and roast it at 300℃ for 1-3h; then switch the H2 / Ar mixed gas to a 1% O2 / N2 (v / v) mixed gas, and passivate it at room temperature for 1h to obtain a black solid powder Pt / WO3; then the black solid powder Pt / W An equal volume of O3 was immersed in a deionized water solution containing tetrahydrate manganese nitrate (Mn(NO3)2•4H2O, McLean, ≥98%Mn) solute, stirred for 60 minutes until it became a slurry, and then immersed overnight to obtain a blue slurry solid; the blue slurry solid was placed in a 110°C drying oven and dried for 12 hours, and then ground into a blue solid powder; the blue solid powder was placed in a tubular furnace and introduced with a 10% H2 / Ar (v / v) mixed gas and calcined at 700°C for 1-5 hours; then the H2 / Ar mixed gas was switched to a 1% O2 / N2 (v / v) mixed gas, and passivated at room temperature for 1 hour to obtain a tungsten oxide-supported platinum manganese catalyst 2wt%Mn / 2wt%Pt / W. Example

[0027] Take 1g of tungsten oxide as a carrier, immerse an equal volume of it in a deionized water solution containing hexahydrate chloroplatinic acid (H2PtCl6•6H2O, Aladdin, ≥37.5% Pt), stir for 60min until it becomes a slurry, and then let it stand overnight to obtain a slurry solid; put the slurry solid into a 110℃ drying oven and dry it for 12h, then grind it into a solid powder; put the solid powder into a tube furnace and pass it through a 10% H2 / Ar (v / v) mixed gas, and roast it at 300℃ for 1-3h; then switch the H2 / Ar mixed gas to a 1% O2 / N2 (v / v) mixed gas, and passivate it at room temperature for 1h to obtain a black solid powder Pt / WO3; then the black solid powder Pt / W An equal volume of O3 was immersed in a deionized water solution containing tetrahydrate manganese nitrate (Mn(NO3)2•4H2O, McLean, ≥98%Mn) solute, stirred for 60 minutes until it became a slurry, and then immersed overnight to obtain a blue slurry solid; the blue slurry solid was placed in a 110°C drying oven and dried for 12 hours, and then ground into a blue solid powder; the blue solid powder was placed in a tubular furnace and introduced with a 10% H2 / Ar (v / v) mixed gas, and calcined at 700°C for 1-5 hours; then the H2 / Ar mixed gas was switched to a 1% O2 / N2 (v / v) mixed gas, and passivated at room temperature for 1 hour to obtain a tungsten oxide-supported platinum manganese catalyst 4wt%Mn / 2wt%Pt / W. Example

[0028] Take 1g of tungsten oxide as a carrier, immerse an equal volume of it in a deionized water solution containing hexahydrate chloroplatinic acid (H2PtCl6•6H2O, Aladdin, ≥37.5% Pt), stir for 60min until it becomes a slurry, and then let it stand overnight to obtain a slurry solid; put the slurry solid into a 110℃ drying oven and dry it for 12h, then grind it into a solid powder; put the solid powder into a tube furnace and pass it through a 10% H2 / Ar (v / v) mixed gas, and roast it at 300℃ for 1-3h; then switch the H2 / Ar mixed gas to a 1% O2 / N2 (v / v) mixed gas, and passivate it at room temperature for 1h to obtain a black solid powder Pt / WO3; then the black solid powder Pt / W An equal volume of O3 was immersed in a deionized water solution containing tetrahydrate manganese nitrate (Mn(NO3)2•4H2O, McLean, ≥98%Mn) solute, stirred for 60 minutes until it became a slurry, and then immersed overnight to obtain a blue slurry solid; the blue slurry solid was placed in a 110°C drying oven and dried for 12 hours, and then ground into a blue solid powder; the blue solid powder was placed in a tubular furnace and introduced with a 10% H2 / Ar (v / v) mixed gas, and calcined at 700°C for 1-5 hours; then the H2 / Ar mixed gas was switched to a 1% O2 / N2 (v / v) mixed gas, and passivated at room temperature for 1 hour to obtain a tungsten oxide-supported platinum manganese catalyst 8wt%Mn / 2wt%Pt / W. Example

[0029] Take 1g of tungsten oxide as a carrier, immerse an equal volume of it in a deionized water solution containing hexahydrate chloroplatinic acid (H2PtCl6•6H2O, Aladdin, ≥37.5% Pt), stir for 60min until it becomes a slurry, and then let it stand overnight to obtain a slurry solid; put the slurry solid into a 110℃ drying oven and dry it for 12h, then grind it into a solid powder; put the solid powder into a tube furnace and pass it through a 10% H2 / Ar (v / v) mixed gas, and roast it at 300℃ for 1-3h; then switch the H2 / Ar mixed gas to a 1% O2 / N2 (v / v) mixed gas, and passivate it at room temperature for 1h to obtain a black solid powder Pt / WO3; then the black solid powder Pt / W An equal volume of O3 was immersed in a deionized water solution containing tetrahydrate manganese nitrate (Mn(NO3)2•4H2O, McLean, ≥98%Mn) solute, stirred for 60 minutes until it became a slurry, and then immersed overnight to obtain a blue slurry solid; the blue slurry solid was placed in a 110°C drying oven and dried for 12 hours, and then ground into a blue solid powder; the blue solid powder was placed in a tubular furnace and introduced with a 10% H2 / Ar (v / v) mixed gas, and calcined at 700°C for 1-5 hours; then the H2 / Ar mixed gas was switched to a 1% O2 / N2 (v / v) mixed gas, and passivated at room temperature for 1 hour to obtain a tungsten oxide-supported platinum manganese catalyst 16wt%Mn / 2wt%Pt / W.

[0030] Application Example 1

[0031] Catalyst activity evaluation: The reaction was carried out in a 50ml high-pressure reactor equipped with a thermocouple and an external magnetic stirrer. First, 0.05g of 2wt%Mn / 2wt%Pt / W catalyst was accurately weighed with an analytical balance, and 0.05g of catalyst and 10ml of glycerol methanol solution (3wt%) were placed in the above reactor. The reactor was purged with hydrogen six times to exhaust the air, and the initial pressure was set to 6MPa. The reactor was rapidly heated to 240°C at a stirring speed of 600rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled rapidly. After cooling, the gaseous products were collected with an air bag and analyzed, the reaction liquid product was centrifuged to separate the catalyst and the reaction liquid, and the supernatant was taken for gas phase analysis.

[0032] Application Example 2

[0033] Catalyst activity evaluation: The reaction was carried out in a 50ml high-pressure reactor equipped with a thermocouple and an external magnetic stirrer. First, 0.05g of 4wt%Mn / 2wt%Pt / W catalyst was accurately weighed with an analytical balance, and 0.05g of catalyst and 10ml of glycerol methanol solution (3wt%) were placed in the above reactor. The reactor was purged with hydrogen six times to exhaust the air, and the initial pressure was set to 6MPa. The reactor was rapidly heated to 240°C at a stirring speed of 600rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled rapidly. After cooling, the gaseous products were collected with an air bag and analyzed, the reaction liquid product was centrifuged to separate the catalyst and the reaction liquid, and the supernatant was taken for gas phase analysis.

[0034] Application Example 3

[0035] Catalyst activity evaluation: The reaction was carried out in a 50ml high-pressure reactor equipped with a thermocouple and an external magnetic stirrer. First, 0.05g of 8wt%Mn / 2wt%Pt / W catalyst was accurately weighed with an analytical balance, and 0.05g of catalyst and 10ml of glycerol methanol solution (3wt%) were placed in the above reactor. The reactor was purged with hydrogen six times to exhaust the air, and the initial pressure was set to 6MPa. The reactor was rapidly heated to 240°C at a stirring speed of 600rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled rapidly. After cooling, the gaseous products were collected with an air bag and analyzed, the reaction liquid product was centrifuged to separate the catalyst and the reaction liquid, and the supernatant was taken for gas phase analysis.

[0036] Application Example 4

[0037] Catalyst activity evaluation: The reaction was carried out in a 50ml high-pressure reactor equipped with a thermocouple and an external magnetic stirrer. First, 0.05g of 16wt%Mn / 2wt%Pt / W catalyst was accurately weighed with an analytical balance, and 0.05g of catalyst and 10ml of glycerol methanol solution (3wt%) were placed in the above reactor. The reactor was purged with hydrogen six times to exhaust the air, and the initial pressure was set to 6MPa. The reactor was rapidly heated to 240°C at a stirring speed of 600rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled rapidly. After cooling, the gaseous products were collected with an air bag and analyzed, the reaction liquid product was centrifuged to separate the catalyst and the reaction liquid, and the supernatant was taken for gas phase analysis.

[0038] Application Example 5

[0039] Catalyst activity evaluation: The reaction was carried out in a 50 ml autoclave equipped with a thermocouple and an external magnetic stirrer. First, 0.05 g of 8 wt% Mn / 2 wt% Pt / W catalyst was accurately weighed on an analytical balance, and 0.05 g of catalyst and 10 ml of sorbitol methanol solution (3 wt%) were placed in the above reactor. The reactor was purged six times with hydrogen to exhaust the air, and the initial pressure was set to 6 MPa. The reactor was rapidly heated to 240 ° C at a stirring speed of 600 rpm. After 12 hours of reaction, the reactor was quickly transferred to cold water and cooled rapidly. After cooling, the gaseous products were collected with an air bag and analyzed, the reaction liquid product was centrifuged to separate the catalyst and the reaction liquid, and the supernatant was taken for gas phase analysis.

[0040] Application Example 6

[0041] Catalyst activity evaluation: The reaction was carried out in a 50ml high-pressure reactor equipped with a thermocouple and an external magnetic stirrer. First, 0.05g of 8wt%Mn / 2wt%Pt / W catalyst was accurately weighed with an analytical balance, and 0.05g of catalyst and 10ml of sorbitol methanol solution (3wt%) were placed in the above reactor. The reactor was purged with hydrogen six times to exhaust the air, and the initial pressure was set to 6MPa. The reactor was rapidly heated to 220°C at a stirring speed of 600rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled rapidly. After cooling, the gaseous products were collected with an air bag and analyzed, the reaction liquid product was centrifuged to separate the catalyst and the reaction liquid, and the supernatant was taken for gas phase analysis.

[0042] Application Example 7

[0043] Catalyst activity evaluation: The reaction was carried out in a 50ml high-pressure reactor equipped with a thermocouple and an external magnetic stirrer. First, 0.05g of 8wt%Mn / 2wt%Pt / W catalyst obtained after centrifugation in Application Example 3 and 10ml of glycerol methanol solution (3wt%) were placed in the above reactor. The reactor was purged with hydrogen six times to exhaust the air, and the initial pressure was set to 6MPa. The reactor was rapidly heated to 240°C at a stirring speed of 600rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled rapidly. After cooling, the gaseous products were collected with an air bag and analyzed, the reaction liquid product was centrifuged to separate the catalyst and the reaction liquid, and the supernatant was taken for gas phase analysis.

[0044] Application Example 8

[0045] Catalyst activity evaluation: The reaction was carried out in a 50ml high-pressure reactor equipped with a thermocouple and an external magnetic stirrer. First, 0.05g of 8wt%Mn / 2wt%Pt / W catalyst obtained after centrifugation in Application Example 7 and 10ml of glycerol methanol solution (3wt%) were placed in the above reactor. The reactor was purged with hydrogen six times to exhaust the air, and the initial pressure was set to 6MPa. The reactor was rapidly heated to 240°C at a stirring speed of 600rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled rapidly. After cooling, the gaseous products were collected with an air bag and analyzed, the reaction liquid product was centrifuged to separate the catalyst and the reaction liquid, and the supernatant was taken for gas phase analysis.

[0046] Application Example 9

[0047] Catalyst activity evaluation: The reaction was carried out in a 50ml autoclave equipped with a thermocouple and an external magnetic stirrer. First, 0.05g of 8wt%Mn / 2wt%Pt / W catalyst obtained after centrifugation in Application Example 8 and 10ml of glycerol methanol solution (3wt%) were placed in the above reactor. The reactor was purged six times with hydrogen to exhaust the air, and the initial pressure was set to 6MPa. The reactor was rapidly heated to 240°C at a stirring speed of 600rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled rapidly. After cooling, the gaseous products were collected with an air bag and analyzed, the reaction liquid product was centrifuged to separate the catalyst and the reaction liquid, and the supernatant was taken for gas phase analysis.

[0048] Comparison examples

[0049] Catalyst activity evaluation: The reaction was carried out in a 50ml high-pressure reactor equipped with a thermocouple and an external magnetic stirrer. First, 0.05g of 2wt% Pt / WO3 catalyst was accurately weighed with an analytical balance, and 0.05g of catalyst and 10ml of glycerol methanol solution (3wt%) were placed in the above reactor. The reactor was purged with hydrogen six times to exhaust the air, and the initial pressure was set to 6MPa. The reactor was rapidly heated to 240°C at a stirring speed of 600rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled rapidly. After cooling, the gaseous products were collected with an air bag and analyzed, the reaction liquid product was centrifuged to separate the catalyst and the reaction liquid, and the supernatant was taken for gas phase analysis.

[0050] The gas phase analysis results of the above-mentioned application examples 1 to 9 and the control example are shown in Table 1.

[0051] Table 1

[0052] Case Raw materials and solvents Reaction conditions catalyst Conversion rate Product yield Application Example 1 10ml 3% glycerol methanol solution <![CDATA[240℃12h6MPa H2]]> 2wt%Mn / 2wt%Pt / W 100% 56% Application Example 2 10ml 3% glycerol methanol solution <![CDATA[240℃12h6MPa H2]]> 4wt%Mn / 2wt%Pt / W 100% 67% Application Example 3 10ml 3% glycerol methanol solution <![CDATA[240℃12h6MPa H2]]> 8wt%Mn / 2wt%Pt / W 100% 83% Application Example 4 10ml 3% glycerol methanol solution <![CDATA[240℃12h6MPa H2]]> 16wt%Mn / 2wt%Pt / W 100% 78% Application Example 5 10ml3% sorbitol methanol solution <![CDATA[240℃12h6MPa H2]]> 8wt%Mn / 2wt%Pt / W 100% 28% Application Example 6 10ml3% sorbitol methanol solution <![CDATA[220℃12h6MPa H2]]> 8wt%Mn / 2wt%Pt / W 100% 11% Application Example 7 10ml 3% glycerol methanol solution <![CDATA[240℃12h6MPa H2]]> 8wt%Mn / 2wt%Pt / W after the first cycle 100% 73% Application Example 8 10ml 3% glycerol methanol solution <![CDATA[240℃12h6MPa H2]]> 8wt%Mn / 2wt%Pt / W after the second cycle 100% 68% Application Example 9 10ml 3% glycerol methanol solution <![CDATA[240℃12h6MPa H2]]> 8wt%Mn / 2wt%Pt / W after the third cycle 100% 71% Comparison examples 10ml 3% glycerol methanol solution <![CDATA[240℃12h6MPa H2]]> 2wt%Pt / WO3 100% 6%

[0053] It can be seen from Table 1 that after loading manganese, the product distribution changes from n-propanol to 1,2-propylene glycol. With the increase of manganese loading, the selectivity of 1,2-propylene glycol increases from 56% to 83%. After further increasing the manganese loading, the selectivity of 1,2-propylene glycol decreases slightly. This may be due to the excessive manganese loading, which leads to a decrease in the specific surface area of ​​the carrier. Through three catalyst cycle experiments, it was found that the product selectivity was stable at around 70%. Not only was the selectivity of propylene glycol in the catalytic conversion experiment of glycerol through sorbitol also 28%, proving that the catalyst has a high selectivity for the preparation of 1,2-propylene glycol by hydrogenolysis of polyols.

[0054] The technical solution of the present invention is not limited to the above-mentioned specific embodiments. All technical variations made according to the technical solution of the present invention fall within the protection scope of the present invention.

Claims

1. Application of a tungsten oxide-supported platinum manganese catalyst in catalyzing the hydrogenolysis of polyols to prepare 1,2-propylene glycol, characterized in that: The preparation method of tungsten oxide supported platinum manganese catalyst comprises the following steps: S1. Using tungsten oxide as a carrier, immerse an equal volume of a deionized water solution containing chloroplatinic acid hexahydrate as a solute, stir evenly until it becomes a slurry, and then let it stand overnight to obtain a slurry solid; S2, putting the slurry solid into a drying oven, drying it, and then grinding it into solid powder; S3, placing the solid powder in a tube furnace, introducing H2 / Ar mixed gas, and calcining at 300°C for 1-3h, wherein the concentration of H2 in the H2 / Ar mixed gas is 5-40%; then switching the H2 / Ar mixed gas to O2 / N2 mixed gas, wherein the concentration of O2 in the O2 / N2 mixed gas is 1%, and passivating at room temperature for 1h to obtain black solid powder Pt / WO3; S4, immersing an equal volume of black solid powder Pt / WO3 into a deionized water solution containing manganese nitrate tetrahydrate as a solute, stirring evenly until it becomes a slurry, and then immersing overnight to obtain a blue slurry solid; S5, putting the blue slurry solid into a drying oven, drying it, and then grinding it into a blue solid powder; S6, placing the blue solid powder in a tube furnace, introducing H2 / Ar mixed gas, and calcining at 700°C for 1-5h, wherein the concentration of H2 in the H2 / Ar mixed gas is 5-40%; then switching the H2 / Ar mixed gas to O2 / N2 mixed gas, wherein the concentration of O2 in the O2 / N2 mixed gas is 1%, and passivating at room temperature for 1h to obtain tungsten oxide-supported platinum manganese catalyst Mn / Pt / W; The platinum loading amount of the tungsten oxide-loaded platinum-manganese catalyst is 1-3wt%, and the manganese loading amount is 1-16wt%; the polyol is one of glycerol, erythritol, xylitol, and sorbitol.