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CN116078380A - Tungsten oxide loaded platinum-manganese catalyst and preparation method and application thereof - Google Patents

Tungsten oxide loaded platinum-manganese catalyst and preparation method and application thereof Download PDF

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Publication number
CN116078380A
CN116078380A CN202211730147.7A CN202211730147A CN116078380A CN 116078380 A CN116078380 A CN 116078380A CN 202211730147 A CN202211730147 A CN 202211730147A CN 116078380 A CN116078380 A CN 116078380A
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tungsten oxide
manganese catalyst
supported platinum
solid
catalyst
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翁育靖
张明威
张玉龙
孙琦
邹敏
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Henan University of Technology
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Henan University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6562—Manganese
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a tungsten oxide supported platinum-manganese catalyst, a preparation method and application thereof, wherein the tungsten oxide supported platinum-manganese catalyst can efficiently catalyze the hydrogenolysis of polyhydric alcohols such as glycerol and the like to generate propylene glycol, and the experiment is carried out under a high-pressure reaction kettle, so that few byproducts are generated, the operation is simple, and the environment is protected and pollution is avoided; the prepared tungsten oxide loaded platinum-manganese catalyst has very good reaction activity and stability, and the selectivity of 1, 2-propylene glycol is about 70% after the catalyst is subjected to three-cycle experiments.

Description

Tungsten oxide loaded platinum-manganese catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a tungsten oxide supported platinum-manganese catalyst, a preparation method and application thereof.
Background
Fossil energy is the main energy consumed globally, the global consumption is still mainly the traditional energy, along with the rapid development of society economy, the supply of fossil energy is more and more intense, the problems of environmental pollution and climate change brought by the fossil energy need to be solved urgently, and the conversion from the fossil energy with heavy pollution to clean and renewable green novel energy which is beneficial to the sustainable development of society is the main direction of the energy development at present. Biomass has great application prospect as renewable energy sources for replacing petroleum products, and more biomass energy sources are used for replacing or completely replacing fossil fuels, so that carbon dioxide in the atmosphere is not increased, but is reduced, because more and more carbon is stored in green plants. The polyols include glycerol, erythrose, xylitol, sorbitol, and the like. Glycerol, for example, is a major byproduct of biodiesel production from soybean oil or animal fat oil, and is about 10wt% of biodiesel production, and since glycerol is largely excessive and the price is continuously low, it is industrially important to convert excessive glycerol and other polyols into high value-added fine chemicals.
1, 2-propanediol is a colorless transparent viscous liquid, and because of its low solidifying point, it can be mixed with water or glycol in proper proportion to make the solidifying point of mixed liquor drop to-60 deg.C, and is a good antifreezing agent, and because of its non-toxicity, viscosity and good hygroscopicity, it can be extensively used as solvent, hygroscopic agent and lubricant in the fields of medicine, food, cosmetics, cleaning agent and coating material, etc.. In the pharmaceutical industry, 1, 2-propanediol is used as an excipient for various ointments, ointments and pills, as a solvent and as an adjuvant for medical injections; in the food industry, 1, 2-propanediol is used as an emulsifier and the like.
At present, the method for producing 1, 2-propylene glycol at home and abroad mainly hydrolyzes propylene oxide, namely, propylene oxide is hydrolyzed under the action of an acid catalyst to synthesize 1, 2-propylene glycol in one step, a company utilizing the technology has Lyondell, dow, basfshell and the like, but propylene oxide has the defects of low melting point, flammability, toxicity and the like, and the production process also has the defects of severe production conditions, serious corrosion of production equipment, high cost, large environmental pollution and the like.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a tungsten oxide supported platinum-manganese catalyst, and a preparation method and application thereof.
In order to achieve the above purpose, the invention is implemented according to the following technical scheme:
the first object of the invention is to provide a preparation method of a tungsten oxide supported platinum manganese catalyst, which comprises the following steps:
s1, immersing a tungsten oxide carrier into deionized water solution containing hexahydrated chloroplatinic acid solute in an equal volume, uniformly stirring to slurry, and standing overnight to obtain slurry solid;
s2, placing the pasty solid into a drying box for drying, and grinding the pasty solid into solid powder;
s3, putting the solid powder into a tube furnace, and introducing H 2 Roasting Ar mixed gas at 300 ℃ for 1-3 hours; then H is taken up 2 Switching of Ar mixture to O 2 /N 2 Passivating the mixed gas for 1h at room temperature to obtain black solid powder Pt/WO 3 ；
S4, black solid powder Pt/WO 3 Immersing the mixture into deionized water solution containing tetrahydrated manganese nitrate solute in an equal volume, uniformly stirring to slurry, and immersing overnight to obtain blue-color slurry solid;
s5, placing the blue paste solid into a drying oven for drying, and grinding the blue paste solid into blue solid powder;
s6, placing the blue solid powder into a tube furnace, and introducing H 2 Roasting Ar mixed gas at 700 ℃ for 1-5h; then H is taken up 2 Switching of Ar mixture to O 2 /N 2 And passivating the mixed gas for 1h at room temperature to obtain the tungsten oxide supported platinum-manganese catalyst Mn/Pt/W.
Preferably, the stirring time in the steps S1 and S4 is 10-60min.
Preferably, the drying time in the drying box in the steps S2 and S5 is 6-18h, and the drying temperature is 110 ℃.
Preferably, the H 2 H in Ar gas mixture 2 The concentration of (2) is 5-40%.
Preferably, the O 2 /N 2 O in the mixed gas 2 The concentration of (2) was 1%.
A second object of the present invention is to provide a tungsten oxide-supported platinum manganese catalyst prepared by the above method. The tungsten oxide loaded platinum-manganese catalyst has a platinum loading of 1-3wt% and a manganese loading of 1-16wt%.
A third object of the present invention is to provide a use of the tungsten oxide supported platinum manganese catalyst according to claim 8 for catalyzing the hydrogenolysis of polyols to prepare 1, 2-propanediol.
Preferably, the polyol is one of glycerol, erythritol, xylitol, and sorbitol.
Compared with the prior art, the invention creatively provides the tungsten oxide supported platinum-manganese catalyst, which can efficiently catalyze the hydrogenolysis of polyhydric alcohols such as glycerol and the like to generate propylene glycol, and the experiment is carried out under a high-pressure reaction kettle, so that the catalyst has few byproducts, is simple to operate, is green and has no pollution; the prepared tungsten oxide loaded platinum-manganese catalyst has very good reaction activity and stability, and the selectivity of 1, 2-propylene glycol is about 70% after the catalyst is subjected to three-cycle experiments.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. The specific embodiments described herein are for purposes of illustration only and are not intended to limit the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples are commercially available unless otherwise specified.
The detection and analysis of the product are carried out by gas chromatography of Shimadzu, and the products such as 1, 2-propanediol, n-propanol, 1, 3-propanediol, 3-methoxy-1, 2-propanediol and the like can be well separated and quantitatively detected by adopting a FID detector and an HP-INNOWAX chromatographic column under the condition.
Example 1
1g of tungsten oxide is taken as a carrier, and is immersed in an equal volume containing chloroplatinic acid hexahydrate (H) 2 PtCl 6 ·6H 2 O, alatine, more than or equal to 37.5 percent Pt), stirring for 60 minutes to slurry, and standing overnight to obtain slurry solid; drying the pasty solid in a drying oven at 110 ℃ for 12 hours, and grinding the pasty solid into solid powder; solids are put intoThe powder is put into a tube furnace and 10 percent of H is introduced 2 Roasting Ar (v/v) mixed gas at 300 ℃ for 1-3h; then H is taken up 2 The Ar gas mixture is switched to 1%O 2 /N 2 (v/v) the mixture was passivated at room temperature for 1h to give black solid powder Pt/WO 3 The method comprises the steps of carrying out a first treatment on the surface of the And then black solid powder Pt/WO 3 Isovolumetric immersion of a solution containing manganese nitrate tetrahydrate (Mn (NO) 3 ) 2 ·4H 2 O, micarin, deionized water solution with Mn of more than or equal to 98 percent) solute, stirring for 60 minutes to slurry state, and then dipping overnight to obtain blue paste solid; drying the blue paste solid in a drying oven at 110 ℃ for 12 hours, and grinding the blue paste solid into blue solid powder; placing the blue solid powder into a tube furnace, and introducing 10% H 2 Roasting the Ar (v/v) mixed gas at 700 ℃ for 1-5h; then H is taken up 2 The Ar gas mixture is switched to 1%O 2 /N 2 (v/v) the mixture was passivated at room temperature for 1h to give a tungsten oxide supported platinum manganese catalyst 2wt% Mn/2wt% Pt/W.
Example 2
1g of tungsten oxide is taken as a carrier, and is immersed in an equal volume containing chloroplatinic acid hexahydrate (H) 2 PtCl 6 ·6H 2 O, alatine, more than or equal to 37.5 percent Pt), stirring for 60 minutes to slurry, and standing overnight to obtain slurry solid; drying the pasty solid in a drying oven at 110 ℃ for 12 hours, and grinding the pasty solid into solid powder; the solid powder was placed in a tube furnace and 10% H was introduced 2 Roasting Ar (v/v) mixed gas at 300 ℃ for 1-3h; then H is taken up 2 The Ar gas mixture is switched to 1%O 2 /N 2 (v/v) the mixture was passivated at room temperature for 1h to give black solid powder Pt/WO 3 The method comprises the steps of carrying out a first treatment on the surface of the And then black solid powder Pt/WO 3 Isovolumetric immersion of a solution containing manganese nitrate tetrahydrate (Mn (NO) 3 ) 2 ·4H 2 O, micarin, deionized water solution with Mn of more than or equal to 98 percent) solute, stirring for 60 minutes to slurry state, and then dipping overnight to obtain blue paste solid; drying the blue paste solid in a drying oven at 110 ℃ for 12 hours, and grinding the blue paste solid into blue solid powder; placing the blue solid powder into a tube furnace, and introducing 10% H 2 Roasting the Ar (v/v) mixed gas at 700 ℃ for 1-5h; then H is taken up 2 The Ar gas mixture is switched to 1%O 2 /N 2 (v/v) the mixture was passivated at room temperature for 1h to give an oxidationThe tungsten supported platinum manganese catalyst was 4wt% Mn/2wt% Pt/W.
Example 3
1g of tungsten oxide is taken as a carrier, and is immersed in an equal volume containing chloroplatinic acid hexahydrate (H) 2 PtCl 6 ·6H 2 O, alatine, more than or equal to 37.5 percent Pt), stirring for 60 minutes to slurry, and standing overnight to obtain slurry solid; drying the pasty solid in a drying oven at 110 ℃ for 12 hours, and grinding the pasty solid into solid powder; the solid powder was placed in a tube furnace and 10% H was introduced 2 Roasting Ar (v/v) mixed gas at 300 ℃ for 1-3h; then H is taken up 2 The Ar gas mixture is switched to 1%O 2 /N 2 (v/v) the mixture was passivated at room temperature for 1h to give black solid powder Pt/WO 3 The method comprises the steps of carrying out a first treatment on the surface of the And then black solid powder Pt/WO 3 Isovolumetric immersion of a solution containing manganese nitrate tetrahydrate (Mn (NO) 3 ) 2 ·4H 2 O, micarin, deionized water solution with Mn of more than or equal to 98 percent) solute, stirring for 60 minutes to slurry state, and then dipping overnight to obtain blue paste solid; drying the blue paste solid in a drying oven at 110 ℃ for 12 hours, and grinding the blue paste solid into blue solid powder; placing the blue solid powder into a tube furnace, and introducing 10% H 2 Roasting the Ar (v/v) mixed gas at 700 ℃ for 1-5h; then H is taken up 2 The Ar gas mixture is switched to 1%O 2 /N 2 (v/v) the mixture was passivated at room temperature for 1h to give a tungsten oxide supported platinum manganese catalyst 8wt% Mn/2wt% Pt/W.
Example 4
1g of tungsten oxide is taken as a carrier, and is immersed in an equal volume containing chloroplatinic acid hexahydrate (H) 2 PtCl 6 ·6H 2 O, alatine, more than or equal to 37.5 percent Pt), stirring for 60 minutes to slurry, and standing overnight to obtain slurry solid; drying the pasty solid in a drying oven at 110 ℃ for 12 hours, and grinding the pasty solid into solid powder; the solid powder was placed in a tube furnace and 10% H was introduced 2 Roasting Ar (v/v) mixed gas at 300 ℃ for 1-3h; then H is taken up 2 The Ar gas mixture is switched to 1%O 2 /N 2 (v/v) the mixture was passivated at room temperature for 1h to give black solid powder Pt/WO 3 The method comprises the steps of carrying out a first treatment on the surface of the And then black solid powder Pt/WO 3 Isovolumetric immersion of a solution containing manganese nitrate tetrahydrate (Mn (NO) 3 ) 2 ·4H 2 O, micarin, deionized water solution with Mn of more than or equal to 98 percent) solute, stirring for 60 minutes to slurry state, and then dipping overnight to obtain blue paste solid; drying the blue paste solid in a drying oven at 110 ℃ for 12 hours, and grinding the blue paste solid into blue solid powder; placing the blue solid powder into a tube furnace, and introducing 10% H 2 Roasting the Ar (v/v) mixed gas at 700 ℃ for 1-5h; then H is taken up 2 The Ar gas mixture is switched to 1%O 2 /N 2 (v/v) the mixture was passivated at room temperature for 1h to give a tungsten oxide supported platinum manganese catalyst 16wt% Mn/2wt% Pt/W.
Application example 1
Catalyst activity evaluation: the reaction was carried out in a 50ml autoclave equipped with a thermocouple and externally connected with a magnetic stirrer. First, 0.05g of 2wt% Mn/2wt% Pt/W catalyst was accurately weighed out with an analytical balance, and 0.05g of catalyst and 10ml of glycerol methanol solution (3 wt%) were placed in the above reactor. The reactor was purged six times with hydrogen to vent air, and the initial pressure was set at 6MPa. The reactor was rapidly heated to 240℃with stirring at 600 rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled. After cooling, collecting the gas product with a gas bag, analyzing, centrifugally separating the catalyst and the reaction liquid from the reaction liquid product, and taking the supernatant for gas phase analysis.
Application example 2
Catalyst activity evaluation: the reaction was carried out in a 50ml autoclave equipped with a thermocouple and externally connected with a magnetic stirrer. First, 0.05g of 4wt% Mn/2wt% Pt/W catalyst was accurately weighed out with an analytical balance, and 0.05g of catalyst and 10ml of glycerol methanol solution (3 wt%) were placed in the above reactor. The reactor was purged six times with hydrogen to vent air, and the initial pressure was set at 6MPa. The reactor was rapidly heated to 240℃with stirring at 600 rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled. After cooling, collecting the gas product with a gas bag, analyzing, centrifugally separating the catalyst and the reaction liquid from the reaction liquid product, and taking the supernatant for gas phase analysis.
Application example 3
Catalyst activity evaluation: the reaction was carried out in a 50ml autoclave equipped with a thermocouple and externally connected with a magnetic stirrer. First, 0.05g of 8wt% Mn/2wt% Pt/W catalyst was accurately weighed out with an analytical balance, and 0.05g of the catalyst and 10ml of glycerol methanol solution (3 wt%) were placed in the above reactor. The reactor was purged six times with hydrogen to vent air, and the initial pressure was set at 6MPa. The reactor was rapidly heated to 240℃with stirring at 600 rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled. After cooling, collecting the gas product with a gas bag, analyzing, centrifugally separating the catalyst and the reaction liquid from the reaction liquid product, and taking the supernatant for gas phase analysis.
Application example 4
Catalyst activity evaluation: the reaction was carried out in a 50ml autoclave equipped with a thermocouple and externally connected with a magnetic stirrer. First, 0.05g of 16wt% Mn/2wt% Pt/W catalyst was accurately weighed out with an analytical balance, and 0.05g of the catalyst and 10ml of glycerol methanol solution (3 wt%) were placed in the above reactor. The reactor was purged six times with hydrogen to vent air, and the initial pressure was set at 6MPa. The reactor was rapidly heated to 240℃with stirring at 600 rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled. After cooling, collecting the gas product with a gas bag, analyzing, centrifugally separating the catalyst and the reaction liquid from the reaction liquid product, and taking the supernatant for gas phase analysis.
Application example 5
Catalyst activity evaluation: the reaction was carried out in a 50ml autoclave equipped with a thermocouple and externally connected with a magnetic stirrer. First, 0.05g of 8wt% Mn/2wt% Pt/W catalyst was accurately weighed out with an analytical balance, and 0.05g of the catalyst and 10ml of sorbitol methanol solution (3 wt%) were placed in the above-mentioned reactor. The reactor was purged six times with hydrogen to vent air, and the initial pressure was set at 6MPa. The reactor was rapidly heated to 240℃with stirring at 600 rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled. After cooling, collecting the gas product with a gas bag, analyzing, centrifugally separating the catalyst and the reaction liquid from the reaction liquid product, and taking the supernatant for gas phase analysis.
Application example 6
Catalyst activity evaluation: the reaction was carried out in a 50ml autoclave equipped with a thermocouple and externally connected with a magnetic stirrer. First, 0.05g of 8wt% Mn/2wt% Pt/W catalyst was accurately weighed out with an analytical balance, and 0.05g of the catalyst and 10ml of sorbitol methanol solution (3 wt%) were placed in the above-mentioned reactor. The reactor was purged six times with hydrogen to vent air, and the initial pressure was set at 6MPa. The reactor was rapidly heated to 220 ℃ with stirring at 600 rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled. After cooling, collecting the gas product with a gas bag, analyzing, centrifugally separating the catalyst and the reaction liquid from the reaction liquid product, and taking the supernatant for gas phase analysis.
Application example 7
Catalyst activity evaluation: the reaction was carried out in a 50ml autoclave equipped with a thermocouple and externally connected with a 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 (3 wt%) were placed in the above reactor. The reactor was purged six times with hydrogen to vent air, and the initial pressure was set at 6MPa. The reactor was rapidly heated to 240℃with stirring at 600 rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled. After cooling, collecting the gas product with a gas bag, analyzing, centrifugally separating the catalyst and the reaction liquid from the reaction liquid product, and taking the supernatant for gas phase analysis.
Application example 8
Catalyst activity evaluation: the reaction was carried out in a 50ml autoclave equipped with a thermocouple and externally connected with a 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 (3 wt%) were placed in the above reactor. The reactor was purged six times with hydrogen to vent air, and the initial pressure was set at 6MPa. The reactor was rapidly heated to 240℃with stirring at 600 rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled. After cooling, collecting the gas product with a gas bag, analyzing, centrifugally separating the catalyst and the reaction liquid from the reaction liquid product, and taking the supernatant for gas phase analysis.
Application example 9
Catalyst activity evaluation: the reaction was carried out in a 50ml autoclave equipped with a thermocouple and externally connected with a 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 (3 wt%) were placed in the above reactor. The reactor was purged six times with hydrogen to vent air, and the initial pressure was set at 6MPa. The reactor was rapidly heated to 240℃with stirring at 600 rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled. After cooling, collecting the gas product with a gas bag, analyzing, centrifugally separating the catalyst and the reaction liquid from the reaction liquid product, and taking the supernatant for gas phase analysis.
Comparative examples
Catalyst activity evaluation: the reaction was carried out in a 50ml autoclave equipped with a thermocouple and externally connected with a magnetic stirrer. First, 0.05g of 2wt% Pt/WO was accurately weighed with an analytical balance 3 Catalyst, 0.05g of catalyst and 10ml of glycerol methanol solution (3 wt%) were placed in the above reactor. The reactor was purged six times with hydrogen to vent air, and the initial pressure was set at 6MPa. The reactor was rapidly heated to 240℃with stirring at 600 rpm. After 12h of reaction, the reactor was quickly transferred to cold water and cooled. After cooling, collecting the gas product with a gas bag, analyzing, centrifugally separating the catalyst and the reaction liquid from the reaction liquid product, and taking the supernatant for gas phase analysis.
The results of the gas phase analysis of the above application example 1 to application example 9 and comparative example are shown in table 1.
TABLE 1
Figure SMS_1
Figure SMS_2
Figure SMS_3
As can be seen from Table 1, the manganese is supported, the product distribution is converted into 1, 2-propanediol from n-propanol, the selectivity of 1, 2-propanediol is improved from 56% to 83% along with the increase of manganese loading, and after the manganese loading is further increased, the selectivity of 1, 2-propanediol is slightly reduced, which is probably caused by the reduction of the specific surface of the carrier due to the overlarge manganese loading, and the selectivity of the product is found to be stabilized at about 70% through three catalyst circulation experiments, and the selectivity of propylene glycol in the catalytic conversion experiment of glycerin through sorbitol is 28% as well, so that the catalyst has higher selectivity for preparing 1, 2-propanediol by hydrogenolysis of polyalcohol.
The technical scheme of the invention is not limited to the specific embodiment, and all technical modifications made according to the technical scheme of the invention fall within the protection scope of the invention.

Claims (9)

1. The preparation method of the tungsten oxide supported platinum-manganese catalyst is characterized by comprising the following steps of:
s1, immersing a tungsten oxide carrier into deionized water solution containing hexahydrated chloroplatinic acid solute in an equal volume, uniformly stirring to slurry, and standing overnight to obtain slurry solid;
s2, placing the pasty solid into a drying box for drying, and grinding the pasty solid into solid powder;
s3, putting the solid powder into a tube furnace, and introducing H 2 Roasting Ar mixed gas at 300 ℃ for 1-3 hours; then H is taken up 2 Switching of Ar mixture to O 2 /N 2 Passivating the mixed gas for 1h at room temperature to obtain black solid powder Pt/WO 3 ；
S4, black solid powder Pt/WO 3 Immersing the mixture into deionized water solution containing tetrahydrated manganese nitrate solute in an equal volume, uniformly stirring to slurry, and immersing overnight to obtain blue-color slurry solid;
s5, placing the blue paste solid into a drying oven for drying, and grinding the blue paste solid into blue solid powder;
s6, placing the blue solid powder into a tube furnace, and introducing H 2 Roasting Ar mixed gas at 700 ℃ for 1-5h; then H is taken up 2 Switching of Ar mixture to O 2 /N 2 And passivating the mixed gas for 1h at room temperature to obtain the tungsten oxide supported platinum-manganese catalyst Mn/Pt/W.
2. The method for preparing the tungsten oxide supported platinum manganese catalyst according to claim 1, wherein the method comprises the following steps: the stirring time in the steps S1 and S4 is 10-60min.
3. The method for preparing the tungsten oxide supported platinum manganese catalyst according to claim 1, wherein the method comprises the following steps: and the drying time in the drying box in the steps S2 and S5 is 6-18h, and the drying temperature is 110 ℃.
4. The method for preparing the tungsten oxide supported platinum manganese catalyst according to claim 1, wherein the method comprises the following steps: the H is 2 H in Ar gas mixture 2 The concentration of (2) is 5-40%.
5. The method for preparing the tungsten oxide supported platinum manganese catalyst according to claim 1, wherein the method comprises the following steps: the O is 2 /N 2 O in the mixed gas 2 The concentration of (2) was 1%.
6. A tungsten oxide supported platinum manganese catalyst prepared by the method of any one of claims 1-5.
7. The tungsten oxide-supported platinum manganese catalyst according to claim 6, wherein: the tungsten oxide loaded platinum-manganese catalyst has a platinum loading of 1-3wt% and a manganese loading of 1-16wt%.
8. Use of the tungsten oxide supported platinum manganese catalyst according to claim 7 for catalyzing the hydrogenolysis of polyols to produce 1, 2-propanediol.
9. The use of the tungsten oxide supported platinum manganese catalyst according to claim 8 for the preparation of 1, 2-propanediol by catalytic polyol hydrogenolysis, characterized in that: the polyalcohol is one of glycerol, erythritol, xylitol and sorbitol.
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JP2013010707A (en) * 2011-06-29 2013-01-17 Daicel Corp Production method for polyol hydrogenolysis product
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