Pt-w-m ternary catalyst for catalyzing hydrogenolysis of glycerol, and preparation method and application thereof

Abstract

The application provides a Pt-W-M ternary catalyst for catalyzing glycerol hydrogenolysis and a preparation method thereof. x The Pt-W-M / SiO2 metal catalyst is prepared by sequentially loading Pt, W and a metal additive M onto a silica carrier by using an impregnation method and then performing calcination, wherein the content of Pt accounts for 1.0-10% of the total mass of the catalyst, the content of W accounts for 0.2-1.0% of the total mass of the catalyst, and the content of the metal additive M accounts for 0.01-0.5% of the total mass of the catalyst; and the metal additive M is selected from any one of iron, cobalt, molybdenum, iridium, rhenium, ruthenium and manganese. The catalyst Pt-W-M / SiO2 prepared by the application can realize high conversion rate and high selectivity of glycerol aqueous solution to generate 1,3-propanediol under certain hydrogen pressure and temperature.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a Pt-WM ternary catalyst for catalytic hydrogenolysis of glycerol, its preparation method, and its application. Background Technology

[0002] 1,3-Propanediol (1,3-PDO), as an important chemical raw material, can be directly used to synthesize antifreeze, plasticizers, detergents, preservatives, and emulsifiers, and is widely used in the food, cosmetics, and pharmaceutical industries. Its primary application is in the reaction with terephthalic acid to prepare a novel polyester, PTT, with excellent properties. PTT fibers possess excellent resilience, dyeability, and biodegradability, and have broad application potential in numerous fields such as the apparel industry and engineering plastics.

[0003] In recent years, the hydrogenolysis of glycerol, a biodiesel byproduct, to produce 1,3-propanediol has attracted considerable attention due to its economic advantages. However, the development of catalysts remains a key challenge in implementing this technology. Extensive research has focused on developing catalysts with high activity and selectivity, with current research primarily concentrating on Ir-Re and Pt-W catalyst systems. For example, patent document CN106807371B demonstrates that by adjusting the atomic ratio of the active components Ir and Re in the catalyst, under optimal conditions, a glycerol conversion rate of 60.9% and a 1,3-propanediol selectivity of 31.1% can be achieved. Compared to Ir-Re catalysts, Pt-W catalysts exhibit higher 1,3-propanediol selectivity and the metal is relatively inexpensive, thus showing greater promise for application.

[0004] In patent document CN113262783A, WO3 with aerobic vacancies is described. x Using methylcyclopentadiene platinum as a carrier and methylcyclopentadiene platinum as a precursor, ALD (atomic layer deposition) technology was used on WO3. x Loading Pt and depositing it for 240 cycles yields Pt(240) / WO3. In the optimal example 9, a glycerol conversion of 65.23% and a 1,3-propanediol selectivity of 48.34% can be obtained. Although this method improves the utilization of precious metals, the complex and time-consuming preparation method limits its industrial application, and WO3... x The catalyst prepared using the support has poor hydrothermal stability, and W species will leach out during the reaction.

[0005] In patent document CN112044435A, rutile titanium dioxide is used as a carrier, and platinum and tungsten active components are loaded through a two-step impregnation method. After ultrasonic dispersion, calcination and reduction, a catalyst Pt-WO is obtained. x / TiO2, in which the conversion of glycerol can reach 74.5% and the selectivity of 1,3-propanediol can reach 51.2%. However, the preparation process of catalysts using TiO2 as a support is complex and time-consuming, and the conversion rate is only 40% after 12 hours of reaction, indicating a low catalytic reaction rate. In patent document CN107096564B, SAPO-34 support was prepared by hydrothermal synthesis, and Pt-WO catalyst was prepared by sequentially loading Pt and W with equal volumes of impregnation. x The SAPO-34 catalyst, in optimal Example 4, achieved a glycerol conversion of 48% and a 1,3-propanediol selectivity of 18.8%. However, the hydrothermal synthesis of SAPO-34 molecular sieves involves a long process and low yield per batch, making large-scale industrial production difficult. Patent document CN108144609A describes the preparation of WO3 using an equal-volume impregnation method. x Pt nanoparticles were synthesized from γ-Al₂O₃ via a colloidal method using polyvinylpyrrolidone and sodium borohydride, thus preparing the catalyst 6Pt₁₀W / γ-Al₂O₃. The glycerol conversion was 66.41%, and the 1,3-propanediol selectivity was 51.6%. Pt-WO₃ x Although the γ-Al2O3 catalyst exhibits good catalytic activity for the hydrogenolysis of glycerol, the preparation of this catalytic system requires the introduction of the toxic solvent sodium borohydride, which does not conform to the concept of green chemistry. Moreover, the catalyst is prone to deactivation during the reaction.

[0006] Although high selectivity for 1,3-propanediol has been achieved through different preparation methods and support combinations, the glycerol hydrogenolysis activity still needs further improvement. Researchers often introduce suitable exogenous metal components into the support lattice to promote metal dispersion, adjust the geometry and electron distribution of the bimetallic catalyst, and thus modulate its performance. For example, in patent document CN108607553B, Nb is doped into the lattice of tungsten oxide support using a solvothermal method to prepare an Nb-W composite support. The resulting catalyst achieved a glycerol conversion of 40% and a 1,3-propanediol selectivity of 29.7%. Similarly, in patent document CN116924888A, a niobium-tungsten composite oxide support was prepared using a sol-gel method, and then platinum was loaded using an impregnation method. The resulting Pt / Nb-W catalyst achieved a glycerol conversion of 100% and a 1,3-propanediol selectivity of 75.2%. However, the sol-gel method requires the introduction of hydrofluoric acid and concentrated ammonia, making the preparation process complex and inconsistent with green chemical engineering principles. In patent document CN110026191B, a TiO2-GeO2-WO3 support was prepared by adding GeO2 sol dropwise to TiO2 sol and then adding tungsten salt. The catalyst TiO2-GeO2-WO3 / Pt was then prepared by impregnation with a Pt solution. In the best example 9, the glycerol conversion rate was 63% and the 1,3-propanediol selectivity was 60.2%. In patent document CN107199036B, using a silicon-aluminum composite oxide as a support, SiO2 was doped into Al2O3, and W and Pt species were loaded sequentially using an equal-volume impregnation method. The resulting catalyst achieved a glycerol conversion rate of 53% and a 1,3-propanediol selectivity of 24.3% in the best example 6. In patent document CN106944050B, a WO3-Al2O3-SiO2 support prepared using the sol-gel method, after loading Pt, showed a glycerol conversion rate of 28.4% and a 1,3-propanediol selectivity of 39.0%. However, introducing additives into the support lattice requires extremely precise and demanding preparation process conditions, or even toxic reaction environments, to maintain the unique pore structure. This makes the catalyst preparation process complicated and greatly increases the catalyst production cost.

[0007] On the other hand, the performance of the catalyst can also be modulated by introducing other metal promoters during the loading of the active metal onto the support. For example, in patent documents CN105618045B and CN106824191B, catalysts prepared by solvothermal method and equal volume impregnation method introduce the promoter metals Au and Mo. However, the catalyst needs to be vacuum dried during the preparation process, and the introduced reducing agent sodium borohydride is a toxic solvent. In patent document CN110560057B, a catalyst prepared by equal volume impregnation method introduces one or more of the promoters Au, Ir, Ag, Mo, Re, Al, Na, La, Ce, Fe, Zr, and Zn to prepare the catalyst Mo / Pt / Au / WO.x Although the Pt-Au / WO3-Al2O3 catalyst prepared by sol-gel method and wet impregnation in CN114762825A achieves a 1,3-propanediol yield exceeding 25%, the preparation process still requires the introduction of hydrochloric acid and ammonia to adjust the pH, making the process cumbersome and demanding high corrosion resistance of equipment. This increases the production cost of the catalyst and limits its application in glycerol hydrogenolysis. The Pt-Ru-WO3 catalyst prepared by equal-volume impregnation method in CN109851473B... x The catalyst Pt-Ir / WO prepared from Al2O3 and CN116764632A by equal-volume impregnation and enhanced impregnation x Although Al2O3 does not require the introduction of strong acids and toxic solvents, the preparation process is relatively complex, and the yield of 1,3-propanediol does not exceed 20%.

[0008] Current research on glycerol hydrogenolysis catalysts mainly focuses on the Pt-W system. Whether it's preparing composite supports, improving catalyst preparation processes, or adding promoters, all these methods contribute to increasing the yield of 1,3-propanediol to varying degrees. However, existing catalyst preparation processes are cumbersome and involve the use of strong acids, strong bases, and toxic solvents. The glycerol hydrogenolysis reaction conditions for these catalysts are generally around 200℃ and 8MPa. These stringent preparation conditions and high reaction temperatures and pressures increase the cost of industrial applications of the catalysts, weakening the economic viability of the glycerol hydrogenolysis to 1,3-propanediol process. To achieve milder reaction conditions and further improve the yield of the direct hydrogenolysis of glycerol to 1,3-propanediol, it is necessary to further innovate and improve catalyst preparation methods and develop novel catalysts based on existing technologies. Summary of the Invention

[0009] To address the problems of complex preparation processes, strong acids, and toxic solvents involved in the hydrogenolysis of glycerol to 1,3-propanediol catalysts, and the difficulty in scaling up the catalyst production process, this invention provides a green, clean, simple, and large-scale Pt-WM ternary metal catalyst preparation method and catalyst, which improves the catalyst's reactivity, enhances the selectivity of the target product 1,3-propanediol, and increases the yield of 1,3-propanediol.

[0010] To achieve the above objectives, the technical solution of the present invention is as follows: a Pt-WM ternary catalyst for catalytic hydrogenolysis of glycerol, wherein the Pt-WM ternary catalyst has a silica support, the content of Pt accounts for 1-10% of the total mass of the catalyst, the content of W accounts for 0.2-1.0% of the total mass of the catalyst, and the content of metal promoter M accounts for 0.01-0.5% of the total mass of the catalyst, and the metal promoter M is selected from any one of iron, cobalt, molybdenum, iridium, rhenium, ruthenium, and manganese.

[0011] The present invention is further configured such that the content of Pt accounts for 2.0 to 6.0% of the total mass of the catalyst.

[0012] The present invention is further configured such that the content of W accounts for 0.4 to 0.8% of the total mass of the catalyst, preferably 0.5 to 0.7%.

[0013] The present invention is further configured such that the content of the metal auxiliary agent M accounts for 0.01 to 0.2% of the total mass of the catalyst.

[0014] This invention provides a method for preparing a Pt-WM ternary catalyst, wherein Pt, W, and a metal additive M are sequentially loaded onto a silica support using an impregnation method, followed by calcination to obtain the Pt-WM ternary catalyst Pt-WO. x -M / SiO2.

[0015] The present invention is further configured such that the precursor of metal Pt is chloroplatinic acid and / or tetraammineplatinum nitrate. The Pt is loaded onto the silica support by preparing the precursor of metal Pt into an aqueous solution of the precursor of metal Pt, immersing it in the silica support in an equal volume, letting it stand for 1 to 24 hours, and then drying it at 50 to 150°C for 1 to 24 hours to obtain Pt / SiO2.

[0016] The present invention is further configured such that the precursor of metal W is selected from at least one of ammonium tungstate, ammonium metatungstate and ammonium paratungstate, and the loading process of metal W is to prepare the precursor of metal W into an aqueous solution of metal W precursor, then impregnate it on Pt / SiO2 in equal volume, let it stand for 1 to 24 h, and then dry it at 50 to 150 °C for 1 to 24 h to obtain Pt-W / SiO2.

[0017] The present invention is further configured such that the loading process of metal M is as follows: the precursor of metal additive M is prepared into an aqueous solution of metal additive M, and then impregnated onto Pt-W / SiO2 in equal volume. After standing for 1 to 24 hours, it is dried at 50 to 150°C for 1 to 24 hours, and then calcined at 300 to 600°C for 1 to 24 hours to obtain Pt-WM / SiO2 metal catalyst.

[0018] The present invention is further configured such that the precursor of the metal auxiliary agent M is selected from any one of ferric nitrate, cobalt nitrate, molybdenum nitrate, chloroiridium acid, ammonium perrhenate, ruthenium chloride, and manganese acetate.

[0019] This invention provides an application of the above-mentioned Pt-WM ternary catalyst for the selective hydrogenolysis of glycerol to produce 1,3-propanediol.

[0020] The present invention is further configured such that the Pt-WM ternary catalyst does not require reduction before use.

[0021] The present invention is further configured such that the glycerol solution is an aqueous glycerol solution with a glycerol mass concentration of 5-100%.

[0022] The present invention further specifies that the catalytic reaction conditions are as follows: the mass ratio of Pt-WM ternary catalyst to glycerol is 0.1 to 3, the reaction temperature is 140 to 180°C, the pressure is 2 to 10 MPa, and the time is 1 to 24 h.

[0023] The present invention further specifies that the catalytic reaction conditions are: the mass ratio of Pt-WM ternary catalyst to glycerol is 1:(1.5-5).

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] (1) The preparation process of the catalyst of the present invention is simple and does not involve strong acids and toxic solvents, making the preparation process more green and clean.

[0026] (2) The catalyst of the present invention is used for the hydrogenolysis of glycerol to produce 1,3-propanediol. The reaction conditions are mild and no reduction is required before use. It can also significantly improve the catalytic activity of the catalyst. Detailed Implementation

[0027] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally operated under conventional conditions. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those skilled in the art.

[0028] The silica carrier used in the following examples is G6, which was purchased from Fuji Silysia Chemical Co., Ltd., Japan.

[0029] Example 1

[0030] Using commercial SiO2 (G6) as a carrier, an equal volume of chloroplatinic acid aqueous solution was impregnated onto G6. After aging for 12 hours, it was dried in an oven at 110℃ for 12 hours to obtain Pt / G6. An equal volume of ammonium metatungstate aqueous solution was impregnated onto Pt / G6. After aging for 12 hours, it was dried in an oven at 110℃ for 12 hours to obtain Pt-W / G6. An equal volume of a mixed aqueous solution of chloroiridium acid precursor was impregnated onto the Pt-W / G6. After aging for 12 hours, it was dried in an oven at 110℃ for 12 hours, and then calcined in a muffle furnace at 500℃ for 3 hours to obtain the catalyst 4Pt-0.6WO. x -0.05Ir / G6, Pt mass fraction is 4%, W mass fraction is 0.6%, and Ir mass fraction of the additive is 0.05%.

[0031] A batch reactor was selected, using 20g of a 5wt% glycerol aqueous solution, 0.2g of catalyst, at a reaction temperature of 140℃, a reaction pressure of 6MPa, and a reaction time of 8h. The reaction products were analyzed, and the results are shown in Table 1.

[0032] Example 2

[0033] Compared with Example 1, the difference is that chloroiridic acid was replaced with ferric nitrate to prepare the catalyst 4Pt-0.6WO. x -0.05Fe / G6. The catalytic reaction results are shown in Table 1.

[0034] Example 3

[0035] Compared with Example 1, the difference is that chloroiridic acid was replaced with cobalt nitrate to prepare the catalyst 4Pt-0.6WO. x -0.05Co / G6. The catalytic reaction results are shown in Table 1.

[0036] Example 4

[0037] Compared with Example 1, the difference is that chloroiridic acid was replaced with molybdenum nitrate to prepare the catalyst 4Pt-0.6WO. x -0.05Mo / G6. The catalytic reaction results are shown in Table 1.

[0038] Example 5

[0039] Compared with Example 1, the difference is that chloroiridium acid was replaced with ammonium perrhenate to prepare the catalyst 4Pt-0.6WO. x -0.05Re / G6. The catalytic reaction results are shown in Table 1.

[0040] Example 6

[0041] Compared with Example 1, the difference is that chloroiridic acid was replaced with ruthenium chloride to prepare the catalyst 4Pt-0.6WO. x -0.05Ru / G6. The catalytic reaction results are shown in Table 1.

[0042] Example 7

[0043] Compared with Example 1, the difference is that chloroiridium acid was replaced with manganese acetate to prepare catalyst 4Pt-0.6WO. x -0.05Mn / G6. The catalytic reaction results are shown in Table 1.

[0044] Example 8

[0045] Compared with Example 1, the difference is that the mass fraction of the auxiliary agent Ir was changed to 0.01%, resulting in the catalyst 4Pt-0.6WO. x -0.01Ir / G6. The catalytic reaction results are shown in Table 1.

[0046] Example 9

[0047] Compared with Example 1, the difference is that the mass fraction of the auxiliary agent Ir was changed to 0.1%, resulting in the catalyst 4Pt-0.6WO. x -0.1Ir / G6. The catalytic reaction results are shown in Table 1.

[0048] Example 10

[0049] Compared with Example 1, the difference is that the mass fraction of the auxiliary agent Ir was changed to 0.2%, resulting in the catalyst 4Pt-0.6WO. x -0.2Ir / G6. The catalytic reaction results are shown in Table 1.

[0050] Example 11

[0051] Compared with Example 1, the difference is that the mass fraction of the auxiliary agent Ir was changed to 0.5%, resulting in the catalyst 4Pt-0.6WO. x -0.5Ir / G6. The catalytic reaction results are shown in Table 1.

[0052] Example 12

[0053] Compared with Example 1, the difference is that the mass fraction of W is changed to 0.2%, resulting in the catalyst 4Pt-0.2WO. x -0.05Ir / G6. The catalytic reaction results are shown in Table 1.

[0054] Example 13

[0055] Compared with Example 1, the difference is that the mass fraction of W is changed to 0.4%, resulting in the catalyst 4Pt-0.4WO. x -0.05Ir / G6. The catalytic reaction results are shown in Table 1.

[0056] Example 14

[0057] Compared with Example 1, the difference is that the mass fraction of W is changed to 0.8%, resulting in the catalyst 4Pt-0.2WO. x -0.05Ir / G6. The catalytic reaction results are shown in Table 1.

[0058] Example 15

[0059] Compared with Example 1, the difference is that the mass fraction of W is replaced with 1%, resulting in the catalyst 4Pt-1WO. x -0.05Ir / G6. The catalytic reaction results are shown in Table 1.

[0060] Example 16

[0061] Compared with Example 1, the difference lies in the different conditions of the catalytic reaction. The catalytic reaction was carried out in a batch reactor, using 15g of a 3wt% glycerol aqueous solution, 0.3g of catalyst, at a reaction temperature of 180℃, a reaction pressure of 5MPa, and a reaction time of 12h. The results of the catalytic reaction are shown in Table 1.

[0062] Example 17

[0063] Compared with Example 1, the difference lies in the catalytic reaction conditions. A batch reactor was used for the catalytic reaction, with 15g of a 3wt% glycerol aqueous solution, 0.15g of catalyst, a reaction temperature of 180℃, a reaction pressure of 5MPa, and a reaction time of 12h. The catalytic reaction results are shown in Table 1.

[0064] Example 18

[0065] The difference between Example 16 and Example 26 lies in the composition of the catalyst. The catalyst preparation process is as follows: using commercial SiO2 (G6) as a support, an equal volume of chloroplatinic acid aqueous solution was impregnated onto G6. After aging for 12 hours, it was dried in an oven at 110°C for 12 hours to obtain Pt / G6. An equal volume of ammonium metatungstate aqueous solution was impregnated onto Pt / G6. After aging for 12 hours, it was dried in an oven at 110°C for 12 hours to obtain Pt-W / G6. An equal volume of a mixed aqueous solution of chloroiridium acid precursor was impregnated onto the Pt-W / G6. After aging for 12 hours, it was dried in an oven at 110°C for 12 hours, and then calcined in a muffle furnace at 500°C for 3 hours to obtain catalyst 2Pt-0.6WO. x The catalyst composition was -0.05Ir / G6, with Pt mass fraction of 2%, W mass fraction of 0.6%, and Ir mass fraction of 0.05%. A batch reactor was used for the catalytic reaction. 15g of a 3wt% glycerol aqueous solution was used, along with 0.3g of catalyst. The reaction temperature was 180℃, the reaction pressure was 5MPa, and the reaction time was 12h. The catalytic reaction results are shown in Table 1.

[0066] Example 19

[0067] The difference compared to Example 1 lies in the number of times the catalyst is recycled. The catalyst preparation process involves washing and drying the catalyst after one reaction to obtain catalyst 4Pt-0.6WO3. x -0.05Ir / G6-2 nd The treated catalyst is then placed in the reactor for reaction.

[0068] A batch reactor was selected, using 20g of a 5wt% glycerol aqueous solution, 0.2g of catalyst, at a reaction temperature of 140℃, a reaction pressure of 6MPa, and a reaction time of 8h. The reaction products were analyzed, and the results are shown in Table 1.

[0069] Example 20

[0070] The difference compared to Example 1 lies in the number of times the catalyst is recycled. The catalyst preparation process involves washing and drying the catalyst after two reactions to obtain catalyst 4Pt-0.6WO3. x -0.05Ir / G6-3 rd The treated catalyst is then placed in the reactor for reaction.

[0071] Example 21

[0072] The difference compared to Example 1 lies in the number of times the catalyst is recycled. The catalyst preparation process involves washing and drying the catalyst after three reactions to obtain catalyst 4Pt-0.6WO3. x -0.05Ir / G6-4 th The treated catalyst is then placed in the reactor for reaction.

[0073] Comparative Example 1

[0074] Using commercial SiO2 (G6) as a carrier, an equal volume of chloroplatinic acid solution was impregnated onto G6. After aging for 12 hours, it was dried in an oven at 110℃ for 12 hours to obtain Pt / G6. Then, an equal volume of ammonium metatungstate aqueous solution was impregnated onto Pt / G6, aged for 12 hours, dried in an oven at 110℃ for 12 hours, and then calcined in a muffle furnace at 500℃ for 3 hours to obtain 4Pt-0.6WO3. x / G6 catalyst, with a Pt mass fraction of 4% and a W mass fraction of 0.6%.

[0075] A batch reactor was selected, using 20 g of a 5 wt% glycerol aqueous solution and 0.2 g of catalyst. The reaction temperature was 140℃, the reaction pressure was 6 MPa, and the reaction time was 8 h. After the reaction, the liquid products were analyzed by liquid chromatography, and the external standard method was used for quantitative analysis of the liquid products. The reaction results are shown in Table 1.

[0076] Comparative Example 2

[0077] The difference from Example 1 lies in the pretreatment of the catalyst. The resulting catalyst was 4Pt-0.6WO3. x -0.05Ir / G6 is reduced in the liquid phase and then reacted. The specific operation of the liquid phase reduction is to put the catalyst and water into a batch reactor and reduce it for 3 hours at 200°C and 6MPa. After that, glycerol is added to the reactor to react.

[0078] A batch reactor was selected, using 20g of a 5wt% glycerol aqueous solution, 0.2g of catalyst, at a reaction temperature of 140℃, a reaction pressure of 6MPa, and a reaction time of 8h. The reaction products were analyzed, and the results are shown in Table 1.

[0079] Comparative Example 3

[0080] The difference from Example 1 lies in the pretreatment of the catalyst. The resulting catalyst was 4Pt-0.6WO3. x -0.05Ir / G6 is reduced in the gas phase and then reacted. The specific operation of the gas phase reduction is as follows: the catalyst is placed in a reduction furnace and reduced at 200°C under a hydrogen atmosphere for 3 hours, followed by passivation under an O2 / Ar atmosphere for 20 minutes. The treated catalyst is then placed in a reactor for reaction.

[0081] Comparative Example 4

[0082] The difference from Example 1 lies in the pretreatment of the catalyst. The resulting catalyst was 4Pt-0.6WO3. x -0.05Ir / G6 was reduced by hydrogen and then reacted. The specific operation of hydrogen-induced reduction was as follows: the catalyst was placed in a reduction furnace and reduced at 200°C in a hydrogen and water vapor atmosphere for 3 hours, followed by passivation in an O2 / Ar atmosphere for 20 minutes, and then the treated catalyst was placed in the reactor for reaction.

[0083] Comparative Example 5

[0084] The difference between Example 16 and Example 26 lies in the composition of the catalyst. The catalyst preparation process is as follows: using commercial SiO2 (G6) as a support, an equal volume of chloroplatinic acid aqueous solution was impregnated onto G6. After aging for 12 hours, it was dried in an oven at 110°C for 12 hours to obtain Pt / G6. An equal volume of ammonium metatungstate aqueous solution was impregnated onto Pt / G6. After aging for 12 hours, it was dried in an oven at 110°C for 12 hours to obtain Pt-W / G6. An equal volume of a mixed aqueous solution of chloroiridium acid precursor was impregnated onto the Pt-W / G6. After aging for 12 hours, it was dried in an oven at 110°C for 12 hours, and then calcined in a muffle furnace at 500°C for 3 hours to obtain catalyst 2Pt-7.5WO. x -0.1Ir / G6, Pt mass fraction is 2%, W mass fraction is 7.5%, and Ir mass fraction of the additive is 0.1%.

[0085] The catalytic reaction was carried out in a batch reactor, using 15g of a 3wt% glycerol aqueous solution, 0.3g of catalyst, at a reaction temperature of 180℃, a reaction pressure of 5MPa, and a reaction time of 12h. The results of the catalytic reaction are shown in Table 1.

[0086] Table 1 Comparison of catalytic performance in the hydrogenolysis of glycerol to 1,3-propanediol

[0087]

[0088]

[0089] As can be seen from the results in Table 1, the prepared Pt-WO x The addition of a second metal auxiliary component to the / G6 catalyst can significantly affect the conversion rate of the glycerol solution and the yield of 1,3-propanediol, and the loading of metal W and the loading of the second metal auxiliary have a significant impact on the yield of propylene glycol.

[0090] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent transformations or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A Pt-WM ternary catalyst for the catalytic hydrogenolysis of glycerol to 1,3-propanediol, characterized in that, In the Pt-WM ternary catalyst, the support is a silica support, the content of Pt accounts for 1~10% of the total mass of the catalyst, the content of W accounts for 0.4~0.8% of the total mass of the catalyst, and the content of metal promoter M accounts for 0.01~0.2% of the total mass of the catalyst, and the metal promoter M is selected from any one of molybdenum, iridium and rhenium. The Pt-WM ternary catalyst is prepared by impregnating Pt, W and metal additive M onto a silica support in sequence, followed by calcination.

2. The Pt-WM ternary catalyst according to claim 1, characterized in that, The Pt content accounts for 2.0 to 6.0% of the total mass of the catalyst.

3. A method for preparing the Pt-WM ternary catalyst as described in claim 1 or 2, characterized in that, Pt-WM ternary catalyst Pt-WO was prepared by sequentially loading Pt, W, and metal additive M onto a silica support using an impregnation method, followed by calcination. x -M / SiO2.

4. The method for preparing the Pt-WM ternary catalyst according to claim 3, characterized in that, The precursor of metallic Pt is chloroplatinic acid and / or tetraammineplatinum nitrate. Pt is loaded onto the silica support by preparing the precursor of metallic Pt into an aqueous solution, immersing it in the silica support in equal volume, letting it stand for 1 to 24 hours, and then drying it at 50 to 150°C for 1 to 24 hours to obtain Pt / SiO2.

5. The method for preparing the Pt-WM ternary catalyst according to claim 3, characterized in that, The precursor of metal W is selected from at least one of ammonium tungstate, ammonium metatungstate and ammonium paratungstate. The loading process of metal W is to prepare the precursor of metal W into an aqueous solution of metal W precursor, then impregnate it on Pt / SiO2 in equal volume, let it stand for 1 to 24 h, and then dry it at 50 to 150 °C for 1 to 24 h to obtain Pt-W / SiO2.

6. The method for preparing the Pt-WM ternary catalyst according to claim 3, characterized in that, The loading process of metal M involves preparing an aqueous solution of the precursor of metal additive M, impregnating it in an equal volume onto Pt-W / SiO2, allowing it to stand for 1-24 hours, drying it at 50-150℃ for 1-24 hours, and then calcining it at 300-600℃ for 1-24 hours to obtain the Pt-WM / SiO2 metal catalyst.

7. An application of the Pt-WM ternary catalyst as described in claim 1 or 2, characterized in that, Used for the selective hydrogenolysis of glycerol to produce 1,3 The reaction of propylene glycol.

8. The application according to claim 7, characterized in that, Pt-WM ternary catalysts do not require reduction before use.

9. The application according to claim 7, characterized in that, The glycerol solution is an aqueous glycerol solution with a glycerol mass concentration of 5-100%.

10. The application according to claim 7, characterized in that, The conditions for the catalytic reaction are as follows: the mass ratio of Pt-WM ternary catalyst to glycerol is 0.1~3, the catalytic reaction temperature is 140~180℃, the hydrogen pressure is 2~10MPa, and the hydrogenolysis time is 1~24h.

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