Preparation method of catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol

Abstract

The invention discloses a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, and the catalyst preparation method is as follows: 1) CoNi-MOF material is prepared by mixed solvent thermal crystallization reaction or M-MOF / MOx is prepared by further oxide-loaded CoNi-MOF material; 2) the material is subjected to pyrolysis treatment to obtain CoNi@C catalyst derived from CoNi-MOF or M@C / MOx catalyst derived from M-MOF / MOx. It is applied to catalyze the selective hydrogenation reaction of glycidol, the catalyst preparation method of the present invention is simple and easy to operate, low in cost, high in hydrogenation reaction conversion rate, good in product selectivity, and is applied to catalyze the selective hydrogenation reaction of glycidol to prepare 1,3-propylene glycol compounds, greatly improving the conversion rate of the substrate and the selectivity of the target product.

Description

Technical Field

[0001] The invention relates to the field of chemistry and chemical engineering, and in particular to a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol. Background Art

[0002] Epoxides are a very important class of organic chemical raw materials and intermediates. These compounds contain a three-membered oxygen ring structure in their molecules. Under the action of acidic or alkaline catalysts, their three-membered oxygen rings are easily opened and can undergo addition reactions with a variety of nucleophilic substances such as water, alcohols, amines, ammonia, phenols or carboxylic acids, so they are widely used. Among them, glycidol (also known as glycidol, abbreviated as GLD) has a simple glycerol skeleton and special structure and functional groups, so it has broad application prospects in organic synthesis. 1,3-Propanediol is an important chemical raw material and has important applications in medicine, food, cosmetics and organic synthesis. It can be used as a solvent, antifreeze agent, emulsifier, plasticizer, detergent, preservative and lubricant, etc., and has broad application prospects.

[0003] There are many methods for synthesizing 1,3-propylene glycol, including ethylene oxide hydroformylation, acrolein hydration, acetalization, glycerol hydrogenolysis, biomass fermentation, etc. At present, the industrialized production methods are mainly acrolein hydration hydrogenation, ethylene oxide hydroformylation and biofermentation. Among them, the intermediate product 3-hydroxypropanal involved in the acrolein hydration hydrogenation and ethylene oxide hydroformylation methods is unstable and easily produces acetal, which is not conducive to separation. In addition, the subsequent product purification process requires evaporation of a large amount of water, which consumes a lot of energy; the biofermentation method has a slow reaction, low production efficiency, many impurities, and cannot be expanded. The production scale is also difficult to purify the product. The selective hydrogenation of glycerol to prepare 1,3-propylene glycol has a simple production process and provides a new way for the synthesis of 1,3-propylene glycol. Generally speaking, the production of propylene glycol by glycerol hydrogenolysis is carried out through a dehydration-hydrogenation route, which is a catalytic reaction system composed of a metal for hydrogenation and an acid catalyst for dehydration. However, in addition to the production of 1,3-propylene glycol, other by-products such as 1,2-propylene glycol are produced during the glycerol hydrogenolysis reaction. 1,2-propylene glycol is further hydrogenated to produce n-propanol and isopropanol. Therefore, the catalytic performance of the catalyst currently used to prepare 1,3-propylene glycol by glycerol hydrogenolysis still needs to be further improved. Patent CN111333488A discloses a method for preparing 1,3-propylene glycol using glycerol as a raw material using a loop reactor. The method uses glycerol as a raw material and Pt / WO3 / Al2O3 as a catalyst, and prepares it by hydrogenation reaction in a loop reactor. This method can improve the utilization rate of the catalyst, but the process is relatively complicated and is not conducive to industrial production. Patent CN115594565A discloses a process for preparing 1,3-propylene glycol by hydrogenation of glycerol, which adopts a Venturi reactor reaction and cooperates with a membrane separation process, uses a noble metal-based catalyst, and the active component of the catalyst is Ru, Pd, Pt or Rh. Although continuous production of 1,3-propylene glycol can be achieved, by-products (n-propanol and isopropanol) need to be added to the reaction to inhibit the production of 1,2-propylene glycol during the reaction, thereby improving the selectivity of 1,3-propylene glycol, but the reaction and separation process are relatively complicated. Patent CN115445652A discloses a catalyst for preparing 1,3-propylene glycol by selective hydrogenation of glycerol, and its preparation method and application. The metal active component in the catalyst is composed of Pt and metal M in a mass ratio of 1: (0.05-2.5), wherein the metal M is selected from one or more of Au, Ru, Pd, Cu, and Ni; the conversion rate of glycerol catalyzed by the catalyst prepared by the process is mostly less than 80%, and the selectivity of the product 1,3-propylene glycol is less than 55%, and the overall economic benefit is not good.

[0004] At present, there are few reports on the direct selective hydrogenation of glycidol to 1,3-propylene glycol. In view of the technical defects of the existing technology, it is necessary to develop a catalyst with low raw material cost and simple preparation steps, so that it has good catalytic hydrogenation performance for glycidol and high selectivity for the product 1,3-propylene glycol under mild reaction conditions. Summary of the invention

[0005] The purpose of the present invention is to solve the shortcomings of the above-mentioned background technology, and to provide a method for preparing a catalyst for the high selective hydrogenation of glycidol to 1,3-propylene glycol. The catalyst provided by the present invention is M@Cx derived from M-MOF or M@C / MOx derived from M-MOF / MOx supported by oxides. The outstanding feature of the catalyst is that the preparation method is simple and easy to operate, and it has excellent catalytic performance, and can be used to catalyze the high selective hydrogenation of glycidol to prepare 1,3-propylene glycol compounds. The method first obtains M-MOF material by a mixed solvent thermal crystallization method, and then obtains M@Cx catalyst by pyrolysis treatment; or M-MOF material is loaded on an oxide carrier to obtain M-MOF / MOx, and then obtains M@C / MOx catalyst by pyrolysis treatment. The obtained catalyst is applied to catalyze the high selective hydrogenation of glycidol to prepare 1,3-propylene glycol, and not only the reaction conditions are relatively mild, but also the conversion rate is relatively high.

[0006] The technical solution of the present invention is: a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, characterized in that it comprises the following steps:

[0007] 1) placing metal salts including cobalt salt and nickel salt in a container, sequentially adding DMF, water and ethanol as a mixed solvent, stirring and dissolving them sufficiently to obtain a solution A;

[0008] 2) placing terephthalic acid in a polytetrafluoroethylene liner, sequentially adding DMF, water and ethanol as a mixed solvent, stirring and dissolving the mixture sufficiently to obtain a solution B;

[0009] 3) adding solution A and solution B to a polytetrafluoroethylene liner to obtain a mixed solution C, stirring at room temperature for 2 to 6 hours, placing the liner into a reactor, and performing a crystallization reaction at 100 to 180° C. for 12 to 72 hours, then taking out the reactor and performing an aging treatment at room temperature for 2 to 3 days, and performing a purification treatment and a drying treatment after the reaction to obtain an M-MOF material;

[0010] 4) The M-MOF is directly pyrolyzed or loaded on an oxide carrier and then pyrolyzed to obtain a catalyst.

[0011] In the present invention, M-MOF is directly pyrolyzed to obtain M-MOF-derived nano M@Cx catalyst; M-MOF is loaded on an oxide carrier MOx to obtain M-MOF / MOx material, which is then pyrolyzed to obtain M-MOF / MOx-derived nano M@C / MOx catalyst.

[0012] Preferably, in step 1), the cobalt salt is selected from one of cobalt nitrate and cobalt acetate, and the nickel salt is selected from one of nickel nitrate and nickel acetate; and the molar ratio of the cobalt salt to the nickel salt in the metal salt is 1-4:1-4.

[0013] Preferably, the mixed solvent in step 1) and the mixed solvent in step 2) are obtained by mixing DMF, water and ethanol in a volume ratio of 3:1:1, the concentration of the metal salt in solution A is 0.1-0.2 mol / L, and the concentration of terephthalic acid in solution B is 0.1-0.2 mol / L.

[0014] Preferably, in step 3), the purification treatment is specifically as follows: after suction filtration, the obtained filter cake is washed with ethanol for 3 to 5 times, and then washed with DMF for 3 to 5 times, and the filter cake is collected by filtration; the drying treatment is specifically as follows: vacuum drying at 90 to 100° C. for 8 to 12 hours to obtain the M-MOF material.

[0015] Preferably, in step 3), the crystallization reaction temperature is 150-170° C., and the crystallization reaction time is 24-72 hours.

[0016] Preferably, the specific steps of the pyrolysis treatment in step 4) include: placing in a vacuum tube furnace, introducing nitrogen with a 30% hydrogen content for pyrolysis treatment, the pyrolysis temperature is 300-600°C, and the time is 1-2h. In step 4), the M-MOF material or the M-MOF / MOx material is subjected to the same pyrolysis treatment as above to obtain M-MOF-derived M@Cx or M-MOF / MOx-derived M@C / MOx. Furthermore, the pyrolysis temperature is 300-500°C.

[0017] Preferably, the step of loading the M-MOF material on the oxide carrier in step 4) comprises: dispersing the M-MOF material in water, adding the oxide carrier MOx, wherein MOx is selected from one of γ-Al2O3 and SiO2, and the mass of the M-MOF material accounts for 7-10% of the total mass of the M-MOF material and the oxide carrier MOx; after sufficient stirring, loading and reacting at 80-90°C for 10-12h, then evaporating the reaction solution to remove water, and vacuum drying at 90-100°C for 8-12h to complete the loading.

[0018] The present invention also provides a catalyst, which is prepared by any of the above methods for preparing the catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of propylene oxide.

[0019] The present invention also provides an application of the catalyst, wherein the catalyst is used for catalyzing the highly selective hydrogenation of glycidol to prepare 1,3-propylene glycol.

[0020] Preferably, the method for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol comprises the following steps: adding a catalyst, glycidol, and a solvent into an intermittent pressure reactor, replacing the air in the reactor with H2 three times, then charging H2 to make the hydrogen pressure in the reactor reach 1-3.0 MPa, turning on magnetic stirring (speed 400 rpm / min), heating the reactor to make the hydrogenation reaction temperature 90-130°C, reacting for 3-6 hours to carry out the selective hydrogenation reaction of glycidol to obtain a 1,3-propylene glycol compound. Furthermore, the hydrogenation reaction temperature is preferably 110-130°C.

[0021] Preferably, the amount of the catalyst is 1.0 to 10.0 mg per 1 mmol of glycidol; the mass fraction of glycidol in the reaction solution is 5 to 30%; the reaction solvent is selected from one of methanol, ethanol, isopropanol, and tetrahydrofuran, each containing 3.0 mg / L NaOH. Here, the reaction solution is a mixture of glycidol and a solvent, and the catalyst is solid and dispersed in the reaction solution without dissolving.

[0022] Preferably, 1.0 to 10.0 mg of the M-MOF-derived M@Cx catalyst is used for every 1 mmol of glycidol.

[0023] Preferably, 5.0 to 10.0 mg of the M-MOF / MOx-derived M@C / MOx catalyst is used for every 1 mmol of glycidol.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] First, the present invention uses cheap metal cobalt salt, nickel salt and ligand terephthalic acid as raw materials, prepares M-MOF material through mixed solvent thermal crystallization reaction, and directly obtains nano CoNi@C catalyst through pyrolysis treatment, and applies it to the reaction of preparing 1,3-propylene glycol compound by highly selective hydrogenation of glycidol. At present, there are few reports on the selective hydrogenation of glycidol to prepare 1,3-propylene glycol. The catalyst used in the method disclosed in this technology is low in price, which can significantly reduce the production cost, and the hydrogenation reaction conversion rate is high and the product selectivity is good, which will provide a positive technical reference for the development of this field.

[0026] Secondly, the M-MOF / MOx prepared by the present invention is a composite material prepared by loading M-MOF onto the oxide MOx, so the M@C / MOx catalyst derived therefrom has high metal dispersion, and the highly exposed metal active sites are conducive to the diffusion of reactant molecules and product molecules and the formation of intermediates during the catalytic reaction, providing an ideal reaction site for the occurrence of the catalytic reaction. This low-cost, simple synthesis, and reproducible preparation method is conducive to the large-scale application of cobalt-nickel catalysts in the selective hydrogenation of glycidol compounds.

[0027] Third, according to the above steps, 1,3-propylene glycol compounds are produced, the process is simple, the catalyst is cheap, the catalytic activity is high, and the selectivity of the target product is high. The conversion of glycidol in the present invention can reach 100%, and the selectivity of the product 1,3-propylene glycol is also as high as 94.3%, which greatly reduces the generation of the hydrogenation product 1,2-propylene glycol. Compared with the prior art, the catalyst for preparing 1,3-propylene glycol by selective hydrogenation of glycidol provided by the present invention adopts a specific content of bimetallic active components, achieves overall good interaction, has high stability, maintains high catalytic activity and selectivity for high-concentration glycidol solutions, and is suitable for preparing 1,3-propylene glycol by hydrogenation of glycidol. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Select the hydrogenation reaction process for glycidol;

[0029] Figure 2 X-ray diffraction patterns of Co1Ni1-MOF and Co1Ni1@C-300 prepared in Example 1 of the present invention;

[0030] Figure 3 Scanning electron microscope images of Co1Ni1-MOF, Co4Ni1-MOF, Co-MOF and Ni-MOF prepared in Example 1, Example 2, Comparative Example 2 and Comparative Example 3 of the present invention;

[0031] Figure 4 This is a diagram showing the catalytic hydrogenation reaction results of Example 1 of the present invention and Comparative Examples 1, 2, 3 and 4. DETAILED DESCRIPTION

[0032] The following specific examples further illustrate the present invention in detail.

[0033] Example 1

[0034] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0035] 1) Weigh 5 mmol of total substance and 1:1 molar ratio of cobalt acetate and nickel nitrate respectively into a 100 mL beaker, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution A (the concentration of metal salt in solution A is 0.1 mol / L);

[0036] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.1 mol / L);

[0037] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 2 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 150°C for 48 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a Bush funnel was used for suction filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain Co1Ni1-MOF material.

[0038] 4) Pyrolysis treatment of the CoNi-MOF material to obtain a nano CoNi@C catalyst derived from CoNi-MOF. The Co1Ni1-MOF material was placed in a vacuum tube furnace and pyrolyzed by nitrogen containing 30% hydrogen at a temperature of 300°C for 2 hours to obtain a nano Co1Ni1@C-300 catalyst derived from Co1Ni1-MOF.

[0039] (2) A method for using a CoNi-MOF-derived nano-CoNi@C catalyst to catalyze the highly selective hydrogenation of propylene oxide to prepare 1,3-propylene glycol compounds, comprising the following steps: 50 mg of a Co1Ni1-MOF-derived Co1Ni1@C-300 catalyst, 13.5 mmol of propylene oxide, and 9.0 g of a solvent methanol (containing 3.0 mg / L NaOH) are added to an intermittent pressure reactor, and the air in the reactor is replaced with H2 three times. Then, H2 is introduced to make the hydrogen pressure in the reactor reach 3.0 MPa, magnetic stirring is started (speed 400 rpm / min), and the reactor is heated to make the hydrogenation reaction temperature 130°C. The reaction is carried out for 5 hours to carry out a selective hydrogenation reaction of propylene oxide to obtain a 1,3-propylene glycol compound.

[0040] Example 2

[0041] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0042] 1) Weigh 5 mmol of total substance and 4:1 molar ratio of cobalt nitrate and nickel nitrate respectively into a 100 mL beaker, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution A (the concentration of metal salt in solution A is 0.1 mol / L);

[0043] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 15 mL of DMF, 5 mL of water and 5 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.2 mol / L);

[0044] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 6 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 170°C for 24 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a Bush funnel was used for suction filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain Co4Ni1-MOF material.

[0045] 4) Pyrolysis treatment of the CoNi-MOF material to obtain a nano CoNi@C catalyst derived from CoNi-MOF. The CoNi-MOF material was placed in a vacuum tube furnace and pyrolyzed by nitrogen containing 30% hydrogen at a temperature of 400°C for 2 hours to obtain a nano Co4Ni1@C-400 catalyst derived from Co4Ni1-MOF.

[0046] (2) A method for using a CoNi-MOF-derived nano-CoNi@C catalyst to catalyze the highly selective hydrogenation of propylene oxide to prepare a 1,3-propylene glycol compound, comprising the following steps: 20 mg of a Co4Ni1-MOF-derived Co4Ni1@C-400 catalyst, 6.75 mmol of propylene oxide, and 9.5 g of solvent ethanol (containing 3.0 mg / L NaOH) are added to an intermittent pressure reactor, and the air in the reactor is replaced with H2 three times. Then, H2 is introduced to make the hydrogen pressure in the reactor reach 2.0 MPa, magnetic stirring is started (speed 400 rpm / min), and the reactor is heated to make the hydrogenation reaction temperature 110°C. The reaction is carried out for 6 hours to carry out a selective hydrogenation reaction of propylene oxide to obtain a 1,3-propylene glycol compound.

[0047] Example 3

[0048] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0049] 1) Weigh 5 mmol of cobalt nitrate and nickel acetate in a molar ratio of 1:4 into a 100 mL beaker, add 15 mL of DMF, 5 mL of water and 5 mL of ethanol to form a mixed solvent, stir and dissolve them to obtain solution A (the concentration of metal salt in solution A is 0.2 mol / L);

[0050] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.1 mol / L);

[0051] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 3 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 150°C for 48 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a Bush funnel was used for suction filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain Co1Ni4-MOF material.

[0052] 4) The CoNi-MOF material was pyrolyzed to obtain a nano CoNi@C catalyst derived from CoNi-MOF. The Co1Ni4-MOF material was placed in a vacuum tube furnace and pyrolyzed by nitrogen containing 30% hydrogen at a temperature of 500°C for 1 hour to obtain a nano Co1Ni4@C-500 catalyst derived from Co1Ni4-MOF.

[0053] (2) A method for using a CoNi-MOF-derived nano-CoNi@C catalyst to catalyze the highly selective hydrogenation of propylene oxide to prepare 1,3-propylene glycol compounds, comprising the following steps: 50 mg of a Co1Ni4-MOF-derived Co1Ni4@C-500 catalyst, 10.0 mmol of propylene oxide, and 9.26 g of isopropanol (containing 3.0 mg / L NaOH) as a solvent are added to an intermittent pressure reactor, the air in the reactor is replaced with H2 three times, and then H2 is introduced to make the hydrogen pressure in the reactor reach 1.0 MPa, magnetic stirring is started (speed 400 rpm / min), the reactor is heated to make the hydrogenation reaction temperature 120°C, and the reaction is carried out for 4 hours to carry out the selective hydrogenation reaction of propylene oxide to obtain a 1,3-propylene glycol compound.

[0054] Example 4

[0055] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0056] 1) Weigh 5 mmol of total substance and 1:2 molar ratio of cobalt nitrate and nickel nitrate respectively into a 100 mL beaker, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution A (the concentration of metal salt in solution A is 0.1 mol / L);

[0057] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.1 mol / L);

[0058] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 4 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 150°C for 24 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a Buchner funnel was used for suction filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain Co1Ni2-MOF material.

[0059] 4) Pyrolysis treatment of the CoNi-MOF material to obtain a nano CoNi@C catalyst derived from CoNi-MOF. The Co1Ni2-MOF material was placed in a vacuum tube furnace and pyrolyzed by nitrogen containing 30% hydrogen at a temperature of 300°C for 2 hours to obtain a nano Co1Ni2@C-300 catalyst derived from Co1Ni2-MOF.

[0060] (2) A method for using a CoNi-MOF-derived nano-CoNi@C catalyst to catalyze the highly selective hydrogenation of propylene oxide to prepare a 1,3-propylene glycol compound, comprising the following steps: 80 mg of a Co1Ni2-MOF-derived Co1Ni2@C-300 catalyst, 27.0 mmol of propylene oxide, and 8.0 g of a solvent, tetrahydrofuran (containing 3.0 mg / L NaOH), are added to an intermittent pressure reactor, the air in the reactor is replaced with H2 three times, and then H2 is introduced to make the hydrogen pressure in the reactor reach 3.0 MPa, magnetic stirring is started (speed 400 rpm / min), the reactor is heated to a hydrogenation reaction temperature of 130°C, and the reaction is carried out for 3 hours to carry out a selective hydrogenation reaction of propylene oxide to obtain a 1,3-propylene glycol compound.

[0061] Example 5

[0062] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0063] 1) Weigh 5 mmol of total substance and 2:1 molar ratio of cobalt nitrate and nickel nitrate respectively into a 100 mL beaker, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution A (the concentration of metal salt in solution A is 0.1 mol / L);

[0064] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.1 mol / L);

[0065] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 2 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 150°C for 24 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a Buchner funnel was used for suction filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain Co2Ni1-MOF material.

[0066] 4) The CoNi-MOF material was pyrolyzed to obtain a CoNi-MOF-derived nano-CoNi@C catalyst. The Co2Ni1-MOF material was placed in a vacuum tube furnace and pyrolyzed by nitrogen containing 30% hydrogen at a temperature of 350°C for 2 hours to obtain a Co2Ni1-MOF-derived nano-Co2Ni1@C-350 catalyst.

[0067] (2) A method for using a CoNi-MOF-derived nano-CoNi@C catalyst to catalyze the highly selective hydrogenation of propylene oxide to prepare 1,3-propylene glycol compounds, comprising the following steps: 101 mg of a Co2Ni1-MOF-derived Co2Ni1@C-300 catalyst, 40.5 mmol of propylene oxide, and 7.0 g of a solvent methanol (containing 3.0 mg / L NaOH) are added to an intermittent pressure reactor, the air in the reactor is replaced with H2 three times, and then H2 is introduced to make the hydrogen pressure in the reactor reach 3.0 MPa, magnetic stirring is started (speed 400 rpm / min), the reactor is heated to make the hydrogenation reaction temperature 130°C, and the reaction is carried out for 5 hours to carry out a selective hydrogenation reaction of propylene oxide to obtain a 1,3-propylene glycol compound.

[0068] Example 6

[0069] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0070] 1) Weigh 5 mmol of total substance in a molar ratio of 1:1 cobalt acetate and nickel nitrate in a 100 mL beaker, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve them to obtain solution A (the concentration of metal salt in solution A is 0.1 mol / L);

[0071] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.1 mol / L);

[0072] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 2 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 150°C for 48 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a Bush funnel was used for suction filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain Co1Ni1-MOF material.

[0073] 4) 0.3 g of the obtained Co1Ni1-MOF material was dispersed in 50 mL of water, 2.7 g of γ-Al2O3 oxide carrier was added, and after sufficient stirring, the reaction was loaded at 90°C for 10 h, and then the reaction solution was evaporated to remove water, and vacuum dried at 100°C for 8 h to obtain Co1Ni1-MOF / Al2O3 material (the loading percentage of Co1Ni1-MOF on the oxide carrier γ-Al2O3 was 10%); then the Co1Ni1-MOF / Al2O3 material was pyrolyzed: the Co1Ni1-MOF / Al2O3 material was placed in a vacuum tube furnace, and nitrogen with a 30% hydrogen content was introduced for pyrolysis treatment. The pyrolysis treatment temperature was 300°C and the time was 2 h to obtain the Co1Ni1-MOF / Al2O3 derived Co1Ni1@C / Al2O3 catalyst.

[0074] (2) A method for preparing 1,3-propylene glycol compound by catalyzing the highly selective hydrogenation of propylene oxide using a Co1Ni1@C / Al2O3 catalyst derived from Co1Ni1-MOF / Al2O3, comprising the following steps: adding 67.5 mg of the Co1Ni1@C / Al2O3 catalyst derived from Co1Ni1-MOF / Al2O3, 13.5 mmol of propylene oxide, and 9.0 g of solvent methanol (containing 3.0 mg / L NaOH) into an intermittent pressure reactor, replacing the air in the reactor with H2 for 3 times, then injecting H2 to make the hydrogen pressure in the reactor reach 3.0 MPa, starting magnetic stirring (rotation speed 400 rpm / min), heating the reactor to make the hydrogenation reaction temperature 130°C, and reacting for 6 hours to carry out the selective hydrogenation reaction of propylene oxide to obtain 1,3-propylene glycol compound.

[0075] Example 7

[0076] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0077] 1) Weigh 5 mmol of total substance in a molar ratio of 1:1 cobalt acetate and nickel nitrate in a 100 mL beaker, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve them to obtain solution A (the concentration of metal salt in solution A is 0.1 mol / L);

[0078] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.1 mol / L);

[0079] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 2 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 160°C for 60 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a Bush funnel was used for suction filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain Co1Ni1-MOF material.

[0080] 4) 0.21 g of the obtained Co1Ni1-MOF material was dispersed in 50 mL of water, 2.79 g of SiO2 oxide carrier was added, and after sufficient stirring, the reaction was loaded at 90°C for 10 h, and then the reaction solution was evaporated to remove water, and vacuum dried at 100°C for 8 h to obtain Co1Ni1-MOF / SiO2 material (the loading percentage of Co1Ni1-MOF on the oxide carrier SiO2 was 7%); then the Co1Ni1-MOF / SiO2 material was pyrolyzed: the Co1Ni1-MOF / SiO2 material was placed in a vacuum tube furnace, and nitrogen with a 30% hydrogen content was introduced for pyrolysis treatment. The pyrolysis temperature was 300°C and the time was 2 h to obtain the Co1Ni1-MOF / SiO2 derived Co1Ni1@C / SiO2 catalyst.

[0081] (2) A method for preparing 1,3-propylene glycol compound by catalyzing the highly selective hydrogenation of propylene oxide using a Co1Ni1-MOF / SiO2-derived Co1Ni1@C / SiO2 catalyst, comprising the following steps: 135 mg of the Co1Ni1@C / SiO2 catalyst derived from Co1Ni1-MOF / SiO2, 13.5 mmol of propylene oxide, and 9.0 g of solvent methanol (containing 3.0 mg / L NaOH) are added to an intermittent pressure reactor, the air in the reactor is replaced with H2 three times, and then H2 is introduced to make the hydrogen pressure in the reactor reach 3.0 MPa, magnetic stirring is started (speed 400 rpm / min), the reactor is heated to make the hydrogenation reaction temperature 120°C, and the reaction is carried out for 6 hours to carry out the selective hydrogenation reaction of propylene oxide to obtain 1,3-propylene glycol compound.

[0082] Example 8

[0083] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0084] 1) Weigh 5 mmol of total substance of cobalt acetate and nickel nitrate in a molar ratio of 4:1 into a 100 mL beaker, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve them to obtain solution A (the concentration of metal salt in solution A is 0.1 mol / L);

[0085] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.1 mol / L);

[0086] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 2 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 170°C for 24 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a Bush funnel was used for suction filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain Co4Ni1-MOF material.

[0087] 4) 0.3 g of the obtained Co4Ni1-MOF material was dispersed in 50 mL of water, 2.7 g of γ-Al2O3 oxide carrier was added, and after sufficient stirring, the reaction was loaded at 90°C for 10 h, and then the reaction solution was evaporated to remove water, and vacuum dried at 100°C for 8 h to obtain Co4Ni1-MOF / Al2O3 material (the loading percentage of Co4Ni1-MOF on the oxide carrier γ-Al2O3 was 10%); then the Co4Ni1-MOF / Al2O3 material was pyrolyzed: the Co4Ni1-MOF / Al2O3 material was placed in a vacuum tube furnace, and nitrogen with a 30% hydrogen content was introduced for pyrolysis treatment. The pyrolysis treatment temperature was 350°C and the time was 2 h to obtain Co4Ni1-MOF / Al2O3 derived Co4Ni1@C / Al2O3 catalyst.

[0088] (2) A method for preparing 1,3-propylene glycol compound by catalyzing the highly selective hydrogenation of propylene oxide using a Co4Ni1@C / Al2O3 catalyst derived from Co4Ni1-MOF / Al2O3, comprising the following steps: 135 mg of the Co4Ni1@C / Al2O3 catalyst derived from Co4Ni1-MOF / Al2O3, 27 mmol of propylene oxide, and 8.0 g of solvent methanol (containing 3.0 mg / L NaOH) are added to an intermittent pressure reactor, the air in the reactor is replaced with H2 three times, and then H2 is introduced to make the hydrogen pressure in the reactor reach 3.0 MPa, magnetic stirring is started (rotation speed 400 rpm / min), the reactor is heated to make the hydrogenation reaction temperature 130°C, and the reaction is carried out for 6 hours to carry out the selective hydrogenation reaction of propylene oxide to obtain 1,3-propylene glycol compound.

[0089] in accordance with Figure 1It can be seen from the hydrogenation reaction process of glycidol that if you want to obtain 1,3-propylene glycol with higher selectivity, glycidol undergoes an anti-Markovnikov hydrogenation reaction process. The CoNi-MOF-derived nano-CoNi@C catalysts we developed have good catalytic activity in Examples 1-8, the conversion rate of glycidol is greater than 85%, and the selectivity of the target product 1,3-propylene glycol is greater than 70%. In particular, the Co1N1-MOF-derived Co1Ni1@C-300 catalyst can convert 100% of glycidol, and the selectivity of the product 1,3-propylene glycol is as high as 94.3%.

[0090] Table 1 shows the reaction conditions and hydrogenation results of different catalysts investigated in Examples 1-8

[0091]

[0092] Examples 9-12

[0093] In Examples 9-12, except for the different "crystallization temperatures" in the following step 3), the rest are the same as in Example 1. The relevant results are shown in the table below.

[0094] The catalyst Co1Ni1@C-300 (50 mg) prepared in Examples 9-12 and 13.5 mmol of propylene oxide, 9.0 g of methanol solvent (containing 3.0 mg / L NaOH) were accurately weighed, the reaction temperature was 130° C., the H2 pressure was 3.0 MPa, and the reaction was carried out for 5 h to obtain 1,3-propylene glycol. The results are shown in Table 2 below:

[0095] Table 2

[0096]

[0097]

[0098] Examples 13-16

[0099] Except for the different "crystallization time" in the following step 3), the other steps of Examples 13-16 are the same as those of Example 1. The relevant results are shown in the table below.

[0100] The catalyst Co1Ni1@C-300 (50 mg) prepared in Examples 13-16 and 13.5 mmol of glycidol and 9.0 g of solvent methanol (containing 3.0 mg / L NaOH) were accurately weighed, the reaction temperature was 130° C., the H2 pressure was 3.0 MPa, and the reaction was carried out for 5 h to obtain 1,3-propylene glycol. The results are shown in Table 3 below:

[0101] Table 3

[0102]

[0103] Examples 17-19

[0104] In Examples 17-19, except for the following step 4) "pyrolysis temperature", the rest are the same as in Example 1. The relevant results are shown in the table below.

[0105] The catalyst Co1Ni1@Cx (50 mg) prepared in Examples 17-19 and 13.5 mmol of glycidol and 9.0 g of methanol (containing 3.0 mg / L NaOH) were accurately weighed, the reaction temperature was 130° C., the H2 pressure was 3.0 MPa, and the reaction was carried out for 5 h to obtain 1,3-propylene glycol. The results are shown in Table 4 below:

[0106] Table 4

[0107]

[0108]

[0109] Examples 20-23

[0110] In Examples 20-23, except for the different "reaction temperatures" during hydrogenation in the following step (2), the rest are the same as in Example 1. The relevant results are shown in the table below.

[0111] The catalyst Co1Ni1@C-300 (50 mg) prepared in Examples 20-23 and 13.5 mmol of propylene oxide, 9.0 g of methanol (containing 3.0 mg / L NaOH) as solvent, and H2 pressure of 3.0 MPa were accurately weighed and reacted for 5 h to obtain 1,3-propylene glycol. The results are shown in Table 5 below:

[0112] Table 5

[0113]

[0114] Examples 24-26

[0115] In Examples 24-26, except for the following differences in "the amount of propylene oxide added and the amount of solvent methanol added", the rest are the same as in Example 1. The relevant results are shown in the table below.

[0116] The catalyst Co1Ni1@C-300 (50 mg) and glycidol prepared in Examples 24-26, and the solvent methanol (containing 3.0 mg / L NaOH) were accurately weighed, the reaction temperature was 130° C., the H2 pressure was 3.0 MPa, and the reaction was carried out for 5 h to obtain 1,3-propylene glycol. The results are shown in Table 6:

[0117] Table 6

[0118]

[0119]

[0120] Comparative Example 1

[0121] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0122] 1) Weigh 5 mmol of total substance of cobalt acetate and nickel nitrate in a molar ratio of 1:1 into a 100 mL beaker, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve them to obtain solution A (the concentration of metal salt in solution A is 0.1 mol / L);

[0123] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.1 mol / L);

[0124] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 2 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 150°C for 48 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a Bush funnel was used for suction filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain Co1Ni1-MOF material.

[0125] (2) A method for directly using CoNi-MOF material as a catalyst for catalytic hydrogenation of propylene oxide and selective hydrogenation to prepare 1,3-propylene glycol compounds, comprising the following steps: 50 mg of Co1Ni1-MOF material, 13.5 mmol of propylene oxide, and 9.0 g of solvent methanol (containing 3.0 mg / L NaOH) are added to an intermittent pressure reactor, and the air in the reactor is replaced with H2 three times. Then, H2 is injected to make the hydrogen pressure in the reactor reach 3.0 MPa, magnetic stirring is turned on (speed 400 rpm / min), and the reactor is heated to make the hydrogenation reaction temperature 130°C. The reaction is carried out for 5 hours to carry out the selective hydrogenation reaction of propylene oxide to obtain 1,3-propylene glycol compounds.

[0126] Comparative Example 2

[0127] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0128] 1) Weigh 5 mmol of cobalt nitrate into a 100 mL beaker, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution A (the concentration of metal salt in solution A is 0.1 mol / L);

[0129] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.1 mol / L);

[0130] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 2 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 150°C for 48 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a Bush funnel was used for suction filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain a single metal Co-MOF material.

[0131] 4) Pyrolysis treatment of the monometallic Co-MOF material to obtain a Co-MOF-derived Co@C catalyst. The Co-MOF material was placed in a vacuum tube furnace and pyrolyzed by nitrogen containing 30% hydrogen at a temperature of 300°C for 2 hours to obtain a monometallic Co-MOF-derived Co@C-300 catalyst.

[0132] (2) A method for preparing 1,3-propylene glycol compounds by catalytic hydrogenation of propylene oxide using a Co@C catalyst derived from a single metal Co-MOF, comprising the following steps: 50 mg of a Co@C-300 catalyst derived from a single metal Co-MOF, 13.5 mmol of propylene oxide, and 9.0 g of a solvent methanol (containing 3.0 mg / L NaOH) are added to an intermittent pressure reactor, the air in the reactor is replaced with H2 three times, and then H2 is introduced to make the hydrogen pressure in the reactor reach 3.0 MPa, magnetic stirring is started (speed 400 rpm / min), the reactor is heated to make the hydrogenation reaction temperature 130°C, and the reaction is carried out for 5 hours to carry out a selective hydrogenation reaction of propylene oxide to obtain a 1,3-propylene glycol compound.

[0133] Comparative Example 3

[0134] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0135] 1) Weigh 5 mmol of nickel nitrate into a 100 mL beaker, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution A (the metal salt concentration in solution A is 0.1 mol / L);

[0136] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 30 mL of DMF, 10 mL of water and 10 mL of ethanol to form a mixed solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.1 mol / L);

[0137] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 2 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 150°C for 48 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a Bush funnel was used for suction filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain a single metal Ni-MOF material.

[0138] 4) The single metal Ni-MOF material is subjected to pyrolysis treatment to obtain a Ni@C catalyst derived from Ni-MOF. The Ni-MOF material is placed in a vacuum tube furnace and pyrolyzed by nitrogen containing 30% hydrogen at a temperature of 300°C for 2 hours to obtain a Ni@C-300 catalyst derived from a single metal Ni-MOF.

[0139] (2) A method for preparing 1,3-propylene glycol compound by catalyzing the selective hydrogenation of propylene oxide using a Ni@C catalyst derived from a single metal Ni-MOF, comprising the following steps: 50 mg of a Ni@C-300 catalyst derived from a single metal Ni-MOF, 13.5 mmol of propylene oxide, and 9.0 g of a solvent methanol (containing 3.0 mg / L NaOH) are added to an intermittent pressure reactor, the air in the reactor is replaced with H2 three times, and then H2 is introduced to make the hydrogen pressure in the reactor reach 3.0 MPa, magnetic stirring is started (speed 400 rpm / min), the reactor is heated to make the hydrogenation reaction temperature 130°C, and the reaction is carried out for 5 hours to carry out the selective hydrogenation reaction of propylene oxide to obtain a 1,3-propylene glycol compound.

[0140] Comparative Example 4

[0141] (1) The present invention provides a method for preparing a catalyst for the highly selective hydrogenation of glycidol to 1,3-propylene glycol, such as Figure 1 As shown, the catalyst preparation method comprises the following steps:

[0142] 1) Weigh 5 mmol of total substance and 1:1 molar ratio of cobalt acetate and nickel nitrate in a 100 mL beaker, add 50 mL of DMF as solvent, stir and dissolve thoroughly to obtain solution A (the concentration of metal salt in solution A is 0.1 mol / L);

[0143] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 50 mL of DMF solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.1 mol / L);

[0144] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 2 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 150°C for 48 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a Bush funnel was used for suction filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain Co1Ni1-MOF-I material.

[0145] 4) Pyrolysis treatment of the CoNi-MOF-I material to obtain a nano CoNi@CI catalyst derived from CoNi-MOF-I. The Co1Ni1-MOF-I material was placed in a vacuum tube furnace, and nitrogen containing 30% hydrogen was introduced for pyrolysis treatment at a temperature of 300°C for 2 hours to obtain a nano Co1Ni1@C-300-I catalyst derived from Co1Ni1-MOF-I.

[0146] (2) A method for preparing 1,3-propylene glycol compound by catalyzing the selective hydrogenation of propylene oxide using nano-CoNi@CI catalyst derived from CoNi-MOF-I, comprising the following steps: 50 mg of Co1Ni1@C-300-I catalyst derived from Co1Ni1-MOF-I, 13.5 mmol of propylene oxide, and 9.0 g of solvent methanol (containing 3.0 mg / L NaOH) are added to an intermittent pressure reactor, and the air in the reactor is replaced with H2 for 3 times. Then, H2 is introduced to make the hydrogen pressure in the reactor reach 3.0 MPa, magnetic stirring is started (speed 400 rpm / min), and the reactor is heated to make the hydrogenation reaction temperature 130°C. The reaction is carried out for 5 hours to carry out the selective hydrogenation reaction of propylene oxide to obtain 1,3-propylene glycol compound.

[0147] Comparative Example 5

[0148] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0149] 1) Weigh 5 mmol of total substance of cobalt acetate and nickel nitrate in a molar ratio of 1:1 into a 100 mL beaker, add 50 mL of water as a solvent, stir and dissolve thoroughly to obtain solution A (the concentration of metal salt in solution A is 0.1 mol / L);

[0150] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 50 mL of water as a solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.1 mol / L);

[0151] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 2 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 150°C for 48 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a Bush funnel was used for suction filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain Co1Ni1-MOF-II material.

[0152] 4) Pyrolysis treatment of the CoNi-MOF-II material to obtain a nano CoNi@C-II catalyst derived from CoNi-MOF-II. The Co1Ni1-MOF-II material was placed in a vacuum tube furnace and pyrolyzed by nitrogen containing 30% hydrogen at a temperature of 300°C for 2 hours to obtain a nano Co1Ni1@C-300-II catalyst derived from Co1Ni1-MOF-II.

[0153] (2) A method for preparing 1,3-propylene glycol compounds by catalyzing the selective hydrogenation of propylene oxide using a nano-CoNi@C-II catalyst derived from CoNi-MOF-II, comprising the following steps: 50 mg of a Co1Ni1@C-300-II catalyst derived from Co1Ni1-MOF-II, 13.5 mmol of propylene oxide, and 9.0 g of a solvent methanol (containing 3.0 mg / L NaOH) are added to an intermittent pressure reactor, and the air in the reactor is replaced with H2 three times. Then, H2 is introduced to make the hydrogen pressure in the reactor reach 3.0 MPa, magnetic stirring is started (speed 400 rpm / min), and the reactor is heated to make the hydrogenation reaction temperature 130°C. The reaction is carried out for 5 hours to carry out the selective hydrogenation reaction of propylene oxide to obtain a 1,3-propylene glycol compound.

[0154] Comparative Example 6

[0155] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0156] 1) Weigh 5 mmol of total substance of cobalt acetate and nickel nitrate in a molar ratio of 1:1 into a 100 mL beaker, add 50 mL of ethanol as a solvent, stir and dissolve thoroughly to obtain solution A (the concentration of metal salt in solution A is 0.1 mol / L);

[0157] 2) Weigh 5 mmol of terephthalic acid into a polytetrafluoroethylene liner, add 50 mL of ethanol as a solvent, stir and dissolve thoroughly to obtain solution B (the concentration of terephthalic acid in solution B is 0.1 mol / L);

[0158] 3) Solution A and solution B were added to a polytetrafluoroethylene liner to obtain a mixed solution C. After stirring at room temperature for 2 hours, the liner was placed in a reactor and subjected to static crystallization reaction at 150°C for 48 hours. The reactor was then taken out and aged at room temperature for 2 days. After the reaction was completed, a suction funnel was used for filtration. The filter cake obtained by filtration was washed with ethanol 3 times and DMF 3 times, and the filter cake was collected by filtration. The drying treatment was specifically as follows: vacuum drying at 100°C for 8 hours to obtain Co1Ni1-MOF-III material.

[0159] 4) Pyrolysis treatment of the CoNi-MOF-III material to obtain a nano CoNi@C-III catalyst derived from CoNi-MOF-III. The Co1Ni1-MOF-III material was placed in a vacuum tube furnace and pyrolyzed by nitrogen containing 30% hydrogen at a temperature of 300°C for 2 hours to obtain a nano Co1Ni1@C-300-III catalyst derived from Co1Ni1-MOF-III.

[0160] (2) A method for preparing 1,3-propylene glycol compound by catalyzing the selective hydrogenation of propylene oxide using nano-CoNi@C-III catalyst derived from CoNi-MOF-III, comprising the following steps: 50 mg of Co1Ni1@C-300-III catalyst derived from Co1Ni1-MOF-III, 13.5 mmol of propylene oxide, and 9.0 g of solvent methanol (containing 3.0 mg / L NaOH) are added to an intermittent pressure reactor, and the air in the reactor is replaced with H2 three times. Then, H2 is introduced to make the hydrogen pressure in the reactor reach 3.0 MPa, magnetic stirring is started (speed 400 rpm / min), and the reactor is heated to make the hydrogenation reaction temperature 130°C. The reaction is carried out for 5 hours to carry out the selective hydrogenation reaction of propylene oxide to obtain 1,3-propylene glycol compound.

[0161] Comparative Example 7

[0162] (1) The present invention provides a method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, the catalyst preparation method comprising the following steps:

[0163] 1) Weigh 5 mmol nickel nitrate into a 100 mL beaker, add 50 mL water as a solvent, stir and dissolve thoroughly, then add 3 g γ-Al2O3, and carry out reaction at 90°C for 3 h under 700 W microwave assisted heating. Then, evaporate the reaction solution to remove water. Dry the solution in vacuum at 100°C for 8 h to obtain 10% Ni-Al2O3 material.

[0164] 2) The 10% Ni-Al2O3 material is subjected to pyrolysis treatment to obtain a 10% Ni / Al2O3 hydrogenation catalyst. The 10% Ni-Al2O3 material is placed in a vacuum tube furnace, and nitrogen containing 30% hydrogen is introduced for pyrolysis treatment. The pyrolysis treatment temperature is 300° C. and the time is 2 hours to obtain a 10% Ni-Al2O3 catalyst derived from 10% Ni-Al2O3.

[0165] (2) A method for preparing 1,3-propylene glycol compound by catalyzing the selective hydrogenation of propylene oxide using a 10% Ni-Al2O3 catalyst derived from 10% Ni-Al2O3. The method comprises the following steps: 50 mg of a 10% Ni-Al2O3 catalyst derived from 10% Ni-Al2O3, 13.5 mmol of propylene oxide, and 9.0 g of a solvent methanol (containing 3.0 mg / L NaOH) are added to an intermittent pressure reactor, and the air in the reactor is replaced with H2 for 3 times. Then, H2 is introduced to make the hydrogen pressure in the reactor reach 3.0 MPa, magnetic stirring is started (rotation speed 400 rpm / min), and the reactor is heated to make the hydrogenation reaction temperature 130°C. The reaction is carried out for 5 hours to carry out the selective hydrogenation reaction of propylene oxide to obtain a 1,3-propylene glycol compound.

[0166] like Figure 4 As shown, compared with Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, Comparative Example 5, Comparative Example 6 and Comparative Example 7, the catalytic activity of the catalyst Co1Ni1@C-300 prepared by the present invention is significantly higher than that of the precursor Co1Ni1-MOF material prepared in Comparative Example 1, the catalyst Co@C-300 prepared by using a single metal cobalt salt in Comparative Example 2, the catalyst Ni@C-300 prepared by using a single metal nickel salt in Comparative Example 3, the catalyst Co1Ni1-MOF-I prepared by using a single solvent DMF in Comparative Example 4, the catalyst Co1Ni1-MOF-II prepared by using a single solvent water in Comparative Example 5, the catalyst Co1Ni1-MOF-III prepared by using a single solvent ethanol in Comparative Example 6, and the 10% Ni-Al2O3 catalyst prepared by using a single metal nickel salt in Comparative Example 7. Therefore, the hydrogenation catalyst Co1Ni1@C-300 prepared by mixed solvent crystallization is an effective catalyst for preparing 1,3-propylene glycol compounds, which are selective hydrogenation products of propylene oxide.

[0167] Performance testing:

[0168] X-ray diffraction

[0169] X-ray diffraction was performed on a Rigaku D / MAX-IIIC X-ray diffractometer (CuKα: ) for determination. Grind the sample thoroughly, take about 20-25 mg of the sample and put it into the tablet press. 2 Pressed into thin sheets under pressure.

[0170] from Figure 2 It can be seen that the XRD spectrum of Co1Ni1-MOF prepared in Example 1 of the present invention has characteristic diffraction peaks of CoNi-MOF. The diffraction peaks with 2θ of 5 to 40° in the figure are all characteristic diffraction peak data of the CoNi-MOF skeleton; the Co1Ni1@C-300 catalyst prepared by pyrolysis of the above Co1Ni1-MOF has a small diffraction peak at 2θ of 8.9° attributed to a small amount of CoNi-MOF remaining after pyrolysis, and the diffraction peaks with 2θ of 44.4°, 51.5° and 76.0° are respectively attributed to the diffraction of the crystal planes of Co and Ni

[111] , Co and Ni

[200] and Co and Ni

[220] . This indicates that most of the cobalt and nickel ions of the Co1Ni1@C-300 catalyst sample after heat treatment in Example 1 are reduced to atomic cobalt and nickel.

[0171] Scanning electron microscope image

[0172] Scanning electron microscope The measurement was carried out on a JSM6510LV scanning electron microscope produced by JEOL Ltd. The scanning voltage was 30 kV.

[0173] from Figure 3 It can be seen that the Co1Ni1-MOF material prepared in Example 1 of the present invention is a flower-shaped crystal material composed of orderly stacked layers. A single layer exposes more metal active sites, which is beneficial to the diffusion of reactant molecules and product molecules and the formation of intermediates during the catalytic reaction, and provides an ideal reaction place for the occurrence of the catalytic reaction; although the Co4Ni1-MOF prepared in Example 2 has some flower-shaped crystal materials, they are of different sizes, and there are also some unformed materials distributed; the Co-MOF prepared in Comparative Example 2 is not a flower-shaped crystal material, and although the Ni-MOF prepared in Comparative Example 3 also has crystals stacked in layers, the crystals are irregular.

Claims

1. A method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol, characterized in that: The steps include: 1) placing metal salts including cobalt salt and nickel salt in a container, adding DMF, water and ethanol as a mixed solvent in sequence, stirring and dissolving them sufficiently to obtain a solution A, wherein the cobalt salt is selected from one of cobalt nitrate and cobalt acetate, the nickel salt is selected from one of nickel nitrate and nickel acetate, the molar ratio of the cobalt salt to the nickel salt in the metal salt is 1:1, the mixed solvent is obtained by mixing DMF, water and ethanol in a volume ratio of 3:1:1, and the concentration of the metal salt in the solution A is 0.1-0.2 mol / L; 2) placing terephthalic acid in a polytetrafluoroethylene liner, adding DMF, water and ethanol as a mixed solvent in sequence, stirring and dissolving the mixture to obtain a solution B, wherein the mixed solvent is obtained by mixing DMF, water and ethanol in a volume ratio of 3:1:1, and the concentration of terephthalic acid in the solution B is 0.1-0.2 mol / L; 3) adding solution A and solution B to a polytetrafluoroethylene liner to obtain a mixed solution C, stirring at room temperature for 2 to 6 hours, placing the liner into a reactor, and performing a crystallization reaction at 100 to 180° C. for 12 to 72 hours, then taking out the reactor and performing an aging treatment at room temperature for 2 to 3 days, and performing a purification treatment and a drying treatment after the reaction to obtain an M-MOF material; 4) directly pyrolyzing the M-MOF or loading it on an oxide carrier and then pyrolyzing it to obtain a catalyst, The steps of loading the M-MOF material on the oxide carrier include: dispersing the M-MOF material in water, adding the oxide carrier MOx, wherein MOx is selected from one of γ-Al2O3 and SiO2, and the mass of the M-MOF material accounts for 7-10% of the mass of the M-MOF material and the oxide carrier MOx; after sufficient stirring, loading and reacting at 80-90° C. for 10-12 hours, then evaporating the reaction solution to remove water, and vacuum drying at 90-100° C. for 8-12 hours to complete the loading. The specific steps of the pyrolysis treatment include: placing in a vacuum tube furnace, introducing nitrogen with a 30% hydrogen content for pyrolysis treatment, the pyrolysis treatment temperature is 300-600° C., and the time is 1-2 hours.

2. The method for preparing a catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol as claimed in claim 1, characterized in that: In step 3), the purification treatment is specifically as follows: after suction filtration, the obtained filter cake is washed with ethanol for 3 to 5 times, and then washed with DMF for 3 to 5 times, and the filter cake is collected by filtration; the drying treatment is specifically as follows: vacuum drying at 90 to 100° C. for 8 to 12 hours to obtain M-MOF material.

3. A catalyst, characterized in that The catalyst is prepared by the preparation method of the catalyst for preparing 1,3-propylene glycol by highly selective hydrogenation of propylene oxide according to any one of claims 1 to 2.

4. A use of the catalyst as claimed in claim 3, characterized in that: The catalyst is used for catalyzing the high-selective hydrogenation of glycidol to prepare the hydrogenation product 1,3-propylene glycol.

5. The use of the catalyst as claimed in claim 4, characterized in that: The method for preparing 1,3-propylene glycol by highly selective hydrogenation of glycidol comprises the following steps: Add the catalyst, propylene oxide and solvent into an intermittent pressure reactor, replace the air in the reactor with H2 for 3 times, then fill H2 to make the hydrogen pressure in the reactor reach 1-3.0 MPa, turn on the magnetic stirring, heat the reactor to make the hydrogenation reaction temperature be 90-130°C, react for 3-6 hours to carry out the selective hydrogenation reaction of propylene oxide to obtain 1,3-propylene glycol compound.

6. The use of the catalyst as claimed in claim 5, characterized in that: The amount of the catalyst is 1.0-10.0 mg per 1 mmol of glycidol; the mass fraction of the glycidol in the reaction solution is 5-30%; the reaction solvent is selected from one of methanol, ethanol, isopropanol and tetrahydrofuran, all containing 3.0 mg / L NaOH.

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