Manganese molybdenum oxide catalyst and preparation method and application method thereof
By preparing manganese molybdenum oxide nanoparticle catalyst, the problem of poor catalytic effect in the prior art was solved, and the effect of efficient catalytic conversion of glucose to formic acid was achieved, which was green and environmentally friendly and economically feasible.
Patent Information
- Application Number
- CN202411361839.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-27
- Publication Date
- 2025-01-03
AI Technical Summary
In the prior art, the catalyst used to convert cellulose-rich biomass to prepare formic acid has poor catalytic effect and is difficult to achieve efficient production.
Manganese molybdenum oxide catalyst is used to prepare a manganese molybdenum oxide nanoparticle catalyst for catalyzing glucose by mixing manganese and molybdenum sources with eutectic solvents and water. Formic acid is prepared by oxidation reaction.
The efficient catalytic effect was achieved, the conversion rate of glucose can reach 99.9%, the yield of formic acid can reach 63.63%, and the preparation method is green, environmentally friendly, economical and feasible, and has good application prospects.
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Figure CN119236920A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of catalyst synthesis, and in particular to a manganese-molybdenum oxide catalyst and a preparation method and an application method thereof. Background Art
[0002] Lignocellulose has the advantages of being widely distributed around the world and easily available. It can fix solar energy on the earth through photosynthesis. Its chemical composition is similar to that of fossil fuels such as coal, oil, and natural gas. Utilizing it as a high-value resource is of great significance for providing alternatives to fossil energy and achieving sustainable development.
[0003] Formic acid (FA) is a simple single-carbon carboxylic acid. At room temperature, formic acid is a colorless liquid with a pungent odor. Formic acid has a special structure, containing hydrogen atoms and carboxyl groups, so it has the properties of both aldehydes and acids. In addition, formic acid can be decomposed into carbon monoxide and water by heat. The above properties determine that formic acid has great potential in production and application, and is widely used in textiles, leather, medicine, agriculture, rubber and other fields. In industry, methyl formate is produced by carbonylation of methanol, and then hydrolyzed to produce formic acid. Methanol and carbonyl groups are mainly produced by coal or natural gas at high temperatures in an unsustainable way. In contrast, producing formic acid from renewable cellulosic biomass would be the first choice.
[0004] However, the catalysts used in the prior art for converting cellulose-rich biomass to produce formic acid have the problem of poor catalytic effect. Summary of the invention
[0005] The purpose of the present application is to provide a manganese-molybdenum oxide catalyst and a preparation method and application method thereof, so as to prepare a manganese-molybdenum oxide catalyst suitable for catalyzing the oxidation reaction of glucose to prepare formic acid, with good catalytic effect and high formic acid yield.
[0006] An embodiment of the present application provides a method for preparing a manganese-molybdenum oxide catalyst, which comprises: mixing a manganese source and a molybdenum source with a target solvent and heating the mixture to obtain a mixed solution, wherein the target solvent comprises a low eutectic solvent and / or water; separating the mixed solution into a solid-liquid state, and washing, drying and calcining the separated solid to obtain a manganese-molybdenum oxide catalyst, wherein the manganese-molybdenum oxide catalyst is manganese-molybdenum oxide nanoparticles.
[0007] The target solvent includes a low eutectic solvent and water, and the ratio of the volume of the low eutectic solvent in the target solvent to the volume of water in the target solvent is (1-10):1.
[0008] The target solvent includes a low eutectic solvent; before heating the manganese source and the molybdenum source with the target solvent to obtain a mixed solution, the method further includes: eutecticizing a hydrogen bond acceptor and a hydrogen bond donor to obtain a low eutectic solvent composed of the hydrogen bond acceptor and the hydrogen bond donor.
[0009] The ratio of the amount of the hydrogen bond acceptor substance in the low eutectic solvent to the amount of the hydrogen bond donor substance in the low eutectic solvent is 1:(1-3).
[0010] The hydrogen bond acceptor comprises choline chloride; and the hydrogen bond donor comprises at least one of lactic acid, glycerol and urea.
[0011] The method comprises: mixing the manganese source and the molybdenum source with the target solvent and heating the mixture to obtain a mixed solution, wherein the mixture comprises: mixing the manganese source and the molybdenum source with the target solvent and heating the mixture at a temperature of 150 to 200° C. for 10 to 15 hours, and then cooling the mixture to room temperature to obtain a mixed solution.
[0012] The separated solid is washed, dried and calcined to obtain a manganese-molybdenum oxide catalyst, including: washing the separated solid to obtain a washed solid; drying the washed solid to obtain a dried solid; calcining the dried solid under a protective gas atmosphere, the calcination temperature is 300-600°C, the calcination heating rate is 1-10°C / min, and the calcination time is 3-5h to obtain a manganese-molybdenum oxide catalyst.
[0013] The manganese source includes at least one of KMnO4, (CH3COO)2Mn·4H2O and Mn(NO3)2; the molybdenum source includes at least one of (NH4)2MoO4, Na2MoO4 and K2MoO4.
[0014] The embodiments of the present application also provide a manganese-molybdenum oxide catalyst, which is prepared by any of the above-mentioned methods for preparing the manganese-molybdenum oxide catalyst.
[0015] The embodiment of the present application also provides an application method of a manganese-molybdenum oxide catalyst, which comprises: mixing the manganese-molybdenum oxide catalyst with glucose and water, and then performing an oxidation reaction to obtain formic acid.
[0016] The manganese-molybdenum oxide catalyst provided in the present application and its preparation method and application method are as follows: a manganese source and a molybdenum source are mixed with a target solvent and then heated to obtain a mixed liquid, wherein the target solvent includes a low eutectic solvent and / or water; the mixed liquid is then solid-liquid separated; and the separated solid is washed, dried and calcined to obtain a manganese-molybdenum oxide catalyst; the manganese-molybdenum oxide catalyst is a manganese-molybdenum oxide nanoparticle, thereby providing a manganese-molybdenum oxide catalyst suitable for catalyzing the oxidation reaction of glucose to prepare formic acid; and the manganese-molybdenum oxide catalyst has a nanostructure (e.g., a nanosphere structure), which ensures that it has good catalytic oxidation activity, and thus has a good catalytic effect, can achieve a high conversion rate of glucose and a high yield of formic acid, for example, the conversion rate of glucose can reach 99.9%, and the yield of formic acid can reach 63.63%, and the preparation method of the manganese-molybdenum oxide catalyst is green and environmentally friendly, economically feasible, and can have good application prospects in the field of biomass energy catalysis. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] The technical solution and other beneficial effects of the present application will be made apparent by describing in detail the specific implementation methods of the present application in conjunction with the accompanying drawings.
[0018] Figure 1 1 is a schematic flow chart of a method for preparing a manganese-molybdenum oxide catalyst provided in an embodiment of the present application;
[0019] Figure 2 is a scanning electron microscope image of the manganese-molybdenum oxide catalyst prepared by the preparation method of the manganese-molybdenum oxide catalyst provided in Example 1 of the present application;
[0020] Figure 3 is a scanning electron microscope image of a manganese-molybdenum oxide catalyst prepared by the preparation method of a manganese-molybdenum oxide catalyst provided in Example 2 of the present application;
[0021] Figure 4 is a scanning electron microscope image of a manganese-molybdenum oxide catalyst prepared by the preparation method of a manganese-molybdenum oxide catalyst provided in Example 3 of the present application;
[0022] Figure 5 is an X-ray diffraction pattern of the manganese-molybdenum oxide catalyst prepared by the preparation method of the manganese-molybdenum oxide catalyst provided in Example 1 of the present application;
[0023] Figure 6 This is a catalytic effect diagram of the manganese-molybdenum oxide catalyst prepared by the preparation method of the manganese-molybdenum oxide catalyst provided in Examples 1, 2 and 3 of the present application. DETAILED DESCRIPTION
[0024] The present application is further described in detail below in conjunction with the accompanying drawings and examples. It is particularly noted that the following examples are only used to illustrate the present application, but are not intended to limit the scope of the present application. Similarly, the following examples are only some embodiments of the present application rather than all embodiments, and all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of this application.
[0025] In the following description of the present application, reference is made to “some embodiments”, which describe a subset of all possible embodiments, but it can be understood that “some embodiments” may be the same subset or different subsets of all possible embodiments and may be combined with each other without conflict.
[0026] In the following description of the present application, the terms "first\second\third" involved are merely used to distinguish similar objects and do not represent a specific ordering of the objects. It can be understood that "first\second\third" can be interchanged with a specific order or sequence where permitted, so that the embodiments of the present application described here can be implemented in an order other than that illustrated or described here.
[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein are only for the purpose of describing the embodiments of this application and are not intended to limit this application.
[0028] The following is a detailed description with reference to specific embodiments. It should be noted that the serial numbers of the following embodiments are not intended to limit the preferred order of the embodiments.
[0029] See also Figure 1 , Figure 1 : is a schematic diagram of a process for preparing a manganese-molybdenum oxide catalyst provided in an embodiment of the present application. The specific process of the preparation method of the manganese-molybdenum oxide catalyst can be as follows:
[0030] Step S11. Mix the manganese source and the molybdenum source with a target solvent and heat them to obtain a mixed solution, wherein the target solvent includes a low eutectic solvent and / or water.
[0031] The manganese source may include at least one of KMnO4, (CH3COO)2Mn·4H2O and Mn(NO3)2, and in some examples, the manganese source may be specifically (CH3COO)2Mn·4H2O. The molybdenum source may include at least one of (NH4)2MoO4, Na2MoO4 and K2MoO4, and in some examples, the molybdenum source may be specifically (NH4)2MoO4.
[0032] In this embodiment, the target solvent may include both deep eutectic solvents (DES) and water, or may include only deep eutectic solvents, or may include only water, wherein the water may specifically be deionized water.
[0033] Specifically, the low eutectic solvent may include a hydrogen bond acceptor and a hydrogen bond donor. Among them, the hydrogen bond acceptor may include choline chloride, and in some examples, the hydrogen bond acceptor may be specifically choline chloride. The hydrogen bond donor may include at least one of lactic acid, glycerol and urea, and in some examples, the hydrogen bond donor may be specifically urea. The ratio of the amount of the hydrogen bond acceptor substance in the above-mentioned low eutectic solvent to the amount of the hydrogen bond donor substance in the low eutectic solvent may be 1: (1 to 3), for example, it may be specifically 1: 2.
[0034] In some embodiments, the target solvent may include at least a low eutectic solvent, and the low eutectic solvent may be composed of a hydrogen bond acceptor and a hydrogen bond donor. Accordingly, before the step S11, the method for preparing the manganese molybdenum oxide catalyst may further include: eutecticizing the hydrogen bond acceptor and the hydrogen bond donor to obtain the low eutectic solvent. Specifically, the hydrogen bond acceptor and the hydrogen bond donor may be mixed, and then stirred at 60 to 100° C. for 30 to 120 minutes to obtain the low eutectic solvent.
[0035] In some examples, the hydrogen bond acceptor and the hydrogen bond donor can be mixed and then stirred at 80°C for 60 minutes to obtain the above-mentioned low eutectic solvent. In addition, in a specific implementation, the hydrogen bond acceptor (e.g., choline chloride) and the hydrogen bond donor (e.g., urea) can be added to a sealed flask, and then heated and stirred in an 80°C oil bath for a certain period of time to obtain the above-mentioned low eutectic solvent.
[0036] Specifically, in the above embodiment where the target solvent includes a low eutectic solvent and water, the ratio of the volume of the low eutectic solvent in the target solvent to the volume of water in the target solvent may be (1-10):1, for example, may be specifically 2:1.
[0037] In some embodiments, the above step S11 may specifically include: heating the manganese source and the molybdenum source after mixing with the target solvent, the heating temperature may be 150-200°C, for example, it may be specifically 180°C, the heating time may be 10-15h, for example, it may be specifically 12h, and then cooling to room temperature to obtain a mixed solution. In addition, during specific implementation, a manganese source (for example, (CH3COO)2Mn·4H2O) and a molybdenum source (for example, (NH4)2MoO4) may be added to a liner (for example, a polytetrafluoroethylene liner), and then the above target solvent (for example, the above low eutectic solvent and deionized water) may be added, and stirred evenly, and then the liner may be placed in a reactor (for example, a stainless steel high-pressure reactor), and then the reactor may be placed in an oven at 180°C for 10h, and then cooled to room temperature to obtain the above mixed solution.
[0038] Furthermore, it should be noted that the inventors of the present application discovered during research and development that the use of a low eutectic solvent and water as the target solvent enables the water in the target solvent to dilute the low eutectic solvent, thereby reducing the viscosity of the low eutectic solvent. This ensures that the low eutectic solvent diluted with water in the target solvent can better infiltrate the manganese source and the molybdenum source during the mixing process of the manganese source and the molybdenum source with the target solvent, thereby facilitating the subsequent generation of a manganese-molybdenum oxide catalyst with a smaller size and better catalytic performance.
[0039] Step S12: separating the mixed liquid into solid-liquid and washing, drying and calcining the separated solid to obtain a manganese-molybdenum oxide catalyst, wherein the manganese-molybdenum oxide catalyst is manganese-molybdenum oxide nanoparticles.
[0040] In this embodiment, the manganese-molybdenum oxide catalyst belongs to a manganese-based catalyst. In addition, it should be noted that the inventors of the present application have found in research and development that compared with precious metal catalysts, manganese-based catalysts are relatively cheap and have good catalytic oxidation activity, and due to their rich valence states, environmental friendliness, low cost and other advantages, they have great application potential in the field of biomass energy catalysis. Therefore, the use of manganese source and molybdenum source to prepare manganese-molybdenum oxide catalysts in this application can ensure that the manganese-molybdenum oxide catalyst has good catalytic oxidation activity and is conducive to reducing costs.
[0041] Specifically, Figures 2 to 4 As shown, the manganese molybdenum oxide catalyst has a nanostructure, which can be spherical or quasi-spherical, and the particle size of the manganese molybdenum oxide catalyst can be 30 to 80 nm. In this way, it is ensured that the manganese molybdenum oxide catalyst has good catalytic oxidation activity, and no volatile organic solvent is required to be added during the preparation of the manganese molybdenum oxide catalyst, and the synthesis method is simple and low-cost, so it can have great application potential in the field of biomass energy catalysis.
[0042] In some embodiments, the above step S12 may specifically include:
[0043] Step S121. Separate the mixed liquid into solid-liquid and wash the separated solid to obtain a washed solid.
[0044] Specifically, the mixed liquid can be separated into solid and liquid by a centrifuge, and the separated solid can be washed with water and ethanol in the centrifuge and then dried to obtain the washed solid.
[0045] Step S122: Dry the washed solid to obtain a dried solid.
[0046] Specifically, the washed solid can be placed in an oven and dried at 80° C. for more than 12 hours to obtain a dried solid.
[0047] Step S123: calcining the dried solid under a protective gas atmosphere to obtain a manganese-molybdenum oxide catalyst.
[0048] Specifically, the dried solid can be calcined in a protective gas atmosphere, the calcination temperature can be 300-600°C, for example, can be specifically 500°C, the calcination heating rate can be 1-10°C / min, for example, can be specifically 10°C / min, and the calcination time can be 3-5h to obtain a manganese-molybdenum oxide catalyst. The protective atmosphere can be nitrogen or argon, for example, can be specifically nitrogen.
[0049] Furthermore, in a specific implementation, the dried solid can be placed in a tubular furnace, and then heated to 500° C. at a heating rate of 10° C. / min and calcined for 4 hours in a N2 atmosphere to obtain the above-mentioned manganese-molybdenum oxide catalyst.
[0050] For ease of understanding, the present application is further described in detail below through three specific embodiments (ie, Embodiment 1, Embodiment 2 and Embodiment 3).
[0051] Example 1
[0052] In Example 1, the specific process of the preparation method of the manganese molybdenum oxide catalyst can be as follows:
[0053] Step S21. Providing a low eutectic solvent, comprising: adding 69.815 g of choline chloride and 60.06 g of urea into a sealed flask, heating and stirring in an oil bath at 80° C. to obtain a low eutectic solvent.
[0054] Step S22. 1.384 g of (CH3COO)2Mn·4H2O and 0.1158 g of (NH4)2MoO4 are added as manganese source and molybdenum source to the polytetrafluoroethylene liner respectively, and then the target solvent is added, the target solvent is 21 g of low eutectic solvent and 9 g of deionized water, and stirred evenly, and then the liner is placed in a stainless steel high-pressure reactor, and then the reactor is placed in an oven at 180°C for 10 hours, and then cooled to room temperature to obtain a mixed solution.
[0055] Step S23. Separate the mixed liquid into solid-liquid and wash the separated solid with water and ethanol. Then, dry the washed solid in an oven at 80°C. Then, place the dried solid in a tubular furnace, heat it to 500°C at a heating rate of 10°C / min and calcine it in a N2 atmosphere for 4 hours to obtain manganese molybdenum oxide catalyst A1.
[0056] Example 2
[0057] The preparation method of the manganese molybdenum oxide catalyst provided in Example 2 is basically the same as the preparation method of the manganese molybdenum oxide catalyst provided in Example 1. The difference between the two is that the target solvent is different. Specifically, the target solution in Example 2 is 30g of deionized water, while the target solvent in Example 1 is 21g of a low eutectic solvent and 9g of deionized water. Accordingly, in Example 2, the specific process of the preparation method of the manganese molybdenum oxide catalyst can be as follows:
[0058] Step S31. Providing a low eutectic solvent, comprising: adding 69.815 g of choline chloride and 60.06 g of urea into a sealed flask, heating and stirring in an oil bath at 80° C. to obtain a low eutectic solvent.
[0059] Step S32. 1.384 g of (CH3COO)2Mn·4H2O and 0.1158 g of (NH4)2MoO4 are added to the polytetrafluoroethylene liner as the manganese source and molybdenum source, respectively, and then the target solvent is added, the target solvent is 30 g of deionized water, and stirred evenly, and then the liner is placed in a stainless steel high-pressure reactor, and then the reactor is placed in an oven at 180°C for 10 hours, and then cooled to room temperature to obtain a mixed solution.
[0060] Step S33. Separate the mixed liquid into solid-liquid and wash the separated solid with water and ethanol. Then, dry the washed solid in an oven at 80°C. Then, place the dried solid in a tubular furnace, heat it to 500°C at a heating rate of 10°C / min and calcine it in a N2 atmosphere for 4 hours to obtain manganese molybdenum oxide catalyst A2.
[0061] Example 3
[0062] The preparation method of the manganese molybdenum oxide catalyst provided in Example 3 is basically the same as the preparation method of the manganese molybdenum oxide catalyst provided in Example 1. The difference between the two is that the target solvent is different. Specifically, the target solution in Example 3 is 30g of a low eutectic solvent, while the target solvent in Example 1 is 21g of a low eutectic solvent and 9g of deionized water. Accordingly, in Example 3, the specific process of the preparation method of the manganese molybdenum oxide catalyst can be as follows:
[0063] Step S41. Providing a low eutectic solvent, comprising: adding 69.815 g of choline chloride and 60.06 g of urea into a sealed flask, heating and stirring in an oil bath at 80° C. to obtain a low eutectic solvent.
[0064] Step S42. 1.384 g of (CH3COO)2Mn·4H2O and 0.1158 g of (NH4)2MoO4 are added to the polytetrafluoroethylene liner as the manganese source and molybdenum source, respectively, and then the target solvent is added, the target solvent is 30 g of a low eutectic solvent, and stirred evenly, and then the liner is placed in a stainless steel high-pressure reactor, and then the reactor is placed in an oven at 180°C for 10 hours, and then cooled to room temperature to obtain a mixed solution.
[0065] Step S43. Separate the mixed liquid into solid-liquid and wash the separated solid with water and ethanol. Then, dry the washed solid in an oven at 80°C. Then, place the dried solid in a tubular furnace, heat it to 500°C at a heating rate of 10°C / min and calcine it in a N2 atmosphere for 4 hours to obtain manganese molybdenum oxide catalyst A3.
[0066] Specifically, by testing the manganese molybdenum oxide catalyst A1, manganese molybdenum oxide catalyst A2 and manganese molybdenum oxide catalyst A3 prepared in the above-mentioned Example 1, Example 2 and Example 3, the scanning electron microscope images of each manganese molybdenum oxide catalyst A1 / A2 / A3 are respectively as shown in Figure 2 , Figure 3 and Figure 4 As shown, and the X-ray diffraction pattern of the manganese molybdenum oxide catalyst A1 is as shown Figure 5 shown.
[0067] Combined with Example 1, Example 2 and Example 3, and combined with Figure 2 , Figure 3 and Figure 4 It can be shown that the addition of the low eutectic solvent in the above target solvent can reduce the size of the manganese molybdenum oxide catalyst, thereby facilitating the formation of a nanostructure. Moreover, the low eutectic solvent in the above target solvent can generate a manganese molybdenum oxide catalyst with a smaller size and more regular morphology after being diluted with water.
[0068] Further, see Figure 5It can be seen that the addition of a low eutectic solvent can also reduce manganese to a lower valence state, thereby obtaining better catalytic performance.
[0069] As can be seen from the above, the preparation method of the manganese-molybdenum oxide catalyst provided in this embodiment is to obtain a mixed liquid by mixing a manganese source and a molybdenum source with a target solvent and then heating them, wherein the target solvent includes a low eutectic solvent and / or water, and then the mixed liquid is separated into a solid-liquid state, and the separated solid is washed, dried and calcined to obtain a manganese-molybdenum oxide catalyst. The manganese-molybdenum oxide catalyst is a manganese-molybdenum oxide nanoparticle, thereby preparing a manganese-molybdenum oxide catalyst suitable for catalyzing the oxidation reaction of glucose to prepare formic acid, and the manganese-molybdenum oxide catalyst has a nanostructure (for example, a nanosphere structure), which ensures that it has good catalytic oxidation activity, and thus has a good catalytic effect, can achieve a high conversion rate of glucose, and a high yield of formic acid, and the preparation method of the manganese-molybdenum oxide catalyst is green and environmentally friendly, economically feasible, and can have good application prospects in the field of biomass energy catalysis.
[0070] In order to better implement the preparation method of the manganese molybdenum oxide catalyst provided in the embodiment of the present application, the embodiment of the present application also provides a manganese molybdenum oxide catalyst (such as Figures 2 to 4 As shown), the manganese-molybdenum oxide catalyst is prepared by the preparation method of the manganese-molybdenum oxide catalyst provided by any of the above embodiments.
[0071] Specifically, the manganese molybdenum oxide catalyst is manganese molybdenum oxide nanoparticles and has a nanostructure (eg, a nanosphere structure).
[0072] In some embodiments, the particle size of the manganese molybdenum oxide catalyst may be 30 to 80 nm.
[0073] Furthermore, it should be noted that the manganese-molybdenum oxide catalyst in the embodiment of the present application is prepared by the preparation method of the manganese-molybdenum oxide catalyst provided in any of the above embodiments, and therefore has all the same beneficial effects, which will not be described in detail in this embodiment.
[0074] Based on the manganese-molybdenum oxide catalyst described in the above embodiment, this embodiment will further describe the manganese-molybdenum oxide catalyst from the perspective of the application method.
[0075] The application method of the manganese-molybdenum oxide catalyst provided in the embodiment of the present application can be applied to the scenario of catalyzing glucose to prepare formic acid. The specific process of the application method of the manganese-molybdenum oxide catalyst can be as follows:
[0076] The manganese molybdenum oxide catalyst is mixed with glucose and water and then subjected to oxidation reaction to obtain formic acid.
[0077] Specifically, the manganese-molybdenum oxide catalyst described in any of the above embodiments of the present application can be mixed with glucose and water and then subjected to an oxidation reaction to obtain formic acid.
[0078] In some embodiments, glucose can be obtained by hydrolysis of cellulose. In addition, in the process of oxidizing glucose to prepare formic acid, the mass ratio of the manganese molybdenum oxide catalyst used to the mass of glucose can be 1: (1-10), for example, it can be specifically 1: 2; the mass ratio of glucose to the volume of water used can be 1 mg: (0.025-0.1) mL, for example, it can be specifically 1 mg: 0.1 mL; the temperature of the oxidation reaction can be 120-180 ° C, for example, it can be specifically 130-160 ° C; the time of the oxidation reaction can be 0-8 hours, for example, it can be specifically 1-6 hours; the pressure of the oxidation reaction can be 2-4 MPa, for example, it can be specifically 3 MPa.
[0079] Furthermore, for ease of understanding, the present application is further described in detail below through three specific application examples (ie, application example 1, application example 2, and application example 3).
[0080] Application Example 1
[0081] In Application Example 1, the specific process of the application method of the manganese-molybdenum oxide catalyst can be as follows:
[0082] 40 mg of the manganese molybdenum oxide catalyst prepared in Example 1 and 80 mg of glucose were placed in a reactor, and then 4 ml of deionized water was added, and oxygen was filled into the reactor to 3 MPa, heated to 150°C, and reacted for 3 hours to obtain formic acid. Figure 6 As shown, the conversion rate of glucose can be 99.9% and the yield of formic acid is 63.63%.
[0083] Application Example 2
[0084] In Application Example 2, the specific process of the application method of the manganese-molybdenum oxide catalyst can be as follows:
[0085] 40 mg of the manganese molybdenum oxide catalyst prepared in Example 2 and 80 mg of glucose were placed in a reactor, and then 4 ml of deionized water was added, and oxygen was filled into the reactor to 3 MPa, heated to 150°C, and reacted for 3 hours to obtain formic acid. Figure 6 As shown, the conversion rate of glucose was 85.67% and the yield of formic acid was 40.14%.
[0086] Application Example 3
[0087] In Application Example 3, the specific process of the application method of the manganese-molybdenum oxide catalyst can be as follows:
[0088] 40 mg of the manganese molybdenum oxide catalyst prepared in Example 3 and 80 mg of glucose were placed in a reactor, and then 4 ml of deionized water was added, and oxygen was filled into the reactor to 3 MPa, heated to 150°C, and reacted for 3 hours to obtain formic acid. Figure 6 As shown, the conversion rate of glucose can be 89.52%, and the yield of formic acid can be 52.91%.
[0089] In this embodiment, Figure 6 As shown, formic acid is prepared by catalyzing the oxidation reaction of glucose using the manganese-molybdenum oxide catalyst described in any of the above embodiments of the present application. Since the manganese-molybdenum oxide catalyst has a nanostructure (for example, a nanosphere structure), it is ensured that it has good catalytic oxidation activity, and thus has a good catalytic effect, and can achieve a high conversion rate of glucose and a high yield of formic acid. For example, the conversion rate of glucose can reach 99.9%, and the yield of formic acid can reach 63.63%.
[0090] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.
[0091] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application shall be included in the protection scope of the present application. The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application shall be included in the protection scope of the present application.
Claims
1. A method for preparing a manganese-molybdenum oxide catalyst, characterized in that: include: The manganese source and the molybdenum source are mixed with a target solvent and then heated to obtain a mixed solution, wherein the target solvent includes a low eutectic solvent and / or water; The mixed liquid is separated into solid and liquid, and the separated solid is washed, dried and calcined to obtain a manganese molybdenum oxide catalyst, wherein the manganese molybdenum oxide catalyst is manganese molybdenum oxide nanoparticles.
2. The preparation method according to claim 1, characterized in that: The target solvent includes a low eutectic solvent and water, and the ratio of the volume of the low eutectic solvent in the target solvent to the volume of water in the target solvent is (1-10):
1.
3. The preparation method according to claim 1, characterized in that: The target solvent includes a low eutectic solvent; before heating the mixture of the manganese source and the molybdenum source with the target solvent to obtain a mixed solution, the method further includes: The hydrogen bond acceptor and the hydrogen bond donor are eutectic to obtain a low eutectic solvent consisting of the hydrogen bond acceptor and the hydrogen bond donor.
4. The preparation method according to claim 3, characterized in that: The ratio of the amount of the hydrogen bond acceptor substance in the deep eutectic solvent to the amount of the hydrogen bond donor substance in the deep eutectic solvent is 1:(1-3).
5. The preparation method according to claim 3, characterized in that: The hydrogen bond acceptor comprises choline chloride; and the hydrogen bond donor comprises at least one of lactic acid, glycerol and urea.
6. The preparation method according to claim 1, characterized in that: The manganese source and the molybdenum source are mixed with the target solvent and then heated to obtain a mixed solution, comprising: The manganese source and the molybdenum source are mixed with the target solvent and then heated at a temperature of 150 to 200° C. for a heating time of 10 to 15 hours, and then cooled to room temperature to obtain a mixed solution.
7. The preparation method according to claim 1, characterized in that: The separated solid is washed, dried and calcined to obtain a manganese-molybdenum oxide catalyst, comprising: washing the separated solid to obtain a washed solid; Drying the washed solid to obtain a dried solid; The dried solid is calcined in a protective gas atmosphere, the calcination temperature is 300-600° C., the calcination heating rate is 1-10° C. / min, and the calcination time is 3-5 hours to obtain a manganese-molybdenum oxide catalyst.
8. The preparation method according to claim 1, characterized in that: The manganese source includes at least one of KMnO4, (CH3COO)2Mn·4H2O and Mn(NO3)2; the molybdenum source includes at least one of (NH4)2MoO4, Na2MoO4 and K2MoO4.
9. A manganese-molybdenum oxide catalyst, characterized in that The method is prepared by the method according to any one of claims 1 to 8.
10. A method for applying a manganese-molybdenum oxide catalyst, characterized in that: include: The manganese-molybdenum oxide catalyst according to claim 9 is mixed with glucose and water and then subjected to oxidation reaction to obtain formic acid.