CN109876823B - Mn-Fe composite metal catalyst and preparation method and application thereof - Google Patents
Mn-Fe composite metal catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method and application of a Mn-Fe composite metal catalyst, and belongs to the technical field of composite catalysts. The Mn-Fe composite metal catalyst provided by the invention comprises MnCO3Crystal modification and Fe2O3A crystalline form; the MnCO3Crystal modification and Fe2O3The molar ratio of the crystal forms is (0.3-3.0): 1; the MnCO3Crystal modification and Fe2O3Crystal form has cell defects. The Mn-Fe composite metal catalyst provided by the invention has higher catalytic efficiency, the Mn-Fe composite metal catalyst provided by the invention is used for catalyzing 5-hydroxymethylfurfural to oxidize and prepare 2, 5-furandicarboxaldehyde, the conversion rate of 5-hydroxymethylfurfural is up to 58%, the selectivity of 2, 5-furandicarboxaldehyde is up to more than 99%, and the Mn-Fe composite metal catalyst has good recycling effect and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of composite catalysts, in particular to a preparation method and application of a Mn-Fe composite metal catalyst.
Background
2, 5-furan dicarbaldehyde is an important fine chemical and intermediate compound, and has potential application value in multiple fields. The 5-hydroxymethylfurfural has a simple molecular structure, contains three functional groups of aldehyde group, hydroxymethyl and furan ring, is a very important biomass platform compound, is an intermediate for synthesizing various fine chemicals and furan-based polymers, and is generally used for preparing 2, 5-furan dicarboxaldehyde by oxidizing 5-hydroxymethylfurfural in the prior art. However, in the process of preparing 2, 5-furandicarboxaldehyde by selective oxidation of 5-hydroxymethylfurfural, hydrolysis reactions of different degrees can occur due to a large amount of hydroxyl groups in 5-hydroxymethylfurfural, and a large amount of byproducts are generated; and because the aldehyde group in the 5-hydroxymethyl furfural and the 2, 5-furan dicarboxaldehyde is relatively active, the aldehyde group is easily over-oxidized to generate the 2, 5-furan dicarboxylic acid. These problems ultimately lead to low yields and low selectivities of 2, 5-furandicarboxaldehyde. Therefore, it is an important research make internal disorder or usurp to find a suitable catalyst system and reaction medium to suppress the side reactions as much as possible and to increase the yield and selectivity of 2, 5-furandicarboxaldehyde.
Chinese patents CN 107417649A, CN 108435230a and CN 104277016a disclose methods for preparing 2, 5-furandicarboxaldehyde by catalytic oxidation of 5-hydroxymethylfurfural using noble metal (e.g., Au, Ru, etc.) supported catalysts, which have good effects, but the activity of the supported noble metal catalyst is closely related to the preparation method thereof, the preparation process of the catalyst is complex, and the noble metal is expensive, so the industrial application of the supported noble metal catalyst is severely restricted.
Chinese patent CN 105968075A discloses the use of non-metallic catalyst g-C3N4M can realize the conversion from 5-hydroxymethylfurfural to 2, 5-furandicarboxaldehyde, the catalyst has poor catalytic effect, the conversion rate of 5-hydroxymethylfurfural is lower than 47.3%, the selectivity of 2, 5-furandicarboxaldehyde is lower than 67.7%, and the conversion rate of reactants and the selectivity of products are lower.
The transition metal catalyst has relatively low price, can show better catalytic activity in a plurality of reaction processes, and particularly can be used for the reaction of preparing 2, 5-furan diformaldehyde by oxidizing 5-hydroxymethylfurfural. However, at present, patent reports on transition metal catalysts are rare, and although the cuprous bromide catalyst reported in the existing patent (CN 104275210a) can obtain a relatively good catalytic effect, the stability of cuprous bromide is poor, and the temperature and pressure required by the reaction are both at relatively high levels, so that the industrial application has certain difficulty.
Disclosure of Invention
The Mn-Fe composite metal catalyst provided by the invention is simple in preparation method, mild in safe reaction conditions, and capable of greatly improving the conversion rate of 5-hydroxymethylfurfural and the selectivity of 2, 5-furandicarboxaldehyde when being applied to the reaction of preparing 2, 5-furandicarboxaldehyde by oxidizing 5-hydroxymethylfurfural.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a Mn-Fe composite metal catalyst, which comprises MnCO3Crystal modification and Fe2O3A crystalline form; the MnCO3Crystal modification and Fe2O3The molar ratio of the crystal forms is (0.3-3.0): 1; the MnCO3Crystal modification and Fe2O3Crystal form has cell defects.
Preferably, the Mn — Fe composite metal catalyst is a brown solid nanoparticle; the MnCO3Crystal modification and Fe2O3All crystal forms are hexagonal crystal systems.
The invention provides a preparation method of the Mn-Fe composite metal catalyst in the technical scheme, which comprises the following steps:
mixing an iron source, a manganese source, ionic liquid, a carbonate donor and a solvent to obtain a reaction solution;
carrying out hydrothermal reaction on the reaction solution to obtain a Mn-Fe composite metal catalyst precursor;
and calcining the Mn-Fe composite metal catalyst precursor to obtain the Mn-Fe composite metal catalyst.
Preferably, the iron source comprises Fe (CH)3COO)3、Fe2(SO4)3、FeCl3And Fe (NO)3)3One or more of the above;
the manganese source comprises Mn (CH)3COO)2、MnSO4、MnCl2And Mn (NO)3)2One or more of them.
Preferably, the molar ratio of the iron source to the manganese source, calculated as iron and manganese, is 1: (0.2-5).
Preferably, the ionic liquid comprises one or more of imidazole chloride salt, imidazole nitrate, imidazole borate and imidazole acetate;
the carbonate donor comprises one or more of hexamethylenetetramine, sodium carbonate, sodium bicarbonate, urea and hydrazine hydrate;
the solvent includes an organic solvent or water.
Preferably, the dosage ratio of the ionic liquid, the carbonate donor and the solvent is (2-10) mmol: (2-30) mmol: (10-40) mL.
Preferably, the temperature of the hydrothermal reaction is 120-180 ℃ and the time is 5-15 h.
Preferably, the calcining temperature is 300-500 ℃, and the calcining time is 3-6 h.
The invention also provides an application of the Mn-Fe composite metal catalyst in the technical scheme or the Mn-Fe composite metal catalyst prepared by the preparation method in the technical scheme in catalyzing 5-hydroxymethylfurfural to prepare 2, 5-furan diformaldehyde.
The invention provides a Mn-Fe composite metal catalyst, which comprises MnCO3Crystal modification and Fe2O3A crystalline form; the MnCO3Crystal modification and Fe2O3The molar ratio of the crystal forms is (0.3-3.0): 1; the MnCO3Crystal modification and Fe2O3Crystal form has cell defects. The Mn-Fe composite metal catalyst provided by the invention is subjected to hydrogen-temperature programmed reduction and X-ray diffraction analysis, and MnCO3、Fe2O3The doping effect is existed between the Mn and Fe, the synergistic effect between the Mn and Fe is enhanced, and simultaneously, the crystal cell defect is formed, thereby being beneficial to the electron transfer and improving the catalytic efficiency of the catalyst. The results of the examples show that when the Mn-Fe composite metal catalyst provided by the invention is used for catalyzing 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxaldehyde, the conversion rate of 5-hydroxymethylfurfural is up to 58%, the selectivity of 2, 5-furandicarboxaldehyde is over 99%, and the recycling effect is good.
The preparation method provided by the invention is simple to operate, low in energy consumption, safe, mild in reaction condition and suitable for industrial production.
Drawings
FIG. 1 is an X-ray diffraction pattern of a Mn-Fe composite metal catalyst prepared in examples 1 and 2 of the present invention;
FIG. 2 is an X-ray diffraction pattern of a Mn-Fe composite metal catalyst prepared in examples 3 and 4 of the present invention;
FIG. 3 is an X-ray diffraction pattern of a Mn-Fe composite metal catalyst prepared in examples 5 and 6 of the present invention.
Detailed Description
The invention provides a Mn-Fe composite metal catalyst, which comprises MnCO3Crystal modification and Fe2O3A crystalline form; the MnCO3Crystal modification and Fe2O3The molar ratio of the crystal forms is (0.3-3.0): 1; the MnCO3Crystal modification and Fe2O3Crystal form has cell defects.
In the present invention, the MnCO3Crystal modification and Fe2O3The crystal form molar ratio is preferably (0.3-3.0): 1, more preferably (0.5 to 2): 1, most preferably (0.8 to 1.2): 1.
in the invention, the Mn-Fe composite metal catalyst is brown solid nano-particles, the particle size of the Mn-Fe composite metal catalyst is 50-60 nm, and in the invention, the MnCO is3Crystal modification and Fe2O3All crystal forms are hexagonal crystal systems.
The Mn-Fe composite metal catalyst provided by the invention has higher catalytic efficiency, the Mn-Fe composite metal catalyst provided by the invention is used for catalyzing 5-hydroxymethylfurfural to oxidize and prepare 2, 5-furandicarboxaldehyde, the conversion rate of 5-hydroxymethylfurfural is up to 58%, the selectivity of 2, 5-furandicarboxaldehyde is up to more than 99%, and the Mn-Fe composite metal catalyst has good recycling effect and is suitable for industrial production.
The invention provides a preparation method of the Mn-Fe composite metal catalyst in the technical scheme, which comprises the following steps:
mixing an iron source, a manganese source, ionic liquid, a carbonate donor and a solvent to obtain a reaction solution;
carrying out hydrothermal reaction on the reaction solution to obtain a Mn-Fe composite metal catalyst precursor;
and calcining the Mn-Fe composite metal catalyst precursor to obtain the Mn-Fe composite metal catalyst.
The method mixes an iron source, a manganese source, ionic liquid, a carbonate donor and a solvent to obtain a reaction solution. In the invention, specifically, an iron source, a manganese source and a part of solvent are mixed to obtain a first solution; mixing the ionic liquid, the carbonate donor and the residual solvent to obtain a second solution; and mixing the second solution with the first solution to obtain a third solution. In the invention, the second solution is preferably mixed with the first solution by uniformly dripping the second solution into the first solution; the dripping speed is preferably 0.5-6 mL/min, and more preferably 1-3 mL/min; the dripping is preferably carried out at room temperature under the stirring condition, and the stirring speed is preferably 200-800 rpm, and more preferably 400-600 rpm.
In the present invention, the iron source preferably includes Fe (CH)3COO)3、Fe2(SO4)3、FeCl3And Fe (NO)3)3More preferably comprises Fe (CH)3COO)3、Fe2(SO4)3、FeCl3Or Fe (NO)3)3. In the present invention, the manganese source preferably comprises Mn (CH)3COO)2、MnSO4、MnCl2And Mn (NO)3)2More preferably comprises Mn (CH)3COO)2、MnSO4、MnCl2Or Mn (NO)3)2. In the present invention, the molar ratio of the iron source to the manganese source is preferably 1: (0.2 to 5), more preferably 1: (0.5 to 4), and most preferably 1: (0.5-2).
In the invention, the ionic liquid preferably comprises one or more of imidazole chloride salt, imidazole nitrate salt, imidazole borate salt and imidazole acetate salt, and more preferably imidazole chloride salt, imidazole nitrate salt, imidazole borate salt or imidazole acetate salt. In the present invention, the imidazolium chloride salt preferably includes one or more of 1-butyl-3-methylimidazolium chloride salt, 1-ethyl-3-methylimidazolium chloride salt, 1-hexyl-3-methylimidazolium chloride salt, and 1-pentyl-3-methylimidazolium chloride salt; the imidazole nitrate preferably comprises one or more of 1-butyl-3-methylimidazole nitrate, 1-ethyl-3-methylimidazole nitrate, 1-hexyl-3-methylimidazole nitrate and 1-pentyl-3-methylimidazole nitrate; the imidazole borate preferably comprises one or more of 1-butyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazole tetrafluoroborate and 1-pentyl-3-methylimidazole tetrafluoroborate; the imidazole acetate preferably comprises one or more of 1-butyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole acetate, 1-hexyl-3-methylimidazole acetate and 1-pentyl-3-methylimidazole acetate. According to the invention, the Mn-Fe composite metal catalyst is more uniformly distributed while keeping a smaller particle size by adding the ionic liquid.
In the present invention, the carbonate donor preferably includes one or more of hexamethylenetetramine, sodium carbonate, sodium bicarbonate, urea and hydrazine hydrate, and more preferably hexamethylenetetramine, sodium carbonate, sodium bicarbonate, urea or hydrazine hydrate. In the invention, the carbonate donor undergoes hydrolysis reaction to release CO in the hydrothermal reaction process3 2-And OH-Ions of Mn with these ions2+And Fe2+Ion reaction to form MnCO3Crystal nuclei and Fe (OH)2Crystal nucleus grows up simultaneously, a precursor of the Mn-Fe composite metal catalyst is formed through dehydration, and the growth process of the nano particles is limited by adding the ionic liquid, so that the nano particles are stabilized and limited in growth.
In the present invention, the solvent preferably includes an organic solvent or water; the organic solvent preferably comprises one or more of methanol, ethanol, isopropanol, N-butanol, dimethyl sulfoxide and N, N-dimethylformamide, and more preferably comprises methanol, ethanol, isopropanol, N-butanol, dimethyl sulfoxide or N, N-dimethylformamide.
In the invention, the dosage ratio of the ionic liquid, the carbonate donor and the solvent is preferably (2-10) mmol: (2-30) mmol: (10-40) mL, more preferably (2-8) mmol: (2-25) mmol: (10-35) mL, most preferably (3-7) mmol: (5-30) mmol: (20-40) mL.
After the reaction solution is obtained, the invention uses the reaction solutionCarrying out hydrothermal reaction to obtain a Mn-Fe composite metal catalyst precursor. In the invention, the temperature of the hydrothermal reaction is preferably 120-180 ℃, more preferably 130-160 ℃, and most preferably 140-150 ℃; the heating rate of heating to the temperature of the hydrothermal reaction is preferably 1-5 ℃/min, and more preferably 2-3 ℃/min; the time of the hydrothermal reaction is preferably 5-15 h, more preferably 8-12 h, and most preferably 9-11 h. The equipment used for carrying out the hydrothermal reaction is not particularly limited, and the equipment well known by the technical personnel in the field can be adopted; in the embodiment of the invention, the reaction solution is placed in a hydrothermal kettle, then the hydrothermal kettle containing the reaction solution is placed in a muffle furnace, and the hydrothermal reaction is carried out by heating in the muffle furnace. In the hydrothermal process, carbonate donor is hydrolyzed to release CO3 2-And OH-Ions of Mn with these ions2+And Fe2+Ion reaction to form MnCO3Crystal nuclei and Fe (OH)2Crystal nucleus grows up simultaneously, a precursor of the Mn-Fe composite metal catalyst is formed through dehydration, and the growth process of the nano particles is limited by adding the ionic liquid, so that the nano particles are stabilized and limited in growth.
After the hydrothermal reaction is finished, preferably, the obtained system is subjected to solid-liquid separation in the invention, and then the obtained solid material is washed and dried to obtain the Mn-Fe composite metal catalyst precursor. The washing mode is not particularly limited in the invention, and the washing mode known to the technicians in the field can be adopted; the washing agent used for washing is preferably ethanol and deionized water, and the washing mode is preferably that ethanol and water are alternately washed for 3-5 times. The drying mode is not particularly limited, and the drying mode known in the field can be adopted, specifically, an oven is adopted for drying; the drying temperature is preferably 40-100 ℃, more preferably 50-90 ℃, and most preferably 60-80 ℃; the drying time is preferably 5-20 h, more preferably 6-15 h, and most preferably 7-10 h.
After obtaining the Mn-Fe composite metal catalyst precursor, the invention calcines the Mn-Fe composite metal catalyst precursor to obtain the Mn-Fe composite metal catalyst.
In the invention, the calcination temperature is preferably 300-500 ℃, more preferably 350-450 ℃, and most preferably 350-400 ℃; the heating rate of the temperature rising to the calcining temperature is preferably 0.5-4.0 ℃/min, and more preferably 1-3 ℃/min; the calcination time is preferably 3-6 h, and more preferably 4-5 h. The equipment used for the calcination in the present invention is not particularly limited, and equipment known to those skilled in the art for carrying out calcination, such as a muffle furnace, may be used. In the calcining process, the method removes residual impurities in the precursor and promotes MnCO3、Fe2O3And through the doping effect among crystal forms, lattice defects are formed, more active sites are exposed, and the activity of the catalyst is improved.
After the calcination reaction is completed, the obtained Mn-Fe composite metal catalyst is preferably stored in a sealed manner at the temperature of 10-20 ℃.
The invention also provides an application of the Mn-Fe composite metal catalyst in the technical scheme or the Mn-Fe composite metal catalyst prepared by the preparation method in the technical scheme in catalyzing 5-hydroxymethylfurfural to prepare 2, 5-furan diformaldehyde. The method for using the Mn-Fe composite metal catalyst in the reaction of catalyzing the 5-hydroxymethylfurfural oxidation to prepare 2, 5-furandicarboxaldehyde is not particularly limited, and the 5-hydroxymethylfurfural oxidation method well known to the technical personnel in the field can be adopted.
In the invention, the Mn-Fe composite metal catalyst is adopted to catalyze the oxidation of 5-hydroxymethylfurfural to prepare 2, 5-furan diformaldehyde, and the method preferably comprises the following steps: mixing the Mn-Fe composite metal catalyst, 5-hydroxymethylfurfural and a solvent, and carrying out an oxidation reaction under the stirring condition to obtain 2, 5-furandicarboxaldehyde.
In the present invention, the mass ratio of the Mn — Fe composite metal catalyst, 5-hydroxymethylfurfural, and solvent is preferably 1: (0.5-2): (50 to 150), more preferably 1: (0.8-1.2): (80-120). In the present invention, the solvent preferably includes water and/or an organic solvent. In the present invention, the organic solvent preferably includes one or more of N, N-dimethylformamide, 1, 4-dioxane, toluene, benzene, ethanol, and dimethyl sulfoxide, and more preferably N, N-dimethylformamide, 1, 4-dioxane, toluene, benzene, ethanol, or dimethyl sulfoxide.
In the present invention, the rotation speed of the stirring is preferably 200 to 800rpm, and more preferably 400 to 600 rpm. In the present invention, the oxidation reaction is preferably carried out in an oxygen atmosphere; the pressure of the oxygen is preferably 0.5 to 1.2MPa, and more preferably 0.6 to 1.0 MPa. In the invention, the temperature of the oxidation reaction is preferably 80-120 ℃, and more preferably 90-100 ℃; the time of the oxidation reaction is preferably 0.5-8 h, and more preferably 1-4 h.
After the reaction is finished, the Mn-Fe composite metal catalyst is recovered through centrifugal separation, washed and dried by deionized water and ethanol, and then calcined, so that the Mn-Fe composite metal catalyst can be recycled. In the present invention, the experimental parameters of washing, drying and calcining are the same as above, and are not described in detail herein.
The preparation method provided by the invention is simple and safe, has mild reaction conditions, and greatly improves the conversion rate of 5-hydroxymethylfurfural and the selectivity of 2, 5-furandicarboxaldehyde when being applied to the reaction of preparing 2, 5-furandicarboxaldehyde by oxidizing 5-hydroxymethylfurfural.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Fully dissolving 5mmol of manganese nitrate and 5mmol of ferric nitrate in 20mL of water to obtain a first solution; fully dissolving 20mmol of hexamethylenetetramine and 1g of 1-butyl-3-methylimidazole acetate in 20mL of water to obtain a second solution; dropwise adding the second solution into the first solution at room temperature at the speed of 2mL/min to obtain a reaction solution;
(2) transferring the reaction liquid obtained in the step (1) to a hydrothermal kettle, placing the hydrothermal kettle in a muffle furnace, heating to 150 ℃ at the heating rate of 2 ℃/min, carrying out hydrothermal reaction for 10 hours, carrying out solid-liquid separation on the obtained system, alternately washing the obtained solid material for 3 times by using water and ethanol, placing the obtained material in a drying oven, and drying for 10 hours at the temperature of 60 ℃ to obtain a Mn-Fe composite metal catalyst precursor;
(3) and (3) placing the Mn-Fe composite metal catalyst precursor obtained in the step (2) in a muffle furnace, calcining for 4h at 350 ℃ to obtain the Mn-Fe composite metal catalyst, and hermetically storing the Mn-Fe composite metal catalyst at room temperature.
Examples 2 to 6
Examples 2-6 were prepared according to the preparation method of example 1, and the specific experimental conditions are shown in table 1.
TABLE 1 Experimental conditions for examples 1-6 preparation of Mn-Fe composite metal catalysts
The Mn-Fe composite metal catalysts prepared in examples 1 to 6 are used as samples for characterization analysis, and the X-ray diffraction (XRD) is shown in figures 1 to 3, wherein the X-ray diffraction experiment is specifically that shooting is carried out on a D8Advance (Bruker) instrument, and a Cu K alpha radiation source light source is used
The operating voltage is 40kV, the operating current is 40mA, and the scanning speed is 10 degrees/min; the results are as follows:
in FIG. 1, the XRD pattern of the Mn-Fe composite metal catalyst prepared in example 1 has sharp MnCO3、Fe2O3And a crystal form characteristic peak shows that the Mn-Fe composite metal catalyst obtained in example 1 has good crystallinity. The XRD pattern of the Mn-Fe composite metal catalyst prepared in example 2 also has obvious MnCO3、Fe2O3Characteristic peaks of crystal form, but by contrast of the intensity of characteristic diffraction peaksA degree of crystallinity weaker than that of the catalyst obtained in example 1;
in FIG. 2, the XRD pattern of the Mn-Fe composite metal catalyst prepared in example 3 has sharp MnCO3、Fe2O3A crystal form characteristic peak, which shows that the Mn-Fe composite metal catalyst obtained in example 3 has good crystallinity; MnCO3The diffraction peak of the crystal form characteristic is weakened compared with that of example 1, which shows that the reduction of the dosage of the hexamethylenetetramine leads to MnCO3The crystal form content is reduced; because the hexamethylenetetramine is dissolved in water at normal temperature and low temperature and then hydrolyzed to generate NH3And formaldehyde, used as NH3The invention adopts hydrothermal reaction at 150 ℃, and the hydrolysis of the hexamethylenetetramine can generate NH3And CO3 2-Therefore, the amount of hexamethylenetetramine used is increased, and CO generated in the solution3 2-The concentration is increased, resulting in MnCO in the catalyst3The content increases and the crystallinity increases. XRD pattern of Mn-Fe composite metal catalyst prepared in example 4 has sharp MnCO3Crystal modification and Fe2O3The characteristic peak of the crystal form shows that the obtained Mn-Fe composite metal catalyst has good crystallinity; MnCO3The diffraction peak of crystal form characteristic is enhanced compared with example 1, which shows that the increase of the dosage of the hexamethylenetetramine leads to MnCO3The content of the crystal form is increased.
In FIG. 3, the XRD patterns of the Mn-Fe composite metal catalysts prepared in examples 5 and 6 also have sharp MnCO3Crystal modification and Fe2O3Characteristic peaks of crystal form, in contrast to the XRD pattern obtained in example 1 of FIG. 1, the amounts of Mn source and Fe source, MnCO, were varied3And Fe2O3The intensity of the characteristic diffraction peak is obviously changed. Shows that the dosage of the manganese source is increased, the dosage of the corresponding iron source is reduced, and the MnCO in the generated Mn-Fe composite metal catalyst3Increased content of crystalline forms, Fe2O3The content of the crystal form is reduced.
Application example 1
50mg of the Mn-Fe composite metal catalyst prepared in example 1, 63mg of 5-hydroxymethylfurfural and 5g of N, N-dimethylformamide were mixed, and stirred and reacted at 90 ℃ for 2 hours at a rotation speed of 500rpm in an oxygen atmosphere with a pressure of 0.8MPa to obtain 2, 5-furandicarboxaldehyde.
Application examples 2 to 21
According to the preparation method of application example 1, the Mn-Fe composite metal catalyst prepared in the example is applied to catalyzing 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxaldehyde. The specific experimental conditions are shown in Table 2.
TABLE 2 Experimental conditions for the preparation of 2, 5-furandicarboxaldehyde using examples 1-21
As can be seen from Table 2, when the Mn-Fe composite metal catalyst provided by the invention is applied to catalyzing 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxaldehyde, the reaction is carried out for 2 hours at 90 ℃ so as to obtain 58% of conversion rate of 5-hydroxymethylfurfural and 100% of selectivity of 2, 5-furandicarboxaldehyde. Meanwhile, by comparing application examples 1-6, the proportion of the metal, the selection of the auxiliary agent, the dosage and the selection of the ionic liquid have obvious influence on the catalytic activity of the Mn-Fe composite metal catalyst. In addition, as can be seen from comparison of application examples 7 to 11, increasing the temperature of the oxidation reaction is advantageous for increasing the reaction conversion rate, but is not advantageous for selecting the product 2, 5-furandicarboxaldehyde. Application examples 12-21 show that the Mn-Fe composite metal catalyst provided by the invention has good catalytic effect and high catalytic efficiency, and can realize rapid reaction. Therefore, the preparation method provided by the invention has the advantages of obvious advantages, simple operation, low energy consumption, safety and mild reaction conditions, and is suitable for industrial production.
The recycling effect of the Mn-Fe composite metal catalyst is as follows:
the Mn-Fe composite metal catalyst prepared in example 2 was recycled 7 times according to the method of application example 1, and the conversion of 5-hydroxymethylfurfural and the selectivity of 2, 5-furandicarboxaldehyde are shown in Table 3.
TABLE 3 Recycling Effect of Mn-Fe composite Metal catalyst
As can be seen from Table 3, after the Mn-Fe composite metal catalyst is recycled for 6 times, the conversion rate of 5-hydroxymethylfurfural is reduced by only 3%, while the selectivity of 2, 5-furandicarboxaldehyde is kept above 99%, and when the catalyst is recycled for 7 times, the conversion rate of 5-hydroxymethylfurfural and the selectivity of 2, 5-furandicarboxaldehyde can still be kept at good levels. The Mn-Fe composite metal catalyst provided by the invention has good stability and high cyclic utilization rate.
As can be seen from the above examples and application examples, the Mn-Fe composite metal catalyst provided by the invention contains MnCO3Crystal form, Fe2O3The two crystal forms, Mn-Fe, have synergistic effect, and the catalytic efficiency of the catalyst is improved. The Mn-Fe composite metal catalyst provided by the invention is used for catalyzing 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxaldehyde, the conversion rate of 5-hydroxymethylfurfural is up to 58%, the selectivity of 2, 5-furandicarboxaldehyde is up to more than 99%, and the Mn-Fe composite metal catalyst has high cyclic utilization rate and is suitable for industrial production.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The Mn-Fe composite metal catalyst is characterized by comprising MnCO3Crystal modification and Fe2O3A crystalline form; the MnCO3Crystal modification and Fe2O3The molar ratio of the crystal forms is (0.3-3.0): 1; the MnCO3Crystal modification and Fe2O3Crystal cell defects exist in the crystal form;
the preparation method of the Mn-Fe composite metal catalyst comprises the following steps:
mixing an iron source, a manganese source, ionic liquid, a carbonate donor and a solvent to obtain a reaction solution; the carbonate donor comprises one or more of hexamethylenetetramine, sodium carbonate, sodium bicarbonate, urea and hydrazine hydrate;
carrying out hydrothermal reaction on the reaction solution to obtain a Mn-Fe composite metal catalyst precursor;
and calcining the Mn-Fe composite metal catalyst precursor to obtain the Mn-Fe composite metal catalyst.
2. The Mn-Fe composite metal catalyst according to claim 1, wherein the Mn-Fe composite metal catalyst is a brown solid nanoparticle; the MnCO3Crystal modification and Fe2O3All crystal forms are hexagonal crystal systems.
3. A method for preparing an Mn-Fe composite metal catalyst as set forth in claim 1 or 2, comprising the steps of:
mixing an iron source, a manganese source, ionic liquid, a carbonate donor and a solvent to obtain a reaction solution; the carbonate donor comprises one or more of hexamethylenetetramine, sodium carbonate, sodium bicarbonate, urea and hydrazine hydrate;
carrying out hydrothermal reaction on the reaction solution to obtain a Mn-Fe composite metal catalyst precursor;
and calcining the Mn-Fe composite metal catalyst precursor to obtain the Mn-Fe composite metal catalyst.
4. The method of claim 3, wherein the iron source comprises Fe (CH)3COO)3、Fe2(SO4)3、FeCl3And Fe (NO)3)3One or more of the above;
the manganese source comprises Mn (CH)3COO)2、MnSO4、MnCl2And Mn (NO)3)2One or more of them.
5. The method according to claim 3 or 4, wherein the molar ratio of the iron source to the manganese source, calculated as iron and manganese, is 1: (0.2-5).
6. The preparation method of claim 3, wherein the ionic liquid comprises one or more of imidazole chloride salt, imidazole nitrate salt, imidazole borate salt and imidazole acetate salt;
the solvent includes an organic solvent or water.
7. The preparation method according to claim 3 or 6, characterized in that the ratio of the ionic liquid, the carbonate donor and the solvent is (2-10) mmol: (2-30) mmol: (10-40) mL.
8. The preparation method according to claim 3, wherein the hydrothermal reaction is carried out at a temperature of 120 to 180 ℃ for 5 to 15 hours.
9. The preparation method according to claim 3, wherein the calcination temperature is 300 to 500 ℃ and the calcination time is 3 to 6 hours.
10. The Mn-Fe composite metal catalyst according to any one of claims 1 to 2 or the Mn-Fe composite metal catalyst prepared by the preparation method according to any one of claims 3 to 9 is applied to the reaction of catalyzing 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxaldehyde.
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