CN114011471A - MnCO3@ ZIF-8 modified catalyst, preparation method and application - Google Patents

MnCO3@ ZIF-8 modified catalyst, preparation method and application Download PDF

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CN114011471A
CN114011471A CN202111451748.XA CN202111451748A CN114011471A CN 114011471 A CN114011471 A CN 114011471A CN 202111451748 A CN202111451748 A CN 202111451748A CN 114011471 A CN114011471 A CN 114011471A
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mnco
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CN114011471B (en
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丁磊
刘若楠
郭孝正
康学青
胡展
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Wanhua Chemical Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses MnCO3The @ ZIF-8 modified catalyst comprises the following steps: 1) slowly pouring the zinc ion source solution into the imidazole monomer solution under the stirring condition, and fully mixing to obtain a reaction solution 1; 2) preparing a manganese ion source solution, slowly pouring the manganese ion source solution into the reaction solution 1 under the stirring condition, and fully mixing to obtain a reaction solution 2; 3) slowly adding a certain amount of imidazole ionic liquid and carbonate donor into the reaction liquid 2 under the stirring condition, continuously stirring and fully mixing to obtain a reaction liquid 3; 4) transferring the reaction liquid 3 into a reaction kettle for solvothermal reaction to obtain MnCO3@ ZIF-8 modified catalyst precursor; 5) washing, drying and roasting the catalyst precursor to obtain MnCO3@ ZIF-8 modified catalyst. The invention providesThe preparation method of the modified catalyst is simple to operate, low in energy consumption, safe, mild in reaction condition and suitable for industrial production.

Description

MnCO3@ ZIF-8 modified catalyst, preparation method and application
Technical Field
The invention relates to a modified catalyst, in particular to MnCO3A @ ZIF-8 modified catalyst, a preparation method and application.
Background
2, 5-furan dicarbaldehyde is an important fine chemical and intermediate compound, and has potential application value in multiple fields. In the prior art, the production of 2, 5-furandicarboxaldehyde relies almost entirely on the oxidation of 5-hydroxymethylfurfural. The 5-hydroxymethylfurfural molecule contains three functional groups of aldehyde group, hydroxymethyl and furan ring, and is an intermediate for synthesizing various fine chemicals and furan-based polymers. Because the functional group in the 5-hydroxymethylfurfural molecule has hydroxyl, the difficulty in controlling the reaction direction is high; the aldehyde group is too active and is easily oxidized excessively to generate 2, 5-furandicarboxylic acid, so that the problems of low yield and low selectivity of the 2, 5-furandicarboxaldehyde in the 5-hydroxymethylfurfural oxidation reaction in the prior art are serious. The development of new catalyst systems to improve the yield and selectivity of 2, 5-furandicarboxaldehyde is an important research direction.
The existing catalyst systems for the 5-hydroxymethylfurfural oxidation reaction are mainly divided into two main types, namely noble metal catalysts and non-noble metal catalysts. The noble metal catalyst generally has better catalytic performance, for example, Chinese patent CN104277016A discloses a supported nano gold catalyst, which can realize the oxidation conversion rate of 88 percent of 5-hydroxymethylfurfural and the selectivity of 98 percent of 2, 5-furan diformaldehyde. However, the problems of complicated preparation process, poor stability, high difficulty in recycling, high price and the like of the noble metal catalyst become pain points which restrict the industrial application of the noble metal catalyst.
The non-noble metal catalyst mainly comprises a non-metal catalyst and a transition metal catalyst. Non-metallic catalysts have been gradually abandoned due to their poor catalytic performance. 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, the patent reports of the transition metal catalyst are rare at present, and Chinese patent CN112851605A discloses a four-component aluminum-based compound used in the reaction system to obtain a good effect, but the preparation process of the catalyst is too complex. Chinese patent CN111548330A discloses a CuMn2O4The preparation method of the spinel catalyst, but the catalyst is used for the 5-hydroxymethylfurfural oxidation reaction and depends on the polar action of an organic solvent. Chinese patent CN110452195A disclosesThe supported copper catalyst has poor catalytic effect, and the selectivity of the 2, 5-furan diformaldehyde is less than 70 percent. In addition, at present, non-noble metals such as manganese, iron base and the like often need to have considerable catalytic efficiency under the conditions of high temperature and high pressure (P is more than 1MPa, T is more than 120 ℃), and strong base and the like are used for adjusting the selectivity of products.
Disclosure of Invention
In order to solve the technical problems, the invention provides MnCO3A @ ZIF-8 modified catalyst, a preparation method and application. The invention adopts a one-pot method to prepare MnCO3The @ ZIF-8 modified catalyst has the advantages of simple method and mild preparation process conditions. MnCO provided by the invention3The @ ZIF-8 modified catalyst is applied to the reaction of preparing 2, 5-furan diformaldehyde by oxidizing 5-hydroxymethylfurfural, and can obtain good 5-hydroxymethylfurfural conversion rate and selectivity of 2, 5-furan diformaldehyde.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
MnCO3The preparation method of the @ ZIF-8 modified catalyst comprises the following steps:
1) respectively preparing a zinc ion source solution and an imidazole monomer solution, slowly pouring the zinc ion source solution into the imidazole monomer solution under the stirring condition, and fully mixing to obtain a reaction solution 1;
2) preparing a manganese ion source solution, slowly pouring the manganese ion source solution into the reaction solution 1 under the stirring condition, and fully mixing to obtain a reaction solution 2;
3) slowly adding a certain amount of imidazole ionic liquid and carbonate donor into the reaction liquid 2 under the stirring condition, continuously stirring and fully mixing to obtain a reaction liquid 3;
4) transferring the reaction liquid 3 into a reaction kettle for solvothermal reaction to obtain MnCO3@ ZIF-8 modified catalyst precursor;
5) washing, drying and roasting the catalyst precursor to finally obtain MnCO3@ ZIF-8 modified catalyst.
Further, in the step 1), the dosage ratio of the zinc ion source solution to the imidazole monomer solution is 1 (5-50), preferably 1 (10-40), more preferably 1 (10-20) in terms of the molar ratio of zinc ions to imidazole monomers; preferably, the zinc ion source solution and the imidazole monomer solution are mixed in equal volumes.
Preferably, the zinc ion source is Zn (CH)3COO)2、ZnSO4、ZnCl2And Zn (NO)3)2One or more of;
preferably, the imidazole monomer is one or more of methylimidazole, 2-methylimidazole, 4-methylimidazole and 2-ethylimidazole.
In the present invention, the reaction solution 1 is obtained, specifically, under the conditions of room temperature and uniform stirring. The room temperature is preferably 20 to 50 deg.C, more preferably 25 to 35 deg.C. The stirring rate is preferably 200-800rpm, more preferably 450-550 rpm.
Further, in the step 2), the dosage ratio of the reaction solution 1 to the manganese ion source solution is 1 (0.1-2), preferably 1 (0.2-1.5), more preferably 1 (0.4-0.8) in terms of the molar ratio of the zinc ions to the manganese ions;
preferably, the source of manganese ions is Mn (CH)3COO)2、MnSO4、MnCl2And Mn (NO)3) One or more of (a).
Further, in the step 3), the dosage ratio of the reaction solution 2 to the imidazole ionic liquid and the carbonate donor is 1 (1-25) to (1-60) in terms of the molar ratio of manganese ions to the imidazole ionic liquid and the carbonate donor;
preferably, the imidazole ionic liquid is one or more of imidazole chloride salt, imidazole nitrate salt, imidazole borate salt and imidazole acetate salt, and more preferably one or more of 1-butyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole nitrate salt, 1-ethyl-3-methylimidazole nitrate salt, 1-butyl-3-methylimidazole acetate salt and 1-ethyl-3-methylimidazole acetate salt. The invention makes MnCO play the role of a template of the ionic liquid by adding the ionic liquid3The particles were more uniformly loaded in ZIF-8 while maintaining a smaller particle size.
Preferably, the carbonate donor is one or more of hexamethylenetetramine, sodium carbonate, sodium bicarbonate, urea and hydrazine hydrate,more preferably one or more of hexamethylenetetramine and urea. In the invention, CO is released by hydrolysis reaction of carbonate donor in the solvothermal process3 2-And reacts with Mn ions to form MnCO3Supported on a ZIF-8 carrier.
Further, in the step 4), the reaction conditions of the solvothermal reaction are as follows: the reaction temperature is 70-180 ℃, preferably 90-160 ℃, more preferably 90-120 ℃, the heating rate for heating to the reaction temperature is 1-5 ℃/min, more preferably 2-3 ℃/min, and the reaction time is 2-10h, preferably 4-8h, more preferably 4-6 h. The apparatus used for carrying out the solvothermal reaction is not particularly limited, and those known to those skilled in the art can be used.
Further, in the step 5), the roasting temperature is 150-. The equipment used in the calcination of the present invention is not particularly limited, and equipment known to those skilled in the art for carrying out calcination may be used. In the present invention, calcination can promote MnCO3The doping synergistic effect between the catalyst and ZIF-8 makes up the defect of insufficient activity of a single transition metal catalyst.
In the above preparation method, the solvent in each raw material solution may be one or more selected from methanol, ethanol, tetrahydrofuran, DMF, isopropanol, n-butanol, dimethyl sulfoxide, and water, preferably one or more selected from methanol, ethanol, and water.
The invention also provides MnCO prepared by the method3The @ ZIF-8 modified catalyst has good catalytic efficiency for the reaction of preparing 2, 5-furandicarboxaldehyde by oxidizing 5-hydroxymethylfurfural, can obtain more than 50% of conversion rate and more than 99% of selectivity, has good recycling effect, and is suitable for industrial production.
The invention also provides MnCO prepared by the method3The application of the @ ZIF-8 modified catalyst is used for catalyzing the oxidation reaction of 5-hydroxymethylfurfural to generate 2, 5-furandicarboxaldehyde. The invention is about said MnCO3The application method of the @ ZIF-8 modified catalyst in the reaction of catalyzing the oxidation of 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxaldehyde is not particularly limited, and a 5-hydroxymethylfurfural oxidation method well known to those skilled in the art can be adopted.
Preferably, the MnCO3The dosage of the @ ZIF-8 modified catalyst in the oxidation reaction is 10-30% of the mass of the 5-hydroxymethylfurfural.
Preferably, the oxidation reaction conditions are: carrying out oxidation reaction at 75-120 deg.C and 0.6-1.0MpaG in oxygen atmosphere.
The invention surprisingly found through research that MnCO3Has good catalytic synergistic effect with ZIF-8 in the oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxaldehyde, wherein ZIF-8 not only has the characteristic of large specific surface area, but also is beneficial to the active ingredient MnCO3The dispersion of the catalyst can obviously improve the catalytic reaction efficiency under the combined action of Mn-Zn metal components, reduce the requirements of reaction conditions and be more beneficial to industrial application. In addition, the invention further discovers that the MnCO is generated due to MnCO3In the invention, firstly, manganese salt existing in the form of ions in solution is added and mixed with the synthetic mother liquor of the metal organic framework, and then a donor component (such as hexamethylenetetramine) capable of slowly releasing carbonate is added, so that MnCO which is more uniformly mixed is generated in the reaction process3The structure of the @ ZIF-8 catalyst is more favorable for improving the reaction efficiency of catalytic reaction. Based on the research content, the invention provides MnCO3A preparation method of a @ ZIF-8 modified catalyst, the prepared catalyst and application thereof.
The preparation method of the modified catalyst provided by the invention is simple to operate, low in energy consumption, safe, mild in reaction condition and suitable for industrial production. In addition, the MnCO3@ ZIF-8 modified catalyst provided by the invention has the advantages of high reaction conversion rate and high selectivity when being applied to the oxidation reaction of 5-hydroxymethylfurfural.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
[ example 1 ] preparation of MnCO3@ ZIF-8 modified catalyst
(1) Adding 10mmol of ZnCl2150mmol of 2-methylimidazole are respectively dissolved in 50mL of methanol, fully stirred at the rotating speed of 500rpm until the 2-methylimidazole is completely dissolved, and then ZnCl is added2Adding the solution into a 2-methylimidazole solution at the speed of 10mL/min to obtain a reaction solution 1;
(2) adding 6mmol of MnCl2Dissolving in 50mL of methanol, fully stirring at the rotation speed of 500rpm until the methanol is completely dissolved, and adding the methanol into the reaction solution 1 at the speed of 10mL/min to obtain a reaction solution 2;
(3) weighing 25mmol of 1-butyl-3-methylimidazolium chloride and 50mmol of hexamethylenetetramine, adding into the reaction solution 2, and fully stirring and dissolving at the rotation speed of 500rpm to obtain a reaction solution 3;
(4) transferring the obtained reaction liquid 3 into a reaction kettle, carrying out solvothermal reaction for 6h at 120 ℃, then carrying out solid-liquid separation on the reaction system, washing the obtained solid material with methanol and fully drying to obtain MnCO3@ ZIF-8 modified catalyst precursor;
(5) placing the catalyst precursor in a muffle furnace, roasting for 4h at 300 ℃, removing impurities, and obtaining MnCO3@ ZIF-8 modified catalyst, denoted as MnCO3@ZIF-8。
[ examples 2 to 6 ]
Preparing different MnCO according to the substantially same method as the example3The @ ZIF-8 modified catalysts were different only in the reaction conditions and parameters shown in Table 1.
TABLE 1 reaction conditions and parameters different in the examples
Figure BDA0003386353340000071
Comparative example 1
Directly as commercial MnCO3As oxidation catalysts。
Comparative example 2
The commercial ZIF-8 material (Aladdin, ZIF-8, 99%) is directly used as an oxidation catalyst.
[ COMPARATIVE EXAMPLE 3 ] preparation of MnO @ ZIF-8 modified catalyst
(1) Adding 10mmol of ZnCl2150mmol of 2-methylimidazole are respectively dissolved in 50mL of methanol, fully stirred at the rotating speed of 500rpm until the 2-methylimidazole is completely dissolved, and then ZnCl is added2Adding the solution into a 2-methylimidazole solution at the speed of 10mL/min to obtain a reaction solution 1;
(2) adding 6mmol of MnCl2Dissolving in 50mL of methanol, fully stirring at the rotation speed of 500rpm until the methanol is completely dissolved, and adding the methanol into the reaction solution 1 at the speed of 10mL/min to obtain a reaction solution 2;
(3) transferring the reaction solution 2 into a reaction kettle, carrying out solvothermal reaction for 6h at 120 ℃, then carrying out solid-liquid separation on a reaction system, washing the obtained solid material with methanol, and fully drying to obtain a catalyst precursor;
(4) and (3) placing the catalyst precursor in a muffle furnace, roasting for 4h at 500 ℃, and removing impurities to obtain the MnO @ ZIF-8 modified catalyst.
Comparative example 4 preparation of MnCO3@ ZIF-8-1 modified catalyst
(1) Adding 10mmol of ZnCl2150mmol of 2-methylimidazole are respectively dissolved in 50mL of methanol, fully stirred at the rotating speed of 500rpm until the 2-methylimidazole is completely dissolved, and then ZnCl is added2Adding the solution into a 2-methylimidazole solution at the speed of 10mL/min to obtain a reaction solution 1;
(2) adding 6mmol of MnCl2Dissolving in 50mL of methanol, fully stirring at the rotation speed of 500rpm until the methanol is completely dissolved, and adding the methanol into the reaction solution 1 at the speed of 10mL/min to obtain a reaction solution 2;
(3) weighing 50mmol of hexamethylenetetramine, adding the hexamethylenetetramine into the reaction solution 2, and fully stirring and dissolving at the rotation speed of 500rpm to obtain a reaction solution 3;
(4) transferring the obtained reaction liquid 3 into a reaction kettle, carrying out solvothermal reaction for 6h at 120 ℃, then carrying out solid-liquid separation on the reaction system, and reactingWashing the obtained solid material with methanol and fully drying to obtain MnCO3@ ZIF-8-1 modifying a catalyst precursor;
(5) placing the catalyst precursor in a muffle furnace, roasting for 4h at 300 ℃, removing impurities, and obtaining MnCO3@ ZIF-8-1 modified catalyst.
[ COMPARATIVE EXAMPLE 5 ] MnCO3@ ZIF-8-2 modified catalyst
(1) Adding 10mmol of ZnCl2150mmol of 2-methylimidazole are respectively dissolved in 50mL of methanol, fully stirred at the rotating speed of 500rpm until the 2-methylimidazole is completely dissolved, and then ZnCl is added2Adding the solution into a 2-methylimidazole solution at the speed of 10mL/min to obtain a reaction solution 1;
(2) 6mmol of commercial MnCO3Adding the mixture into the reaction solution 1 obtained in the step (1), fully stirring and mixing the mixture, transferring the system into a reaction kettle, and carrying out solvothermal reaction for 6 hours at the temperature of 120 ℃. Carrying out solid-liquid separation on the obtained system, washing the obtained solid material by using methanol and fully drying to obtain MnCO3@ ZIF-8-2 precursor;
(5) placing the catalyst precursor in a muffle furnace, roasting for 4h at 300 ℃, removing impurities, and obtaining MnCO3@ ZIF-8-2 modified catalyst.
Comparative example 6
A modified catalyst was prepared in substantially the same manner as in example 1, except that: MnCl in the step (2)2By substitution with equimolar amounts of Co (NO)3)2And preparing to obtain CoCO3@ ZIF-8 modified catalyst.
Comparative example 7
A modified catalyst was prepared in substantially the same manner as in example 1, except that: MnCl in the step (2)2Replacement with equimolar amounts of Cu (NO)3)2And preparing to obtain CuCO3@ ZIF-8 modified catalyst.
[ application example 1 ]
The catalysts prepared in each example and comparative example are respectively used in a reaction system for preparing 2, 5-furan dicarboxaldehyde by oxidizing 5-hydroxymethylfurfural, and the specific method is as follows:
25mg of the catalyst prepared in the example or the comparative example, 100mg of 5-hydroxymethylfurfural and 10mL of deionized water were mixed, and stirred and reacted at 90 ℃ and 500rpm for 2 hours in an oxygen atmosphere of 0.8MPaG to obtain a product liquid, which was sampled and analyzed, and the catalyst was recovered by filtration.
The catalytic effects of the catalysts in each example and comparative example are shown in table 2:
TABLE 2 catalytic performance of the catalysts
Figure BDA0003386353340000091
Figure BDA0003386353340000101
As can be seen from Table 2, the MnCO provided by the present invention3The @ ZIF-8 modified catalyst is applied to the preparation of 2, 5-furandicarboxaldehyde by catalytic oxidation of 5-hydroxymethylfurfural, can obtain higher conversion rate of 5-hydroxymethylfurfural and selectivity of 2, 5-furandicarboxaldehyde, and shows good catalytic activity. Meanwhile, it can be seen from comparative examples 1 to 4 that MnCO according to the present invention3In the preparation method of the @ ZIF-8 modified catalyst, hexamethylenetetramine is selected as a carbonate donor, so that the catalyst has more excellent catalytic performance.
[ application example 2 ]
MnCO recovered in application example 13The @ ZIF-8 sample is washed and dried for multiple times and then is placed in a muffle furnace to be roasted for 4 hours at the temperature of 300 ℃ to obtain a recycled catalyst which is renamed to be MnCO3@ ZIF-8-R. The obtained MnCO3@ ZIF-8-R was used in cycles of 6 according to the method of application example 1, and the product liquid was sampled and analyzed, and the conversion and selectivity of the reaction in each cycle are shown in Table 3:
TABLE 3 catalyst MnCO3@ ZIF-8-R cycle performance test
Number of cycles 5-hydroxymethylfurfural conversion/%) 2, 5-Furan-dimethyl aldehyde Selectivity/%)
1 52 >99
2 51 >99
3 53 >99
4 50 98
5 51 96
6 49 96
As can be seen from the application example 2, the MnCO3@ ZIF-8 modified catalyst provided by the invention has good stability, and can realize activity regeneration through simple washing and roasting.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.

Claims (10)

1. MnCO3The preparation method of the @ ZIF-8 modified catalyst is characterized by comprising the following steps of:
1) respectively preparing a zinc ion source solution and an imidazole monomer solution, slowly pouring the zinc ion source solution into the imidazole monomer solution under the stirring condition, and fully mixing to obtain a reaction solution 1;
2) preparing a manganese ion source solution, slowly pouring the manganese ion source solution into the reaction solution 1 under the stirring condition, and fully mixing to obtain a reaction solution 2;
3) slowly adding a certain amount of imidazole ionic liquid and carbonate donor into the reaction liquid 2 under the stirring condition, continuously stirring and fully mixing to obtain a reaction liquid 3;
4) transferring the reaction liquid 3 into a reaction kettle for solvothermal reaction to obtain MnCO3@ ZIF-8 modified catalyst precursor;
5) washing, drying and roasting the catalyst precursor to finally obtain MnCO3@ ZIF-8 modified catalyst.
2. The MnCO of claim 13The preparation method of the @ ZIF-8 modified catalyst is characterized in that in the step 1), the dosage ratio of the zinc ion source solution to the imidazole monomer solution is 1 (5-50) in terms of the molar ratio of zinc ions to the imidazole monomer;
preferably, the zinc ion source is Zn (CH)3COO)2、ZnSO4、ZnCl2And Zn (NO)3)2One or more of;
preferably, the imidazole monomer is one or more of methylimidazole, 2-methylimidazole, 4-methylimidazole and 2-ethylimidazole.
3. The MnCO of claim 23The preparation method of the @ ZIF-8 modified catalyst is characterized in that in the step 2), the reaction solution 1The dosage ratio of the zinc ion source solution to the manganese ion source solution is 1 (0.1-2) in terms of the molar ratio of the zinc ions to the manganese ions;
preferably, the source of manganese ions is Mn (CH)3COO)2、MnSO4、MnCl2And Mn (NO)3) One or more of (a).
4. The MnCO of claim 33The preparation method of the @ ZIF-8 modified catalyst is characterized in that in the step 3), the dosage ratio of the reaction liquid 2 to the imidazole ionic liquid and the carbonate donor is 1 (1-25) to 1-60 in terms of the molar ratio of manganese ions to the imidazole ionic liquid and the carbonate donor;
preferably, the imidazole ionic liquid is one or more of imidazole chloride salt, imidazole nitrate, imidazole borate and imidazole acetate;
preferably, the carbonate donor is one or more of hexamethylenetetramine, sodium carbonate, sodium bicarbonate, urea and hydrazine hydrate.
5. MnCO according to any one of claims 1 to 43The preparation method of the @ ZIF-8 modified catalyst is characterized in that in the step 4), the reaction conditions of the solvothermal reaction are as follows: the reaction temperature is 70-180 ℃, preferably 90-160 ℃, more preferably 90-120 ℃, and the reaction time is 2-10h, preferably 4-8h, more preferably 4-6 h.
6. MnCO according to any one of claims 1 to 43The preparation method of the @ ZIF-8 modified catalyst is characterized in that in the step 5), the roasting temperature is 150 ℃ and 500 ℃, and the roasting time is 3-6 h.
7. MnCO produced by the method according to any one of claims 1 to 63@ ZIF-8 modified catalyst.
8. MnCO produced by the method according to any one of claims 1 to 63The application of the @ ZIF-8 modified catalyst is characterized in that the catalyst is used for catalyzing the oxidation reaction of 5-hydroxymethylfurfural to generate 2,5-Furan dicarbaldehyde.
9. Use according to claim 8, wherein said MnCO is3The dosage of the @ ZIF-8 modified catalyst in the oxidation reaction is 10-30% of the mass of the 5-hydroxymethylfurfural.
10. Use according to claim 9, wherein the oxidation reaction conditions are: carrying out oxidation reaction at 75-120 deg.C and 0.6-1.0MpaG in oxygen atmosphere.
CN202111451748.XA 2021-12-01 2021-12-01 MnCO 3 Modified catalyst @ ZIF-8, preparation method and application Active CN114011471B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100323881A1 (en) * 2009-06-22 2010-12-23 Shanghai Huayi Acrylic Acid Co., Ltd. Preparation process of a catalyst used for gas phase oxidation of light alkenes to unsaturated aldehydes
JP2013231033A (en) * 2013-05-29 2013-11-14 Momentive Performance Materials Inc Organically-modified trisiloxane surfactant having hydrolysis resistance
CN106887606A (en) * 2017-02-23 2017-06-23 广西大学 One kind " peach-shaped " Mn2 O3The preparation method of/C particles
CN108380246A (en) * 2018-01-23 2018-08-10 湖北大学 A kind of Cu（0）The preparation method and applications of@ZIF-8 catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100323881A1 (en) * 2009-06-22 2010-12-23 Shanghai Huayi Acrylic Acid Co., Ltd. Preparation process of a catalyst used for gas phase oxidation of light alkenes to unsaturated aldehydes
JP2013231033A (en) * 2013-05-29 2013-11-14 Momentive Performance Materials Inc Organically-modified trisiloxane surfactant having hydrolysis resistance
CN106887606A (en) * 2017-02-23 2017-06-23 广西大学 One kind " peach-shaped " Mn2 O3The preparation method of/C particles
CN108380246A (en) * 2018-01-23 2018-08-10 湖北大学 A kind of Cu（0）The preparation method and applications of@ZIF-8 catalyst

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