CN114011471B - MnCO 3 Modified catalyst @ ZIF-8, preparation method and application - Google Patents

MnCO 3 Modified catalyst @ ZIF-8, preparation method and application Download PDF

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CN114011471B
CN114011471B CN202111451748.XA CN202111451748A CN114011471B CN 114011471 B CN114011471 B CN 114011471B CN 202111451748 A CN202111451748 A CN 202111451748A CN 114011471 B CN114011471 B CN 114011471B
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CN114011471A (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 a MnCO 3 Modified catalyst @ ZIF-8, preparation method and application thereof, wherein the method comprises the following steps: 1) Slowly pouring a zinc ion source solution into an 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 solution 3 into a reaction kettle for solvothermal reaction to obtain MnCO 3 Modified catalyst precursor @ ZIF-8; 5) Washing, drying and roasting the catalyst precursor to obtain MnCO 3 Modified catalyst @ ZIF-8. 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.

Description

MnCO 3 Modified catalyst @ ZIF-8, preparation method and application
Technical Field
The invention relates to a modified catalyst, in particular to a MnCO 3 Modified catalyst @ ZIF-8, preparation method and application thereof.
Background
2, 5-furan dicarboxaldehyde 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 almost completely depends on the oxidation of 5-hydroxymethylfurfural. The 5-hydroxymethyl furfural 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-hydroxymethyl furfural molecule has hydroxyl, the reaction direction is difficult to control; the aldehyde group is too active and is easy to be excessively oxidized to generate 2, 5-furandicarboxylic acid, so that the problems of low yield and low selectivity of the 2, 5-furandicarboxaldehyde in the oxidation reaction of 5-hydroxymethylfurfural in the prior art are serious. The development of new catalyst systems to increase the yield and selectivity of 2, 5-furandicarboxaldehyde is an important research direction.
The existing catalyst systems for the oxidation reaction of 5-hydroxymethylfurfural are mainly divided into two main types, namely noble metal catalysts and non-noble metal catalysts. Noble metal catalysts generally have better catalytic performance, for example, chinese patent CN104277016A discloses a supported nano gold catalyst which can realize 88% of oxidation conversion rate of 5-hydroxymethylfurfural and 98% of selectivity of 2, 5-furan dicarboxaldehyde. However, the problems of complex preparation process, poor stability, high recycling difficulty, high price and the like of the noble metal catalyst become pain points for restricting the industrialized application of the noble metal catalyst.
The non-noble metal catalyst mainly comprises a non-metal catalyst and a transition metal catalyst. Nonmetallic catalysts have been increasingly abandoned due to their poor catalytic performance. The transition metal catalyst has relatively low price, can show excellent catalytic activity in a plurality of reaction processes, and especially can be used for preparing 2, 5-furan dicarboxaldehyde by oxidizing 5-hydroxymethylfurfural. However, the patent reports on transition metal catalysts are very rare, and Chinese patent CN112851605A discloses that a four-component aluminum-based compound is used for the reaction system to obtain a better effect, but the catalyst preparation process is too complex. Chinese patent CN111548330A discloses a CuMn 2 O 4 The preparation method of the spinel catalyst, but the catalyst is used for the oxidation reaction of 5-hydroxymethyl furfural, and depends on the polarity of an organic solvent. Chinese patent CN110452195a discloses a supported copper catalyst, but the catalytic effect is poor, and the selectivity of 2, 5-furandicarboxaldehyde is less than 70%. In addition, non-noble metals such as manganese, iron-based and the like are often required to have considerable catalytic efficiency under the conditions of high temperature and high pressure (P > 1MPa, T > 120 ℃), and the selectivity of products is regulated by using strong alkali and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides a MnCO 3 Modified catalyst @ ZIF-8, preparation method and application thereof. The invention adopts a one-pot method to prepare MnCO 3 The modified catalyst of @ ZIF-8 has the advantages of simple method and mild preparation process conditions. MnCO provided by the invention 3 The modified ZIF-8 catalyst is applied to the reaction of preparing 2, 5-furaldehyde by oxidizing 5-hydroxymethylfurfural, and can obtain good conversion rate of 5-hydroxymethylfurfural and selectivity of 2, 5-furaldehyde.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
MnCO 3 The preparation method of the modified ZIF-8 catalyst comprises the following steps:
1) Preparing a zinc ion source solution and an imidazole monomer solution respectively, 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 solution 3 into a reaction kettle for solvothermal reaction to obtain MnCO 3 Modified catalyst precursor @ ZIF-8;
5) Washing, drying and roasting the catalyst precursor to finally obtain MnCO 3 Modified catalyst @ ZIF-8.
Further, in the step 1), the 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) 3 COO) 2 、ZnSO 4 、ZnCl 2 And Zn (NO) 3 ) 2 One or more of the following;
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, at room temperature under uniform stirring. The room temperature is preferably 20 to 50 ℃, more preferably 25 to 35 ℃. The stirring rate is preferably 200 to 800rpm, more preferably 450 to 550rpm.
Further, in the step 2), the ratio of the amount 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 zinc ions to manganese ions;
preferably, the source of manganese ions is Mn (CH) 3 COO) 2 、MnSO 4 、MnCl 2 And Mn (NO) 3 ) One or more of the following.
Further, in the step 3), the dosage ratio of the reaction solution 2 to the imidazole ionic liquid to the carbonate donor is 1 (1-25) to 1-60 in terms of the molar ratio of manganese ions to the imidazole ionic liquid to the carbonate donor;
preferably, the imidazole ionic liquid is one or more of imidazole chloride salt, imidazole nitrate, imidazole borate and imidazole acetate, more preferably one or more of 1-butyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole nitrate, 1-ethyl-3-methylimidazole nitrate, 1-butyl-3-methylimidazole acetate and 1-ethyl-3-methylimidazole acetate. According to the invention, the ionic liquid is added to play a role of a template of the ionic liquid, so that MnCO is prepared 3 The particles are more uniformly distributed in the ZIF-8 while the particle size is kept smaller.
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, the carbonate donor is utilized to generate hydrolysis reaction in the solvothermal process to release CO 3 2- React with Mn ions to form MnCO 3 Supported on 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 from the temperature rising 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 4-6h. The apparatus used for carrying out the solvothermal reaction is not particularly limited and may be any apparatus known to those skilled in the art.
Further, in step 5), the firing temperature is 150 to 500 ℃, preferably 250 to 450 ℃, more preferably 300 to 400 ℃, the heating rate from the firing temperature to the firing temperature is 0.5 to 4.0 ℃/min, more preferably 1 to 3 ℃/min, and the firing time is 3 to 6 hours, preferably 4 to 5 hours. The invention is forThe equipment used for the calcination is not particularly limited, and equipment for carrying out the calcination known to those skilled in the art may be used. In the present invention, roasting can promote MnCO 3 The doping synergistic effect with ZIF-8 makes up the defect of insufficient activity of the single transition metal catalyst.
In the preparation method, the solvent in each raw material solution can be one or more of methanol, ethanol, tetrahydrofuran, DMF, isopropanol, n-butanol, dimethyl sulfoxide and water, preferably one or more of methanol, ethanol and water.
The invention also provides MnCO prepared by the method 3 The modified ZIF-8 catalyst has good catalytic efficiency for the reaction of preparing 2, 5-furan dicarboxaldehyde by oxidizing 5-hydroxymethylfurfural, can obtain more than 50% conversion rate and more than 99% selectivity, has good recycling effect, and is suitable for industrial production.
The invention also provides MnCO prepared by the method 3 The modified ZIF-8 catalyst is used for catalyzing the oxidation reaction of 5-hydroxymethylfurfural to generate 2, 5-furan dicarboxaldehyde. The invention relates to the MnCO 3 The method for using the modified ZIF-8 catalyst in catalyzing the reaction of preparing 2, 5-furandicarboxaldehyde by oxidizing 5-hydroxymethylfurfural is not particularly limited, and a method for oxidizing 5-hydroxymethylfurfural, which is well known to those skilled in the art, can be used.
Preferably, the MnCO 3 The dosage of the modified ZIF-8 catalyst in the oxidation reaction is 10-30% of the mass of the 5-hydroxymethylfurfural.
Preferably, the oxidation reaction conditions are: under the oxygen atmosphere, the oxidation reaction is carried out at 75-120 ℃ and 0.6-1.0 MpaG.
The invention has unexpectedly found that MnCO 3 The catalyst has good catalytic synergistic effect with ZIF-8 in oxidizing 5-hydroxymethylfurfural to generate 2, 5-furan dicarboxaldehyde, wherein the ZIF-8 has the characteristic of large specific surface area and is beneficial to active ingredient MnCO 3 The Mn-Zn metal components can obviously improve the catalytic reaction efficiency under the combined action, reduce the reaction condition requirement and is more beneficial to industrialized application. In addition, the present invention further found that due to MnCO 3 In the invention, firstly manganese salt which exists in a solution in an ionic form is added, and then donor components (such as hexamethylenetetramine) which can slowly release carbonate radicals are added after the manganese salt is mixed with synthesis mother solution of a metal organic framework, so that MnCO with more uniform mixing is generated in the reaction process 3 The structure of the @ ZIF-8 catalyst is more beneficial to improving the reaction efficiency of the catalytic reaction. Based on the above research, the invention provides a MnCO 3 Preparation method of modified ZIF-8 catalyst, 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 applied to the oxidation reaction of 5-hydroxymethylfurfural.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
Preparation of MnCO [ example 1 ] 3 Modified catalyst @ ZIF-8
(1) 10mmol ZnCl 2 150mmol of 2-methylimidazole was dissolved in 50mL of methanol, and the solution was stirred at 500rpm until complete dissolution, followed by ZnCl 2 Adding the solution into 2-methylimidazole solution at a speed of 10mL/min to obtain a reaction solution 1;
(2) 6mmol MnCl 2 Dissolving in 50mL of methanol, fully stirring at 500rpm until the mixture is completely dissolved, and adding the mixture into the reaction solution 1 at a speed of 10mL/min to obtain a reaction solution 2;
(3) 25mmol of 1-butyl-3-methylimidazole chloride and 50mmol of hexamethylenetetramine are weighed and added into the reaction liquid 2, and fully stirred and dissolved at the rotating speed of 500rpm to obtain a reaction liquid 3;
(4) Will getTransferring the obtained reaction solution 3 into a reaction kettle, performing solvothermal reaction for 6 hours at 120 ℃, then performing solid-liquid separation on the reaction system, washing the obtained solid material with methanol, and sufficiently drying to obtain MnCO 3 Modified catalyst precursor @ ZIF-8;
(5) Placing the catalyst precursor in a muffle furnace, roasting for 4 hours at 300 ℃ to remove impurities and obtain MnCO 3 Modified catalyst @ ZIF-8, designated MnCO 3 @ZIF-8。
[ examples 2 to 6 ]
Preparation of different MnCO according to substantially the same method as in example 3 Modified catalyst @ ZIF-8, differing only in the reaction conditions and parameters shown in Table 1.
Table 1, different reaction conditions and parameters in the examples
Figure BDA0003386353340000071
Comparative example 1
Directly as commercially available MnCO 3 As an oxidation catalyst.
Comparative example 2
The oxidation catalyst was directly a commercially available ZIF-8 material (Allatin, ZIF-8, 99%).
Preparation of MnO@ZIF-8 modified catalyst
(1) 10mmol ZnCl 2 150mmol of 2-methylimidazole was dissolved in 50mL of methanol, and the solution was stirred at 500rpm until complete dissolution, followed by ZnCl 2 Adding the solution into 2-methylimidazole solution at a speed of 10mL/min to obtain a reaction solution 1;
(2) 6mmol MnCl 2 Dissolving in 50mL of methanol, fully stirring at 500rpm until the mixture is completely dissolved, and adding the mixture into the reaction solution 1 at a speed of 10mL/min to obtain a reaction solution 2;
(3) Transferring the reaction liquid 2 into a reaction kettle, performing solvothermal reaction for 6 hours at 120 ℃, then performing solid-liquid separation on a reaction system, washing the obtained solid material with methanol, and sufficiently drying to obtain a catalyst precursor;
(4) And (3) placing the catalyst precursor in a muffle furnace, roasting for 4 hours at 500 ℃, and removing impurities to obtain the MnO@ZIF-8 modified catalyst.
Preparation of MnCO [ comparative example 4 ] 3 Modified catalyst @ ZIF-8-1
(1) 10mmol ZnCl 2 150mmol of 2-methylimidazole was dissolved in 50mL of methanol, and the solution was stirred at 500rpm until complete dissolution, followed by ZnCl 2 Adding the solution into 2-methylimidazole solution at a speed of 10mL/min to obtain a reaction solution 1;
(2) 6mmol MnCl 2 Dissolving in 50mL of methanol, fully stirring at 500rpm until the mixture is completely dissolved, and adding the mixture into the reaction solution 1 at a 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 the hexamethylenetetramine at the rotating speed of 500rpm to obtain a reaction solution 3;
(4) Transferring the obtained reaction solution 3 into a reaction kettle, performing solvothermal reaction for 6 hours at 120 ℃, then performing solid-liquid separation on the reaction system, washing the obtained solid material with methanol, and sufficiently drying to obtain MnCO 3 Modified catalyst precursor @ ZIF-8-1;
(5) Placing the catalyst precursor in a muffle furnace, roasting for 4 hours at 300 ℃ to remove impurities and obtain MnCO 3 Modified catalyst @ ZIF-8-1.
Comparative example 5 MnCO 3 Modified catalyst @ ZIF-8-2
(1) 10mmol ZnCl 2 150mmol of 2-methylimidazole was dissolved in 50mL of methanol, and the solution was stirred at 500rpm until complete dissolution, followed by ZnCl 2 Adding the solution into 2-methylimidazole solution at a speed of 10mL/min to obtain a reaction solution 1;
(2) 6mmol of commercially available MnCO 3 Adding the mixture into the reaction liquid 1 obtained in the step (1), fully stirring and mixing, transferring the system into a reaction kettle, and carrying out solvothermal reaction for 6h at 120 ℃. The obtained system is subjected to solid-liquid separation, and the obtained solid material is washed by methanolAnd fully drying to obtain MnCO 3 A @ ZIF-8-2 precursor;
(5) Placing the catalyst precursor in a muffle furnace, roasting for 4 hours at 300 ℃ to remove impurities and obtain MnCO 3 Modified catalyst @ ZIF-8-2.
[ comparative example 6 ]
A modified catalyst was prepared in substantially the same manner as in example 1, except that: mnCl in the step (2) 2 Replaced by equimolar amount of Co (NO 3 ) 2 And preparing CoCO 3 Modified catalyst @ ZIF-8.
[ comparative example 7 ]
A modified catalyst was prepared in substantially the same manner as in example 1, except that: mnCl in the step (2) 2 Replaced by equimolar amount of Cu (NO) 3 ) 2 And preparing CuCO 3 Modified catalyst @ ZIF-8.
[ 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 comparative example, 100mg of 5-hydroxymethylfurfural and 10mL of deionized water were mixed and reacted in an oxygen atmosphere of 0.8MPaG at 90℃and 500rpm for 2 hours 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 Properties of the catalysts
Figure BDA0003386353340000091
Figure BDA0003386353340000101
As can be seen from Table 2, the MnCO provided by the present invention 3 Modified catalyst @ ZIF-8The catalyst is applied to the preparation of 2, 5-furaldehyde by catalytic oxidation of 5-hydroxymethylfurfural, can obtain higher conversion rate of 5-hydroxymethylfurfural and selectivity of 2, 5-furaldehyde, and shows good catalytic activity. Meanwhile, as can be seen from comparison of examples 1 to 4, the present invention provides MnCO 3 In the preparation method of the modified ZIF-8 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 1 3 Washing and drying a ZIF-8 sample for multiple times, placing the sample in a muffle furnace, and roasting the sample at 300 ℃ for 4 hours to obtain a recycled catalyst, which is renamed as MnCO 3 @ ZIF-8-R. The obtained MnCO 3 ZIF-8-R was used in a cycle of 6 times according to the method of application example 1, and the product liquid was sampled and analyzed, and the reaction conversion and selectivity in each cycle were as shown in Table 3:
TABLE 3 catalyst MnCO 3 Test of cycle Performance of @ ZIF-8-R
Number of cycles Conversion of 5-hydroxymethylfurfural/% 2, 5-Furandicarboxaldehyde Selectivity/%
1 52 >99
2 51 >99
3 53 >99
4 50 98
5 51 96
6 49 96
As can be seen from application example 2, the MnCO3@ZIF-8 modified catalyst provided by the invention has good stability, and can realize active regeneration through simple washing and roasting.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.

Claims (17)

1. MnCO 3 The preparation method of the modified ZIF-8 catalyst is characterized by comprising the following steps:
1) Preparing a zinc ion source solution and an imidazole monomer solution respectively, 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) Will beTransferring the reaction solution 3 into a reaction kettle for solvothermal reaction to obtain MnCO 3 Modified catalyst precursor @ ZIF-8;
5) Washing, drying and roasting the catalyst precursor to finally obtain MnCO 3 Modified catalyst @ ZIF-8.
2. MnCO according to claim 1 3 The preparation method of the modified ZIF-8 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 imidazole monomers.
3. MnCO according to claim 2 3 Preparation method of modified ZIF-8 catalyst is characterized in that zinc ion source is Zn (CH) 3 COO) 2 、ZnSO 4 、ZnCl 2 And Zn (NO) 3 ) 2 One or more of the following.
4. MnCO according to claim 2 3 The preparation method of the modified ZIF-8 catalyst is characterized in that imidazole monomer is one or more of 2-methylimidazole, 4-methylimidazole and 2-ethylimidazole.
5. MnCO according to claim 2 3 The preparation method of the modified ZIF-8 catalyst is characterized in that in the step 2), the dosage ratio of the reaction solution 1 to the manganese ion source solution is 1 (0.1-2) in terms of the molar ratio of zinc ions to manganese ions.
6. The MnCO of claim 5 3 Preparation method of modified ZIF-8 catalyst is characterized in that the manganese ion source is Mn (CH) 3 COO) 2 、MnSO 4 、MnCl 2 And Mn (NO) 3 ) 2 One or more of the following.
7. The MnCO of claim 5 3 The preparation method of the modified ZIF-8 catalyst is characterized in that in the step 3), the reaction solution 2 is separated from imidazolesThe dosage ratio of the secondary liquid to the carbonate donor is 1 (1-25) to 1-60 based on the molar ratio of manganese ions to imidazole ionic liquid to carbonate donor.
8. The MnCO of claim 7 3 The preparation method of the modified ZIF-8 catalyst is characterized in that the imidazole ionic liquid is one or more of imidazole chloride, imidazole nitrate, imidazole borate and imidazole acetate.
9. The MnCO of claim 7 3 The preparation method of the modified ZIF-8 catalyst is characterized in that the carbonate donor is one or more of hexamethylenetetramine, sodium carbonate, sodium bicarbonate and urea.
10. MnCO according to any one of claims 1-9 3 The preparation method of the modified ZIF-8 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 ℃ and the reaction time is 2-10 h.
11. MnCO according to claim 10 3 The preparation method of the modified ZIF-8 catalyst is characterized in that in the step 4), the reaction conditions of the solvothermal reaction are as follows: the reaction temperature is 90-160 ℃, and the reaction time is 4-8 h.
12. MnCO according to claim 10 3 The preparation method of the modified ZIF-8 catalyst is characterized in that in the step 4), the reaction conditions of the solvothermal reaction are as follows: the reaction temperature is 90-120 ℃ and the reaction time is 4-6h.
13. MnCO according to any one of claims 1-9 3 The preparation method of the modified ZIF-8 catalyst is characterized in that in the step 5), the roasting temperature is 150-500 ℃ and the roasting time is 3-6 h.
14. MnCO prepared according to the method of any one of claims 1-13 3 Modified catalyst @ ZIF-8.
15. MnCO prepared according to the method of any one of claims 1-13 3 The modified ZIF-8 catalyst is used for catalyzing the oxidation reaction of 5-hydroxymethylfurfural to generate 2, 5-furan dicarboxaldehyde.
16. The use according to claim 15, wherein the MnCO 3 The dosage of the modified ZIF-8 catalyst in the oxidation reaction is 10-30% of the mass of the 5-hydroxymethylfurfural.
17. The use according to claim 16, wherein the oxidation reaction conditions are: under the oxygen atmosphere, the oxidation reaction is carried out at 75-120 ℃ and 0.6-1.0 MpaG.
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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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CN101579631A (en) * 2009-06-22 2009-11-18 上海华谊丙烯酸有限公司 Method for preparing catalyst applied to low-carbon olefin selective oxidization for undersaturation aldehyde preparation

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Publication number Priority date Publication date Assignee Title
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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