CN108993581B - Supported metal polyoxometallate hybrid catalyst and preparation method and application thereof - Google Patents

Supported metal polyoxometallate hybrid catalyst and preparation method and application thereof Download PDF

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CN108993581B
CN108993581B CN201810769251.4A CN201810769251A CN108993581B CN 108993581 B CN108993581 B CN 108993581B CN 201810769251 A CN201810769251 A CN 201810769251A CN 108993581 B CN108993581 B CN 108993581B
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pmo
bmo
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CN108993581A (en
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朱明乔
丁智俊
乌莎贾米尔
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Zhejiang University ZJU
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

Abstract

The invention discloses a supported metal polyoxometalate hybridA catalyst, a preparation method and application thereof. The invention loads nano gold and bismuth on a modified ZSM-5 molecular sieve to prepare a catalyst precursor and prepare a metal polyoxometallate PMo11And BMo11Then the two metal polyhydrochloride salts are loaded on the catalyst precursor by an immersion mixing method to form the loaded metal polyoxometalate hybrid catalyst 1 percent Au-0.5 percent Bi/PMo11+BMo11ZSM-5, wherein the modified ZSM-5 molecular sieve is used as the carrier of the catalyst, Au, Bi and polyoxometallate BMo11And PMo11As the main active component of the catalyst, the loading efficiency is high, and the preparation method is simple. The catalyst provided by the invention has the characteristics of high activity and good selectivity for preparing cyclohexene oxide by molecular oxygen epoxidation of cyclohexene under the solvent-free condition, and meets the requirements of industrial green production.

Description

Supported metal polyoxometallate hybrid catalyst and preparation method and application thereof
Technical Field
The invention relates to a supported metal polyoxometalate hybrid catalyst, a preparation method and application thereof.
Background
Cyclohexene is a very important chemical raw material in industry, and a derivative generated through a series of reactions can be used as an intermediate for synthesizing fine chemical products such as medical and agricultural chemicals, spices and the like, but the cyclohexene oxidation reaction cannot achieve high selectivity due to double bonds and the existence of α -H in the molecular formula, so that the industrial application is difficult to carry out.
The heterogeneous catalyst comprises a metal oxide catalyst, a molecular sieve catalyst, a supported catalyst and the like, for selective oxidation reaction, the nano-gold supported catalyst is one of the hotter catalysts under study, and since the Nature journal (Mathew d. hughes. Tunable gold catalysts for selective hydrogenation units.2005) in 2005 reported that the nano-gold supported catalyst has excellent olefin epoxidation activity, more and more researchers begin to pay attention to the nano-gold catalyst and the catalytic activity thereof in various olefin epoxidation reactions, and meanwhile, the nano-gold is widely applied in various industries. The present nanogold catalyst has been applied to the oxidation of cyclohexane to generate KA oil (mixture of cyclohexanone and cyclohexanol), propylene epoxidation, styrene epoxidation, selective cyclohexene oxidation and the like, and the application in cyclohexene epoxidation is also included. The carrier for loading the nano-gold is generally a porous material, and comprises activated carbon, alumina, a molecular sieve and the like, commonly used molecular sieves comprise a ZSM-5 molecular sieve, an SBA-15 molecular sieve, an MCM-41 molecular sieve and the like, and a metalloporphyrin, a metallophthalocyanine and other metal organic framework structures are adopted as the carrier in literature reports. The single nano-gold load sometimes cannot achieve the required oxidation effect, and the situation that the conversion rate or the selectivity is not ideal occurs, at the moment, auxiliary metal can be added for hybridization load to improve the catalytic capability of the catalyst, which is also one of the commonly used methods for preparing the catalyst.
The metal polyoxometalate catalyst has good application in the oxidation reaction of olefin in recent years, and is a polyoxometalate metal complex formed by the spatial combination of a ligand and a heteroatom in an oxygen atom bridge mode. According to the difference of the coordination atoms and the hetero atoms, the phosphorus-molybdenum polyoxometalates, phosphorus-tungsten polyoxometalates, boron-tungsten polyoxometalates, silicon-tungsten polyoxometalates and the like are classified. The metal polyoxometalates have the advantages of simple preparation, strong catalytic activity and the like, and are particularly applied to the epoxidation reaction of olefin. For example, the urdine and the like in the research group prepare a novel boron tungsten polyoxometalate quaternary ammonium salt catalyst (urdine, cyclohexene epoxidation reaction in a novel tungsten-based catalyst and 2015), cyclohexene can be epoxidized under mild oxidation conditions and with hydrogen peroxide as an oxygen source, the epoxidation selectivity is 65-70%, and the conversion rate is over 50%. It can be seen that the metal polyoxometalates have great potential in the selective oxidation of cyclohexene. Although the metal polyoxate catalyst has the advantages, the catalyst has the defects of difficult recovery and low recycling rate, so that the metal polyoxate catalyst is researched to be loaded on activated carbon, alumina or a molecular sieve to improve the recycling rate. For example, CN201610030368.1 discloses a supported tungsten-gallium polyoxometallate catalyst, which is used for the epoxidation of molecular cyclohexene oxide,reacting for 24 hours under mild conditions, adding 0.06g of catalyst into the mixture, corresponding to 2g of substrate, and reaching a conversion rate of 62.02 percent and an Epoxidation selectivity of 59.13 percent, and also researching the phosphorus-molybdenum Polyoxometalate by using a dipping load method to prepare the catalyst 1 percent Au/PMo (manganese phosphate/phosphorus oxide) by using a method of dipping load11The SBA-15 is used for the epoxidation of cyclohexene by molecular oxygen catalysis, and the conversion rate of 48.17 percent and the epoxidation selectivity of 35.92 percent can be achieved by reacting for 24 hours under the solvent-free and mild conditions.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a supported metal polyoxometalate hybrid catalyst, and a preparation method and application thereof.
The epoxidation reaction which is researched at present mostly adopts oxygen sources such as hydrogen peroxide, tert-butyl hydroperoxide (TBHP) and the like, the oxygen sources have excellent effects in the epoxidation reaction, but have certain defects in the aspects of cost, safety, environmental protection and separation.
The invention tries to combine nano-gold and polyoxometallate as a catalytic activity center, load the catalytic activity center on a modified ZSM-5 molecular sieve, and add an auxiliary metal element Bi to improve the catalytic activity, thereby preparing the supported polyoxometallate hybrid catalyst Au-Bi/PMo11+BMo11the/ZSM-5 is used for cyclohexene molecular oxygen epoxidation reaction, the characterization of the catalyst is carried out, and the influence of different reaction conditions on the performance of the catalyst is examined. No report in the literature that nanogold, an auxiliary metal Bi and a metal polyoxometalate are combined to be used as a catalytic active center, nor are two kinds of metal polyoxometalates BMo11And PMo11Case of mixed use, catalysis of molecular oxygen epoxidation with nano-gold supported catalyst aloneCyclohexene oxide can not achieve a good epoxidation effect, and the epoxidation selectivity is not ideal; the metal polyoxometalates catalyst has the defects of difficult recovery and low recycling rate. According to the invention, after the two are combined and the auxiliary metal is added to hybridize and load on the ZSM-5 molecular sieve, not only can the catalytic reaction activity be improved, but also the repeated utilization rate is obviously improved, and the technical effects are better when the two are combined and used respectively. The invention adopts an impregnation mixing method to load the metal polyoxometalates, thus not only improving the catalytic activity of the catalyst, but also solving the problem of environmental cost caused by metal ion loss in the preparation process.
A supported metal polyoxometallate hybrid catalyst is prepared from Au, Bi and PMo11、BMo11And ZSM-5 molecular sieve, wherein Au, Bi and metal polyoxometallate BMo11And PMo11The catalyst had an apparent mass percentage of Au of 1.0%, an apparent mass percentage of Bi of 0.5%, and BMo as the main active components11And PMo11The weight percentage of the catalyst is 3.33 percent, ZSM-5 is a modified ZSM-5 molecular sieve which is used as a catalyst carrier, the modified ZSM-5 molecular sieve is the ZSM-5 molecular sieve treated by roasting and NaOH solution, Au metal oxide or the mixture of the two, and Bi is Bi metal, Bi metal oxide or the mixture of the two.
The metal polyoxometalates comprise phosphomolybdic polyoxometalates PMo11And boron molybdenum polyoxometalates BMo11The polyoxo cluster metal complex has a steric structure, wherein Mo is taken as a ligand atom, B, P is taken as a heteroatom, and oxygen atoms are bridged together.
A preparation method of the supported metal polyoxometalate hybrid catalyst comprises the following steps:
1) dipping and reducing: preparing a polyvinyl alcohol solution, adding a chloroauric acid solution and a bismuth nitrate solution, stirring for 30min, adding a modified ZSM-5 molecular sieve, stirring for 30min, raising the temperature to 80 ℃, adding urea, stirring for 5h, adding a formaldehyde solution for reduction for 2h, cooling, filtering, washing, and drying in an oven at 90 ℃ to obtain Au-Bi/ZSM-5 serving as a catalyst precursor;
2) dipping and mixing: adding the catalyst precursor obtained in the step 1) into a single-mouth bottle, and adding the metal polyoxometallate PMo11And BMo11Adding deionized water, stirring and dispersing at 50-60 deg.C until water is evaporated to dryness, and oven drying at 90 deg.C to obtain solid Au-Bi/PMo11+BMo11a/ZSM-5 catalyst.
The supported metal polyoxometalate hybrid catalyst is used for selectively epoxidizing cyclohexene to cyclohexene oxide under the solvent-free condition by molecular oxygen.
Compared with the prior art, the invention has the advantages that:
1) the green oxygen source molecular oxygen is adopted, so that the atom utilization rate is higher, and compared with hydrogen peroxide adopted in the prior art, the method is more green and safe, and is more favorable for realizing future industrial production;
2) the reaction condition is mild;
3) a large amount of solvent and co-reducing agent are not added, so that the method is more green and environment-friendly, is easier to separate and reduces the separation cost;
4) the reaction time is shorter than that of the catalyst mentioned in CN201610030368.1, and the method is more beneficial to realizing continuity and industrialization by adopting the current advanced technology microreactor; the catalyst is less in use amount and relatively lower in cost;
5) the carrier adopts a common ZSM-5 molecular sieve, the cost is lower (the price of the ZSM-5 molecular sieve is 0.3-1 yuan/g, and the price of the SBA-15 molecular sieve is 25-40 yuan/g) compared with that of a paper (Umsa Jameel, 2017), and the catalyst is prepared by adopting an impregnation mixing method, so that the epoxidation selectivity is greatly improved, the aim of replacing a high-cost carrier with a cheap carrier is fulfilled, the metal ion loss in the preparation process is reduced, the discharge of a part of sewage containing metal ions is reduced, and the industrialization is more favorably realized;
6) the conversion rate and selectivity of cyclohexene epoxidation are better.
Drawings
FIG. 1 is a PMo metal polyoxometalate11And BMo11XRD pattern of
FIG. 2 is 1% Au-0.5% Bi/PMo11+BMo11XRD pattern of/ZSM-5;
FIG. 3 is 1% Au-0.5% Bi/PMo11+BMo11TEM spectrum of/ZSM-5;
FIG. 4 is 1% Au-0.5% Bi/PMo11+BMo11SEM picture of/ZSM-5;
FIG. 5 is 1% Au-0.5% Bi/PMo11+BMo11EDS spectrum of/ZSM-5.
Detailed Description
The invention is further illustrated below with reference to the figures and examples.
Example 1
Preparation of the supported metal polyoxometalate hybrid catalyst:
1) modification of ZSM-5 molecular sieves: weighing a certain mass of ZSM-5 molecular sieve (white powder), placing the ZSM-5 molecular sieve (white powder) into a 400 ℃ muffle furnace, roasting for 4h to obtain a roasted ZSM-5 carrier (yellow powder), dissolving 1.2g of sodium hydroxide in 75ml of water (the concentration is 0.4 mol/L), heating to 70 ℃, adding 1g of the roasted ZSM-5 carrier, stirring for 1h, immediately taking out the mixture, placing the mixture into an ice bath for cooling to prevent the mixture from continuing to react, performing suction filtration after 15min, washing for 2-3 times by using deionized water, and drying at 70 ℃ to obtain the modified ZSM-5 molecular sieve;
2) loading of Au and Bi (immersion reduction method): weighing 0.15g of polyvinyl alcohol as a dispersing agent, adding 15ml of water, preheating at about 80 ℃ until the polyvinyl alcohol is completely dissolved, cooling, 0.53mL of a chloroauric acid tetrahydrate solution having a concentration of 1g/50mL and 0.29mL of a bismuth nitrate solution having a concentration of 1g/50mL were added (the amounts of the two solutions added were determined depending on the amount of the supported, in the case of 1% Au and 0.5% Bi), stirring at 30 deg.C for 30min, adding 0.5g of ZSM-5 molecular sieve obtained in step 1), stirring for 30min, adding 0.45g of urea as pH regulator, raising the temperature to 80 ℃, stirring for 5h, adding 30mL of formaldehyde solution for reduction for 2h, finally cooling and filtering, washing with deionized water for 2-3 times, and drying in an oven at 90 deg.C for 12h to obtain Au-Bi/ZSM-5 as catalyst precursor, i.e. 1% Au-0.5% Bi/ZSM-5 in this case.
3) Preparation of metal polyoxometalates:
A. weighing 5.32g of sodium molybdate dihydrate and 0.28g of anhydrous disodium hydrogen phosphate, dissolving in 60ml of deionized water, heating to 70-90 ℃, dropwise adding concentrated nitric acid while stirring, adjusting the pH to about 4.3, continuously heating until more than half of the volume of water is evaporated, adding 50-60ml of acetone for cooling and washing, generating a large amount of light yellow solid, performing suction filtration, continuously washing with acetone until the yellow solid disappears, obtaining a white solid, drying the salt obtained by suction filtration and washing in the air at normal temperature for 24 hours, and obtaining the needed metal polyoxometalate PMo11。
B. 7.33g of sodium molybdate and 0.666g of boric acid were weighed out and dissolved in 17.0mL of boiling water, 2.5mL of a 10mol/L hydrochloric acid solution was added dropwise, stirred until the precipitate was dissolved, adjusted to pH 6, the solution was boiled for 1 hour, then stored at 4 ℃ for 24 hours, and the solid was isolated by suction filtration. To the resulting clear solution, 3.3g of KCl was added for salting out, and the precipitate was separated by suction filtration. The resulting solid was dissolved in 33.5mL warm water, salted out with 3.3g KCl, filtered with suction and dried at 120 ℃ for 5h to give BMo11。
4) Loading of metal polyoxometalates (dip mixing method): 0.5g of the catalyst precursor obtained in the step 2) was weighed and added to the polyoxometalate PMo obtained in the step 3) above11And BMo11The mass is 0.0167g (the total load is 6.67 percent in case of 1: 1) in proportion), 15mL of deionized water is added, the mixture is stirred at 50-60 ℃ until the water is evaporated to dryness (about 36 h), and the mixture is placed into a 90 ℃ oven to be dried for 12h to obtain the supported metal polyoxate hybrid catalyst Au-Bi/PMo11+BMo11ZSM-5. The catalyst obtained in this case was 1% Au-0.5% Bi/PMo11+BMo11The XRD of the/ZSM-5 is shown in figure 2, the TEM is shown in figure 3, the SEM is shown in figure 4, and the EDS is shown in figure 5.
The product in the evaluation of the catalyst activity was analyzed by gas chromatography using a capillary column SE-54 (30 m.times.0.32 mm. times.0.5 μm) and a Flame Ionization Detector (FID). N-hexane was used as internal standard.
The method is characterized in that molecular oxygen is used as an oxidant, the reaction is carried out under the conditions of 80 ℃, 0.8MPa, 18h and solvent-free reaction, the cyclohexene conversion rate is 35.94% and the cyclohexene oxide selectivity is 3.39% under the condition of no catalyst; cyclohexene epoxidation experiments were carried out at 80 ℃ under 0.8MPa for 18h with 3 drops of TBHP solution and without solvent, resulting in a cyclohexene conversion of 35.89% and an cyclohexene oxide selectivity of 2.46%. From the above experimental results, it was revealed that in the case where no catalyst was added, although cyclohexene could be oxidized by molecular oxygen, the epoxidation effect was poor, and the selectivity and yield of cyclohexene oxide were very low, so that the addition of a catalyst was indispensable for the reaction of cyclohexene oxidation by molecular oxygen. Most of reports on high catalytic effect of the cyclohexene epoxidation catalyst currently use hydrogen peroxide, tert-butyl hydroperoxide, peracetic acid and the like as oxygen sources, but the oxygen sources are not green enough relative to molecular oxygen and have low atom utilization rate.
Example 2
And (4) evaluating the activity of the catalyst. 1% Au-0.5% Bi/PMo11+BMo110.02 g of/ZSM-5 catalyst was placed in a PTFE-lined autoclave (volume = 20mL) for reaction, 2.0g of cyclohexene was added, 3 drops of TBHP were added, and molecular oxygen as an oxygen source was stirred at 80 ℃ for 18 hours under a pressure of 0.8 MPa. The conversion rate of cyclohexene oxidation was 41.42%, the selectivity for cyclohexene oxide was 38.52%, the selectivity for cyclohexenol was 11.36%, the selectivity for cyclohexenone was 22.49%, and the selectivity for orthocyclohexanediol was 27.63%.
Example 3
And (4) evaluating the activity of the catalyst. 1% Au/PMo110.02 g of/ZSM-5 catalyst was used for the reaction. 2.0g of cyclohexene was added, and 3 drops of TBHP were added, and molecular oxygen as an oxygen source was stirred at 80 ℃ under a pressure of 0.8MPa for reaction for 18 hours. The conversion rate of cyclohexene oxidation was 34.62%, the selectivity for cyclohexene oxide was 37.31%, the selectivity for cyclohexenol was 15.59%, the selectivity for cyclohexenone was 21.30%, and the selectivity for orthocyclohexanediol was 25.79%.
Example 4
And (4) evaluating the activity of the catalyst. 1% Au-0.5% Bi/PMo110.02 g of/ZSM-5 catalyst was used for the reaction. Adding 2.0g of cyclohexene, and 3 drops of TBHP were added, and molecular oxygen as an oxygen source was stirred at 80 ℃ under a pressure of 0.8MPa for 18 hours. The conversion rate of cyclohexene oxidation was 41.76%, the selectivity for cyclohexene oxide was 38.33%, the selectivity for cyclohexenol was 10.64%, the selectivity for cyclohexenone was 24.24%, and the selectivity for orthocyclohexanediol was 26.79%. Although the epoxidation effect in this case is similar to that of example 2, the sum of the selectivities of cyclohexene oxide and cyclohexanediol is lower than that of example 2, indicating BMo11And PMo11The synergistic effect of the compounds has the tendency of inhibiting allylic oxidation and leading the reaction to proceed towards the direction of generating cyclohexene oxide and cyclohexanediol, and is beneficial to the subsequent optimization experiment for improving the yield of the cyclohexene oxide.
Example 5
And (4) evaluating the activity of the catalyst. 1% Au-0.5% Bi/PMo11+BMo110.02 g of/ZSM-5 catalyst was used for the reaction. 2.0g of cyclohexene was added, and 3 drops of TBHP were added, and molecular oxygen as an oxygen source was stirred at 80 ℃ under a pressure of 0.5MPa for reaction for 18 hours. The conversion rate of cyclohexene oxidation was 39.30%, the selectivity for cyclohexene oxide was 40.85%, the selectivity for cyclohexenol was 12.55%, the selectivity for cyclohexenone was 19.85%, and the selectivity for orthocyclohexanediol was 26.75%.
Example 6
And (4) evaluating the activity of the catalyst. 1% Au-0.5% Bi/PMo11+BMo110.02 g of/ZSM-5 catalyst was used for the reaction. 2.0g of cyclohexene was added, and 3 drops of TBHP were added, and molecular oxygen as an oxygen source was stirred at 100 ℃ under a pressure of 0.5MPa for reaction for 18 hours. The conversion rate of cyclohexene oxidation was 39.17%, the selectivity for cyclohexene oxide was 32.21%, the selectivity for cyclohexenol was 17.14%, the selectivity for cyclohexenone was 21.58%, and the selectivity for orthocyclohexanediol was 29.07%.
Example 7
And (4) evaluating the activity of the catalyst. 1% Au-0.5% Bi/PMo11+BMo110.02 g of/ZSM-5 catalyst was used for the reaction. 2.0g of cyclohexene was added, and 3 drops of TBHP were added, and molecular oxygen as an oxygen source was stirred at 80 ℃ under a pressure of 0.5MPa for reaction for 36 hours. The conversion rate of cyclohexene oxidation obtained is 42.33 percent, and the cyclohexene oxide is obtainedThe selectivity of (A) was 33.62%, the selectivity of cyclohexenol was 11.46%, the selectivity of cyclohexenone was 24.46%, and the selectivity of orthocyclohexanediol was 30.46%.
Example 8
And (4) evaluating the activity of the catalyst. 1% Au-0.5% Bi/PMo11+BMo110.01 g of/ZSM-5 catalyst was used for the reaction. 2.0g of cyclohexene was added, and 3 drops of TBHP were added, and molecular oxygen as an oxygen source was stirred at 80 ℃ under a pressure of 0.5MPa for reaction for 18 hours. The conversion rate of cyclohexene oxidation was 30.45%, the selectivity for cyclohexene oxide was 41.59%, the selectivity for cyclohexenol was 13.61%, the selectivity for cyclohexenone was 20.98%, and the selectivity for orthocyclohexanediol was 23.82%.

Claims (5)

1. A supported metal polyoxometallate hybrid catalyst is characterized in that the structural formula of the catalyst is Au-Bi/PMo11+BMo11ZSM-5 with Au, Bi, polyoxometalates BMo11And PMo11The synergistic effect is used as the main active component of the catalyst, the apparent mass percentage of Au is 1.0 percent, the apparent mass percentage of Bi is 0.5 percent, BMo percent11And PMo11The mass percentage of the catalyst is 3.33 percent (1:30), ZSM-5 is a modified ZSM-5 molecular sieve which is used as a carrier of the catalyst, and the modified ZSM-5 molecular sieve is the ZSM-5 molecular sieve which is treated by roasting and NaOH solution.
2. The supported metal polyoxometalate hybrid catalyst of claim 1 wherein the Au is a metal of Au, a metal oxide of Au or a mixture of both; bi is Bi metal, Bi metal oxide or the mixture of the two.
3. The supported metal polyoxometalate hybrid catalyst of claim 1 wherein the metal polyoxometalate comprises phosphomolybdates PMo11And boron molybdenum polyoxometalates BMo11The polyoxo cluster metal complex has a steric structure, wherein Mo is taken as a ligand atom, B, P is taken as a heteroatom, and oxygen atoms are bridged together.
4. A method of preparing the supported metal polyoxometalate hybrid catalyst of claim 1, comprising the steps of:
1) dipping and reducing: preparing a polyvinyl alcohol solution, adding a chloroauric acid solution and a bismuth nitrate solution, stirring for 30min, adding a modified ZSM-5 molecular sieve, stirring for 30min, raising the temperature to 80 ℃, adding urea, stirring for 5h, adding a formaldehyde solution for reduction for 2h, cooling, filtering, washing, and drying in an oven at 90 ℃ to obtain Au-Bi/ZSM-5 serving as a catalyst precursor;
2) dipping and mixing: adding the catalyst precursor obtained in the step 1) into a single-mouth bottle, and adding the metal polyoxometallate PMo11And BMo11Adding deionized water, stirring and dispersing at 50-60 deg.C until water is evaporated to dryness, and oven drying at 90 deg.C to obtain solid Au-Bi/PMo11+BMo11a/ZSM-5 catalyst.
5. Use of a supported metal polyoxometalate hybrid catalyst according to claim 1 in the selective epoxidation of cyclohexene to epoxycyclohexane with molecular oxygen in the absence of solvent.
CN201810769251.4A 2018-07-13 2018-07-13 Supported metal polyoxometallate hybrid catalyst and preparation method and application thereof Active CN108993581B (en)

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