[go: up one dir, main page]

CN117138812A - Composite nanocatalyst and its preparation method and application - Google Patents

Composite nanocatalyst and its preparation method and application Download PDF

Info

Publication number
CN117138812A
CN117138812A CN202311107451.0A CN202311107451A CN117138812A CN 117138812 A CN117138812 A CN 117138812A CN 202311107451 A CN202311107451 A CN 202311107451A CN 117138812 A CN117138812 A CN 117138812A
Authority
CN
China
Prior art keywords
composite
acid
catalyst
composite nano
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311107451.0A
Other languages
Chinese (zh)
Inventor
汪丽华
朱坚
李名明
应思斌
王平
洪鑫
赫励
谢国玲
娄春情
诸葛王平
毛善俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZHEJIANG XINHUA CHEMICAL CO Ltd
Zhejiang University ZJU
Original Assignee
ZHEJIANG XINHUA CHEMICAL CO Ltd
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ZHEJIANG XINHUA CHEMICAL CO Ltd, Zhejiang University ZJU filed Critical ZHEJIANG XINHUA CHEMICAL CO Ltd
Priority to CN202311107451.0A priority Critical patent/CN117138812A/en
Publication of CN117138812A publication Critical patent/CN117138812A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a composite nano catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing polyoxometallate, a template agent and a solvent to obtain a first configuration material, and then mixing the first configuration material with an alumina precursor to obtain a second configuration material; aging the second configuration material to obtain a solid mixture; and finally calcining the solid mixture to obtain the composite nano-catalyst, wherein the composite nano-catalyst is porous nano-alumina loaded with polyoxometallate, and the polyoxometallate is loaded on five-coordination aluminum sites of the porous nano-alumina. The preparation method can anchor polyoxometallate in situ in the process of generating penta-coordinated aluminum sites, so that the obtained composite nano catalyst has excellent oxidation-reduction performance and acidity, and can show excellent catalytic performance in selective oxidation reaction of aldehyde or alcohol, esterification reaction of acid and alcohol or acid and olefin, and alkylation reaction of aromatic compounds.

Description

Composite nano catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a composite nano catalyst and a preparation method and application thereof.
Background
Polyoxometallates (POMs) have adjustable redox and acidic properties, inherent resistance to oxidative decomposition, and excellent photo and electro sensitivity, making them have a broad application prospect. However, since polyoxometalates have a small specific surface area and high solubility in polar solvents, there is a lack of recyclability and reusability. Thus, it is desirable to support it on a high surface area support such as molecular sieves, silica, alumina, carbon materials, zeolites, and the like.
Currently, in the loading mode, the impregnation method is more common, for example, the heteropolyacid is simply loaded on the carrier by the impregnation mode, the interaction between the heteropolyacid and the carrier is an acid-base reaction in nature, and the hydroxyl groups on the surface of the carrier are protonated and then are subjected to neutralization or coordination reaction with counter anions. However, the strategy of anchoring by acid-base reaction is no longer applicable due to lack of protons, and at present, complicated methods such as electrostatic fixation are generally adopted, but nevertheless, the problems of mass transfer, limited fixing capacity or loading capacity, serious leaching and the like still exist. Therefore, it is important to develop a simple anchoring method and to stabilize the existence of POMs on the surface of the carrier.
Disclosure of Invention
In view of the foregoing, it is desirable to provide a composite nanocatalyst, a preparation method thereof, and an application thereof, wherein the preparation method is capable of anchoring polyoxometallate in situ during the process of generating pentadentate aluminum sites, so that the obtained composite nanocatalyst has excellent redox performance and acidity, and is capable of exhibiting excellent catalytic performance in selective oxidation reaction of aldehyde or alcohol, esterification reaction of acid and alcohol or acid and olefin, and alkylation reaction of aromatic compounds.
The invention provides a preparation method of a composite nano catalyst, which comprises the following steps:
mixing polyoxometalate, a template agent and a solvent to obtain a first configuration material;
mixing the first configuration with an alumina precursor to obtain a second configuration;
aging the second configuration material to obtain a solid mixture;
calcining the solid mixture to obtain a composite nano-catalyst, wherein the composite nano-catalyst is porous nano-alumina loaded with polyoxometallate, and the polyoxometallate is loaded on five-coordination aluminum sites of the porous nano-alumina.
In one embodiment, the mass ratio of the polyoxometallate, the template agent and the alumina precursor is 1 (2-4): 4-8.
In one embodiment, the polyoxometalate is selected from at least one of ammonium phosphomolybdate, phosphomolybdic acid, phosphotungstic acid, silicotungstic acid, silicomolybdic acid, sodium phosphotungstate, sodium silicotungstate;
and/or the template agent is at least one selected from polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, polyoxyethylene polyoxypropylene ether block copolymer, cetyltrimethylammonium bromide, sodium oleate, sodium dodecyl benzene sulfonate, stearic acid, sodium stearate and polyethylene glycol;
and/or the alumina precursor is at least one selected from aluminum isopropoxide, triethylaluminum, triisobutylaluminum, aluminum n-butoxide, aluminum nitrate, aluminum chloride and aluminum sulfate.
In one embodiment, the second formulation is aged at a temperature of 30 ℃ to 80 ℃ for a time of 0.5h to 96h;
and/or in the step of calcining the solid mixture, the calcining temperature is 200-500 ℃, the heating rate is 1-20 ℃/min, and the calcining time is 0.5-6 h.
A composite nanocatalyst obtained from the method of preparing a composite nanocatalyst as described above, the composite nanocatalyst comprising a porous nanocapsule alumina and a polyoxometalate supported on pentadentate aluminum sites of the porous nanocapsule alumina.
In one embodiment, the loading of the polyoxometalate is 1-60%, and the specific surface area of the composite nano catalyst is 100m 2 /g-800m 2 Per gram, total pore volume of 0.1cm 3 /g-1cm 3 And/g, the average pore diameter is 1nm-10nm.
The composite nano catalyst is used for catalyzing the selective oxidation reaction of aldehyde.
A composite nano catalyst as described above is used for catalyzing the selective oxidation reaction of alcohols.
The composite nano catalyst is used for catalyzing the esterification reaction of acid and alcohol or acid and olefin.
The composite nano catalyst is used for catalyzing alkylation reaction of aromatic compounds.
According to the preparation method of the composite nano-catalyst, the polyoxometallate is introduced in situ in the synthesis process of the porous nano-alumina carrier, so that the hydrolysis of an aluminum precursor can be catalyzed, and the generation of five-coordination aluminum sites can be promoted, so that the polyoxometallate can be anchored in situ in the process of generating the five-coordination aluminum sites, the method is simple, the polyoxometallate can exist on the porous nano-alumina carrier stably, and meanwhile, the loading capacity of the polyoxometallate, the specific surface area, the total pore volume and the average pore diameter of the composite nano-catalyst can be adjusted.
Therefore, the composite nano catalyst obtained by the invention has excellent oxidation-reduction performance and acidity, can show excellent catalytic performance in selective oxidation reaction of aldehyde, selective oxidation reaction of alcohol, esterification reaction of acid and olefin and alkylation reaction of aromatic compounds, and has wide application prospect.
Drawings
FIG. 1 is a schematic illustration of a composite nanocatalyst prepared according to example 1 27 Al Nuclear Magnetic Resonance (NMR) spectra;
FIG. 2 is a graph showing the adsorption and desorption of nitrogen from the composite nanocatalyst prepared in example 1;
FIG. 3 is a transmission electron microscope image of the composite nanocatalyst prepared in example 1;
FIG. 4 is an X-ray diffraction pattern of the composite nanocatalyst prepared in example 1;
FIG. 5 is a transmission electron microscope image of the composite nanocatalyst prepared in example 2;
FIG. 6 is a transmission electron microscope image of the nanocatalyst prepared in comparative example 2;
FIG. 7 is a graph of stability data for the composite nanocatalyst prepared in example 1, wherein a is the conversion of methylbutyrate and b is the selectivity to methylbutyrate;
FIG. 8 is a graph showing stability data of the composite nanocatalyst prepared in comparative example 1, wherein c is the conversion of 2-methylbutyraldehyde and d is the selectivity of 2-methylbutyrate.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The preparation method of the composite nano catalyst provided by the invention comprises the following steps:
s1, mixing polyoxometalate, a template agent and a solvent to obtain a first configuration material;
s2, mixing the first configuration material with an alumina precursor to obtain a second configuration material;
s3, aging the second configuration material to obtain a solid mixture;
and S4, calcining the solid mixture to obtain a composite nano-catalyst, wherein the composite nano-catalyst is porous nano-alumina loaded with polyoxometallate, and the polyoxometallate is loaded on five-coordination aluminum sites of the porous nano-alumina.
In step S1, the mode of mixing the polyoxometalate, the template agent and the solvent is not limited, alternatively, the polyoxometalate may be dispersed in the solvent to obtain a first mixed solution, the template agent is dispersed in the solvent to obtain a second mixed solution, and the first mixed solution and the second mixed solution are mixed to obtain the first configuration, wherein the mode of mixing the first mixed solution and the second mixed solution is preferably dropwise adding, and the dropwise adding sequence is preferably that the first mixed solution is dropwise added to the second mixed solution.
In an embodiment, the polyoxometalate is at least one selected from ammonium phosphomolybdate, phosphomolybdic acid, phosphotungstic acid, silicotungstic acid, silicomolybdic acid, sodium phosphotungstate and sodium silicotungstate, and different types of polyoxometalates are selected to generate composite nano materials with different morphologies, for example, ammonium phosphomolybdate is selected to generate composite nano materials with a nano-sheet morphology, and phosphomolybdic acid is selected to generate composite nano materials with a nano-sphere morphology.
In one embodiment, the template agent is at least one selected from polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, polyoxyethylene polyoxypropylene ether block copolymer, cetyltrimethylammonium bromide, sodium oleate, sodium dodecylbenzenesulfonate, stearic acid, sodium stearate, and polyethylene glycol.
In an embodiment, the solvent is selected from organic solvents, and may be specifically selected from at least one of ethanol, acetone, tetrahydrofuran, acetonitrile, and ethyl acetate.
In step S2, in the process of mixing the first configuration material with the alumina precursor, the template agent, the alumina precursor and the polyoxometalate can perform intermolecular interactions, such as hydrogen bonding and electrostatic interactions.
It will be appreciated that the order in which the first formulation is mixed with the alumina precursor is not limited, and that it is preferred that the alumina precursor is mixed in the first formulation.
In an embodiment, the alumina precursor is selected from at least one of aluminum isopropoxide, triethylaluminum, triisobutylaluminum, aluminum n-butoxide, aluminum nitrate, aluminum chloride, aluminum sulfate.
In one embodiment, the mass ratio of the polyoxometallate to the template agent to the alumina precursor is 1 (2-4) to 4-8, so that the hydrolysis of the alumina precursor is catalyzed, the generation of penta-coordinated aluminum sites is promoted, and the loading of the polyoxometallate, the specific surface area, the total pore volume and the average pore diameter of the composite nano-catalyst are adjusted.
In the aging process of the second configuration in step S3, along with the volatilization of the solvent, the alumina precursor undergoes hydrolysis reaction in the presence of the crystal water and the physically adsorbed water in the polyoxometalate, so as to generate AlOOH, and forms a solid mixture with the polyoxometalate, the template agent and the like.
In one embodiment, the second formulation is subjected to the aging treatment at a temperature of preferably 30 ℃ to 80 ℃, more preferably 50 ℃ to 60 ℃, and a time of preferably 0.5h to 96h, more preferably 24h to 48h, so that the aging rate and the aging degree can be better controlled at the aging temperature and the aging time.
In the calcining process of the step S4, the template agent is calcined and removed, the AlOOH is dehydrated to generate a porous nano alumina carrier, and unsaturated five-coordinated aluminum sites are formed under the promotion effect of polyoxometallate, so that the polyoxometallate is anchored in situ to form the composite nano catalyst. And because of the strong interaction between the polyoxometallate and the alumina, the dispersion of the polyoxometallate is promoted, meanwhile, electron transfer occurs between the polyoxometallate and the alumina, electrons are obtained from metals in the polyoxometallate, the positive 5-valence content is increased, the electronic structures of the active polyoxometallate and the carrier alumina are improved, and the efficient performance of the catalytic reaction is facilitated.
In one embodiment, in the step of calcining the solid mixture, the calcining temperature is preferably 200 ℃ to 500 ℃, more preferably 300 ℃ to 350 ℃, the heating rate is preferably 1 ℃/min to 20 ℃/min, more preferably 1 ℃/min to 10 ℃/min, the calcining time is preferably 0.5h to 6h, more preferably 3h to 4h, and the calcining condition can not only remove the surfactant better, but also avoid the thermal decomposition of polyoxometalate better.
Therefore, in the preparation method of the composite nano-catalyst, polyoxometallate is introduced in situ in the synthesis process of the porous nano-alumina carrier, so that the hydrolysis of an aluminum precursor can be catalyzed, and the generation of penta-coordination aluminum sites can be promoted, so that the polyoxometallate can be anchored in situ in the process of generating the penta-coordination aluminum sites, the method is simple, the polyoxometallate can exist on the porous nano-alumina carrier stably, and meanwhile, the loading capacity of the polyoxometallate, the specific surface area, the total pore volume and the average pore diameter of the composite nano-catalyst can be adjusted.
The invention also provides a composite nano-catalyst obtained by the preparation method of the composite nano-catalyst, and the composite nano-catalyst comprises porous nano-alumina and polyoxometallate supported on five-coordination aluminum sites of the porous nano-alumina.
In one embodiment, the loading of the polyoxometalate is preferably 1% -60%, more preferably 6% -26%, and the specific surface area of the composite nano-catalyst is preferably 100m 2 /g-800m 2 Preferably 400m 2 /g-700m 2 Per g, the total pore volume is preferably 0.1cm 3 /g-1cm 3 Preferably 0.4cm 3 /g-0.9cm 3 The average pore diameter per gram is preferably 1nm to 10nm, more preferably 2nm to 6nm.
The composite nano catalyst obtained by the invention has excellent oxidation-reduction performance and acidity, and can show excellent catalytic performance in selective oxidation reaction of aldehyde, selective oxidation reaction of alcohol, esterification reaction of acid and olefin and alkylation reaction of aromatic compound.
Therefore, the invention also provides a composite nano catalyst for catalyzing the selective oxidation reaction of aldehyde.
Preferably, the aldehyde is selected from aldehydes having 2 to 10 carbon atoms.
The selective oxidation reaction of the aldehyde can be continuous oxidation reaction or intermittent oxidation reaction, when the selective oxidation reaction of the aldehyde is continuous oxidation reaction, the reaction temperature is 40-150 ℃, the reaction pressure is 0.1-6 MPa, and the mass space velocity of the aldehyde is 0.1h -1 -10h -1 The molar ratio of air to aldehyde is 5:1-500:1; when the aldehyde selective oxidation reaction is intermittent oxidation reaction, the reaction temperature is 40-150 ℃, the reaction pressure is 0.1-6 MPa, and the composite nano catalyst and the catalyst are used for preparing the catalystThe mass ratio of aldehyde is 0.0001:1-0.3:1, and the flow rate of air is 0.1-300 mL/min calculated on the basis of each gram of catalyst.
The invention also provides a composite nano catalyst for catalyzing the selective oxidation reaction of alcohol.
In the selective oxidation reaction of alcohol, the reactants comprise alcohol and oxidant, in one embodiment, the reaction temperature is 40-100 ℃, the molar ratio of the oxidant to the alcohol is 10:1-200:1, the mass ratio of the composite nano catalyst to the alcohol is 0.01:1-0.2:1, and the oxidant is preferably hydrogen peroxide.
The invention also provides a composite nano catalyst for catalyzing the esterification reaction of acid and alcohol or acid and olefin.
In one embodiment, the acid is selected from at least one of 2-methylbutyric acid, acetic acid, propionic acid, salicylic acid, benzoic acid, phenylacetic acid, caproic acid, heptanoic acid, phenylpropionic acid, phenoxyacetic acid, cyclohexyloxyacetic acid, palmitic acid.
In one embodiment, the alcohol is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-hexanol, n-pentanol, benzyl alcohol, leaf alcohol, cyclohexanol, isooctanol, isopferol, o-t-butylcyclohexanol, p-t-butylcyclohexanol, alpha-phenylethanol, beta-phenylethanol, allyl alcohol.
In one embodiment, the alkene is selected from at least one of myrcene, styrene, dicyclopentadiene, cyclopentene.
Wherein, the esterification reaction can be continuous esterification reaction and intermittent esterification reaction, when the esterification reaction is continuous esterification reaction, the reaction temperature is 50 ℃ to 200 ℃, the reaction pressure is 0.1MPa to 6MPa, and the mass airspeed of the acid is 0.1h -1 -10h -1 The molar ratio of the acid to the alcohol or the acid to the alkene is 0.01:1-10:1; when the esterification reaction is an intermittent esterification reaction, the reaction temperature is 50-200 ℃, the reaction pressure is 0-6 MPa, the molar ratio of acid to alcohol or acid to alkene is 0.01:1-10:1, and the mass ratio of the composite nano catalyst to acid is 0.0001:1-0.2:1.
The invention also provides a composite nano catalyst for catalyzing the alkylation reaction of aromatic compounds.
In one embodiment, the alkylation reaction of the aromatic compound is selected from at least one of alkylation reaction of phenol with an olefin having 2 to 4 carbon atoms, alkylation reaction of phenol with an alcohol having 1 to 4 carbon atoms, alkylation reaction of aromatic hydrocarbon with an olefin having 2 to 4 carbon atoms, and alkylation reaction of aromatic hydrocarbon with an alcohol having 1 to 4 carbon atoms.
In one embodiment, the phenol is selected from at least one of phenol, p-cresol, m-cresol, o-cresol; the aromatic hydrocarbon is selected from at least one of benzene, toluene and ethylbenzene; the olefin is selected from at least one of ethylene, propylene and isobutene; the alcohol is at least one selected from methanol, ethanol, isopropanol and tert-butanol.
In one embodiment, the reaction temperature is 150 ℃ to 400 ℃, the reaction pressure in the alkylation reaction is 0.1MPa to 6MPa, and the mass space velocity of the phenol or the aromatic hydrocarbon is 0.1h -1 -10h -1 The molar ratio of the phenol to the olefin, the phenol to the alcohol, the aromatic hydrocarbon to the olefin, and the aromatic hydrocarbon to the alcohol is 0.01:1-10:1.
Hereinafter, the composite nanocatalyst and the preparation method and application thereof will be further described by the following specific examples.
Example 1
20g of a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) was placed in 400mL of absolute ethanol, 2.2g of ammonium phosphomolybdate was dispersed in 80mL of absolute ethanol, and was added dropwise to an ethanol solution of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer at a constant speed, and stirred and mixed uniformly to obtain a first preparation.
40.8g of aluminum isopropoxide was placed in the first formulation and stirred for 6h to give the second formulation.
And (3) placing the second configuration material in an oven at 60 ℃ for aging for 48 hours to obtain a solid mixture, calcining the solid mixture in an air furnace at the temperature of 350 ℃ and the heating rate of 1 ℃/min for 4 hours to obtain the composite nano catalyst.
The composite nanocatalyst obtained in this example 27 As shown in FIG. 1, the Al nuclear magnetic resonance chart shows that the coordination condition and the corresponding percentage content of aluminum in the composite nano-catalyst are shown in FIG. 1, wherein four-coordinated aluminum, five-coordinated aluminum and six-coordinated aluminum coexist, and the five-coordinated aluminum accounts for 19%. And carrying out structural characterization on the obtained composite nano catalyst, wherein the actual load of ammonium phosphomolybdate in the composite nano catalyst is 15%.
The nitrogen adsorption and desorption curve of the composite nano catalyst obtained in the embodiment is shown in fig. 2, and is represented as a typical iv adsorption and desorption curve, and has an i hysteresis loop, which indicates that a large number of mesoporous structures exist in the composite nano catalyst, and the specific surface area of the composite nano catalyst is 560m after calculation 2 Per gram, total pore volume of 0.533cm 3 And/g, average pore diameter of 3.81nm.
The transmission electron microscope diagram of the composite nano-catalyst obtained in this example is shown in fig. 3, and as can be seen from fig. 3, the structure of the composite nano-catalyst is a nano-plate.
The X-ray diffraction pattern of the composite nanocatalyst obtained in this example is shown in fig. 4 and has a diffraction peak of ammonium phosphomolybdate.
Example 2
Example 2 was performed with reference to example 1, except that: the polyoxometallate is selected from phosphomolybdic acid, the actual load of the phosphomolybdic acid in the composite nano catalyst is 13%, and the pentadentate aluminum accounts for 21%. The calculation result of the gas adsorption and desorption test shows that the specific surface area of the composite nano catalyst is 670m 2 Per gram, a total pore volume of 0.936cm 3 And/g, average pore diameter of 5.22nm.
The transmission electron microscope diagram of the composite nano-catalyst obtained in the embodiment is shown in fig. 5, and as can be seen from fig. 5, the structure of the composite nano-catalyst is a three-dimensional nanosphere assembled by nano-sheets.
Example 3
Example 3 was performed with reference to example 1, except that: the polyoxometallate is selected from phosphotungstic acid, the actual loading of the phosphotungstic acid in the composite nano-catalyst is 13%, and the pentadentate aluminum accounts for 20%. The calculation result of the nitrogen adsorption and desorption test shows that the ratio of the composite nano catalystSurface area of 600m 2 Per gram, total pore volume of 0.812cm 3 And/g, average pore diameter of 4.83nm.
Example 4
Example 4 was performed with reference to example 1, except that: the polyoxometalate is selected from silicotungstic acid, the actual load of the silicotungstic acid in the composite nano-catalyst is 17%, and the pentadentate aluminum accounts for 15%. The calculation result of the nitrogen adsorption and desorption test shows that the specific surface area of the composite nano catalyst is 584m 2 Per gram, total pore volume of 0.796cm 3 And/g, average pore diameter of 4.56nm.
Example 5
Example 5 was performed with reference to example 1, except that: the polyoxometallate is selected from silicomolybdic acid, the actual load of the silicomolybdic acid in the composite nano catalyst is 15%, and the pentadentate aluminum accounts for 18%. The calculation result of the nitrogen adsorption and desorption test shows that the specific surface area of the composite nano catalyst is 559m 2 Per gram, total pore volume of 0.712cm 3 And/g, average pore diameter of 4.34nm.
Example 6
Example 6 was performed with reference to example 1, except that: the polyoxometallate is selected from sodium phosphotungstate, the actual loading of the sodium phosphotungstate in the composite nano catalyst is 15%, and the pentadentate aluminum accounts for 19%. The calculation result of the nitrogen adsorption and desorption test shows that the specific surface area of the composite nano catalyst is 620m 2 Per gram, total pore volume of 0.853cm 3 And/g, average pore diameter of 4.96nm.
Example 7
Example 7 was performed with reference to example 1, except that: the polyoxometalate is selected from sodium silicotungstate, the actual loading of the sodium silicotungstate in the composite nano catalyst is 14%, and the pentadentate aluminum accounts for 15%. The calculation result of the nitrogen adsorption and desorption test shows that the specific surface area of the composite nano catalyst is 524m 2 Per gram, total pore volume of 0.699cm 3 And/g, average pore diameter of 4.31nm.
Example 8
Example 8 was performed with reference to example 1, except that: 6.3g of ammonium phosphomolybdate was dispersed in 80mL of absolute ethanol.
The implementation isIn the composite nano catalyst obtained in the example, pentadentate aluminum accounts for 2%, the actual load of ammonium phosphomolybdate is 49%, and the specific surface area is 339m 2 Per gram, total pore volume of 0.456cm 3 And/g, average pore diameter of 5.37nm.
Comparative example 1
And (3) putting 15g of ammonium phosphomolybdate into 500mL of deionized water for dissolution, adding 100g of commercial alumina, uniformly stirring, performing ultrasonic treatment for 6h, drying at 60 ℃ for 48h to obtain a solid mixture, calcining the solid mixture in an air furnace at the temperature of 350 ℃ and the heating rate of 1 ℃/min for 4h to obtain the composite nano catalyst.
Comparative example 2
20g of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is placed in 400mL of absolute ethyl alcohol, 80mL of absolute ethyl alcohol is added into the ethanol solution of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer at a constant speed in a dropwise manner, and the mixture is stirred and mixed uniformly to obtain a first preparation.
40.8g of aluminum isopropoxide was placed in the first formulation and stirred for 6h to give the second formulation.
And (3) placing the second configuration material in an oven at 60 ℃ for aging for 48 hours to obtain a solid mixture, calcining the solid mixture in an air furnace at the temperature of 350 ℃ and the heating rate of 1 ℃/min for 4 hours to obtain the nano catalyst.
The transmission electron microscope image of the nano catalyst obtained in the comparative example is shown in fig. 6, and the catalyst has no special morphology, which shows that the in-situ introduction of polyoxometallate is important for obtaining the composite nano catalyst.
Application example 1
The catalytic performance of the composite nano-catalyst prepared in examples 1-7 in the selective oxidation reaction of 2-methyl butyraldehyde was evaluated by using a reaction kettle, and the operation process was as follows:
0.02g of composite nano catalyst and 40g of 2-methyl butyraldehyde are sequentially added into a 100mL high-pressure reaction kettle, the pressure is increased to 0.5MPa, then air is continuously introduced, the flow rate of the air is 30mL/min, and the temperature is increased to 80 ℃ for reaction. The reaction product was separated and analyzed by using a Shimadzu GC2014 gas chromatograph, wherein the column was HP-INNOWax and the detector was a FID detector. The conversion of 2-methylbutyrate and the selectivity of 2-methylbutyrate were calculated by normalization, and the calculation results are shown in Table 1.
TABLE 1
Catalyst selection Conversion of 2-methylbutanal (%) Selectivity of 2-methylbutyric acid (%)
Example 1 100 94.5
Example 2 97.5 93.6
Example 3 98.7 92.4
Example 4 95.3 93.3
Example 5 96.4 92
Example 6 99.2 93.9
Example 7 98.1 93
As can be seen from Table 1, the composite nanocatalysts prepared in examples 1-7 can all better catalyze the selective oxidation of 2-methyl butyraldehyde, the conversion rate of 2-methyl butyraldehyde is more than 95%, and the selectivity of 2-methyl butyric acid is more than 90%, which indicates that the composite nanocatalysts prepared in examples 1-7 all have excellent 2-methyl butyraldehyde oxidation activity.
Application example 2
The catalytic performance of the composite nanocatalyst prepared in example 1 in catalyzing the selective oxidation reaction of aldehydes having 2 to 10 carbon atoms was evaluated using a reaction vessel, and the reaction conditions and analysis conditions were carried out with reference to application example 1, and the results are shown in table 2.
TABLE 2
As can be seen from Table 2, in the range of 2-10 carbon atoms of aldehyde as the substrate, the conversion rate of aldehyde is more than 90%, and the selectivity of acid is more than 90%, which indicates that the composite nano catalyst prepared in example 1 has better substrate universality.
Application example 3
The composite nanocatalyst prepared in example 1 and the composite nanocatalyst prepared in comparative example 1 were used in the oxidation reaction of 2-methylbutyraldehyde using a fixed bed reactor, and the reaction process was as follows:
stainless steel pipe with outer diameter of 10mm, inner diameter of 6mm and length of 300mm is used as reactor, and 1g of composite nano catalyst is added(particle size 20-40 mesh), the reaction conditions are: the reaction temperature is 80 ℃, the reaction pressure is 0.5MPa, and the mass liquid hourly space velocity of the 2-methyl butyraldehyde is 1h -1 Air was used as an oxidizing agent, the molar ratio of air to 2-methylbutyraldehyde was 50:1, and the analysis conditions were described in application example 1.
The stability data for the composite nanocatalyst prepared in example 1 is shown in fig. 7, and it can be seen that the composite nanocatalyst prepared in example achieves complete conversion of 2-methylbutyrate, selectivity of 2-methylbutyrate is 94%, and shows no sign of deactivation in the 500h stability test.
The stability data of the composite nano-catalyst prepared in comparative example 1 is shown in fig. 8, and it can be seen that the conversion rate of 2-methylbutanal at the initial stage of the reaction is 76%, the selectivity is 92%, and the conversion rate of 2-methylbutanal decreases significantly as the reaction proceeds.
The composite nanocatalyst prepared in example 1 thus has more excellent reactivity and stability.
Application example 4
The catalytic performance of the composite nanocatalyst prepared in example 1 in the selective oxidation of benzyl alcohol was evaluated using a round bottom flask, and the procedure was as follows:
to a 25mL round bottom flask, 0.1g of the composite nano catalyst, 0.6g of benzyl alcohol, 6.15mL of hydrogen peroxide with mass fraction of 30% and 10mL of acetonitrile are sequentially added, and the mixture is condensed and refluxed, and the temperature is raised to 80 ℃ for reaction for 10 hours. After separation, the reaction product was analyzed using an Agilent 7890 gas chromatograph, wherein the column was HP-INNOWax and the detector was a FID detector. The conversion of benzyl alcohol and the selectivity of benzaldehyde were calculated by normalization. The conversion rate of benzyl alcohol is 81%, and the selectivity of benzaldehyde is 100%, which shows that the composite nano catalyst prepared in example 1 can efficiently catalyze the selective oxidation of benzyl alcohol to obtain benzaldehyde.
Application example 5
The catalytic performance of the composite nano catalyst prepared in example 1 in the esterification reaction of 2-methylbutanoic acid with methanol, ethanol, n-propanol, isopropanol and n-hexanol was evaluated by using a reaction kettle, and the operation process is as follows:
0.1g of composite nano catalyst, 20g of 2-methyl butyric acid and corresponding alcohol are sequentially added into a 100mL high-pressure reaction kettle, the molar ratio of acid to alcohol is controlled to be 0.5:1, and the temperature is raised to 95 ℃ for reaction for 9 hours. After separation, the reaction product was analyzed using an Agilent 7890 gas chromatograph, wherein the column was HP-INNOWax and the detector was a FID detector. The conversion of 2-methylbutyric acid and the selectivity of the ester were calculated by normalization, and the calculation results are shown in Table 3.
TABLE 3 Table 3
As can be seen from table 3, the composite nanocatalyst prepared in example 1 was capable of catalyzing the esterification reaction of 2-methylbutyric acid with alcohol, and the conversion rate of 2-methylbutyric acid and the selectivity of the corresponding ester were excellent.
Application example 6
The esterification reaction performance of the composite nano catalyst prepared in example 1 in salicylic acid, methanol, ethanol, n-propanol, n-hexanol, n-pentanol, benzyl alcohol, leaf alcohol, cyclohexanol, isooctanol and isophorone alcohol is evaluated by using a reaction kettle, and the operation process is as follows:
0.1g of composite nano catalyst, 20g of salicylic acid and corresponding alcohol are sequentially added into a 100mL high-pressure reaction kettle, the mol ratio of the acid to the alcohol is controlled to be 0.8:1, and the temperature is raised to 95 ℃ for reaction for 9 hours. After separation, the reaction products were analyzed using an Agilent 1260 liquid chromatograph. The conversion of salicylic acid and the selectivity of esters were calculated by normalization, and the calculation results are shown in table 4.
TABLE 4 Table 4
Substrate(s) Conversion of salicylic acid (%) Selectivity of ester (%)
Methanol 92.1 95.6
Ethanol 92.3 94.7
N-propanol 89.7 94.7
N-hexanol 87.1 95.2
N-amyl alcohol 88.8 95.1
Benzyl alcohol 82.3 93.2
(Phyllol) 86.1 95.4
Cyclohexanol 84.3 95.1
Isooctanol 79.4 95.8
Isofoll alcohol 78.3 92.9
As can be seen from table 4, the composite nanocatalyst prepared in example 1 was able to catalyze the esterification reaction of salicylic acid with alcohol, and the conversion rate of salicylic acid and the selectivity of the corresponding ester were excellent.
Application example 7
The catalytic performance of the composite nano catalyst prepared in example 1 in the esterification reaction of acetic acid, propionic acid, benzoic acid, phenylacetic acid and benzyl alcohol was evaluated by using a reaction kettle, and the operation process is as follows:
0.1g of composite nano catalyst, 20g of benzyl alcohol and corresponding acid are sequentially added into a 100mL high-pressure reaction kettle, the molar ratio of the acid to the alcohol is controlled to be 1.2:1, and the temperature is raised to 95 ℃ for reaction for 9 hours. After separation, the reaction product was analyzed using an Agilent 7890 gas chromatograph, wherein the column was HP-INNOWax and the detector was a FID detector. The conversion of benzyl alcohol and the selectivity of ester were calculated by normalization method, and the calculation results are shown in Table 5.
TABLE 5
Substrate(s) Conversion of benzyl alcohol (%) Selectivity of ester (%)
Acetic acid 88.7 96.1
Propionic acid 88.3 96.4
Benzoic acid 83.2 95.9
Phenylacetic acid 83.6 94.3
As can be seen from table 5, the composite nanocatalyst prepared in example 1 was capable of catalyzing esterification of benzyl alcohol with acid, and the conversion rate of benzyl alcohol and the selectivity of the corresponding ester were excellent.
Application example 8
The catalytic performance of the composite nano catalyst prepared in example 1 in the esterification reaction of acetic acid, caproic acid, heptanoic acid, phenylpropionic acid, phenoxyacetic acid, cyclohexyloxyacetic acid and allyl alcohol was evaluated by using a reaction kettle, and the operation process was as follows:
0.1g of composite nano catalyst, 20g of allyl alcohol and corresponding acid are sequentially added into a 100mL high-pressure reaction kettle, the molar ratio of the acid to the alcohol is controlled to be 1.2:1, and the temperature is raised to 95 ℃ for reaction for 9 hours. After separation, the reaction product was analyzed using an Agilent 7890 gas chromatograph, wherein the column was HP-INNOWax and the detector was a FID detector. The conversion of allyl alcohol and the selectivity of ester were calculated by normalization method, and the calculation results are shown in table 6.
TABLE 6
Substrate(s) Conversion of allyl alcohol (%) Selectivity of ester (%)
Acetic acid 95.7 90.3
Caproic acid 92.3 89.7
Heptanoic acid 91.9 90.2
Phenylpropionic acid 91.1 87.6
Phenoxyacetic acid 90.5 90.7
Cyclohexyloxyacetic acid 86.6 92.1
As can be seen from table 6, the composite nanocatalyst prepared in example 1 was able to efficiently catalyze the esterification reaction of allyl alcohol with acid.
Application example 9
The catalytic performance of the composite nano catalyst prepared in example 1 in the esterification reaction of acetic acid with myrcene, styrene, dicyclopentadiene and cyclopentene is evaluated by adopting a reaction kettle, and the operation process is as follows:
0.1g of composite nano catalyst, 20g of acetic acid and corresponding alkene are sequentially added into a 100mL high-pressure reaction kettle, the molar ratio of the acid to the alkene is controlled to be 3:1, nitrogen is pressurized to 2MPa, and the temperature is raised to 110 ℃ for reaction for 12 hours. After separation, the reaction product was analyzed using an Agilent 7890 gas chromatograph, wherein the column was HP-INNOWax and the detector was a FID detector. The conversion of the alkene and the selectivity of the ester were calculated by normalization, and the calculation results are shown in Table 7.
TABLE 7
Substrate(s) Conversion of alkene (%) Selectivity of ester (%)
Myrcene 96.4 85.3
Styrene 94.3 78.4
Dicyclopentadiene 96.9 89.9
Cyclopentene (cyclopentene) 87.6 82.8
As can be seen from table 7, the composite nanocatalyst prepared in example 1 was able to efficiently catalyze the esterification reaction of alkene with acetic acid.
Application example 10
The catalytic performance of the composite nano catalyst prepared in example 1 in continuous esterification reaction of acetic acid with o-tert-butylcyclohexanol, p-tert-butylcyclohexanol, alpha-phenethyl alcohol and beta-phenethyl alcohol was evaluated by using a fixed bed reactor:
stainless steel pipe with outer diameter of 10mm, inner diameter of 6mm and length of 300mm is used as a reactor, 1g of composite nano catalyst (particle size of 20-40 meshes) is added, the reaction temperature is 120 ℃, the reaction pressure is 1MPa, and the mass space velocity of alcohol is 1h -1 The molar ratio of acetic acid to alcohol was 3:1, and the analysis conditions were as described in application example 9, and the results are shown in Table 8.
TABLE 8
Substrate(s) Conversion of alcohol (%) Selectivity of ester (%)
O-tert-butylcyclohexanol 99.5 99.4
Para-tert-butylcyclohexanol 99.8 98.7
Alpha-phenethyl alcohol 98.7 98.2
Beta-phenethyl alcohol 99.6 98.6
As can be seen from table 8, the composite nanocatalyst prepared in example 1 was able to efficiently catalyze the continuous esterification reaction of acetic acid with the corresponding alcohol.
Application example 11
The catalytic performance of the composite nanocatalyst prepared in example 1 in the esterification reaction of palmitic acid and methanol was evaluated using a round-bottom flask, and the procedure was as follows:
into a 25mL round bottom flask, 0.1g of composite nano catalyst, 1g of palmitic acid and 12.5mL of methanol are added in sequence, the mixture is condensed and refluxed, and the temperature is raised to 60 ℃ for reaction for 12h. After separation, the reaction product was analyzed using an Agilent 7890 gas chromatograph, wherein the column was HP-INNOWax and the detector was a FID detector. The conversion of palmitic acid and the selectivity of methyl palmitate were calculated using normalization. Wherein the conversion of palmitic acid is 89% and the selectivity of methyl palmitate is 100%. The composite nano catalyst prepared in the embodiment 1 can efficiently catalyze the esterification reaction of the biomass derivative palmitic acid and methanol.
Application example 12
The catalytic performance of the composite nano-catalyst prepared in examples 1-7 in the esterification reaction of lauryldiacid and methanol was evaluated by using a reaction kettle, and the operation process was as follows:
0.02g of composite nano catalyst, 10g of lauroyl diacid and 60g of methanol are sequentially added into a 100mL high-pressure reaction kettle, and the temperature is raised to 80 ℃ for reaction for 12 hours. After separation, the reaction product was analyzed by using a Shimadzu GC2014 gas chromatograph, wherein the column was HP-INNOWax and the detector was a FID detector. The conversion of laurenedioic acid and the selectivity of dimethyl laurenedioate were calculated by normalization method, and the calculation results are shown in Table 9.
TABLE 9
Catalyst selection Conversion of lauryldiacid (%) Selectivity of dimethyl laurate (%)
Example 1 95.1 89.7
Example 2 93.7 88.6
Example 3 93.4 86.8
Example 4 92.1 89.1
Example 5 94.1 89.5
Example 6 92.1 90.6
Example 7 93.1 87.9
As can be seen from Table 9, the composite nanocatalysts prepared in examples 1-7 can efficiently catalyze the esterification reaction of lauryldiacid and methanol, and the composite nanocatalysts prepared in examples 1-7 have excellent esterification activity.
Application example 13
The catalytic performance of the composite nanocatalyst prepared in example 1 in a continuous alkylation reaction of phenol, p-cresol, m-cresol, o-cresol and methanol was evaluated using a fixed bed reactor, and the procedure was as follows:
stainless steel pipe with outer diameter of 10mm, inner diameter of 6mm and length of 300mm is used as a reactor, 1g of composite nano catalyst (particle size of 20-40 meshes) is added, the reaction temperature is 180 ℃, the reaction pressure is 0.2MPa, and the mass airspeed of phenol is 0.5h -1 The molar ratio of methanol to phenol was 3:1, and the analysis conditions were as described in application example 9, and the results are shown in Table 10.
Table 10
Substrate(s) Conversion of phenol (%) Selectivity of target product (%)
Phenol (P) 87.6 85.3
Para-cresol 76.4 80.2
M-cresol 74.5 81.2
O-cresol 72.1 80.4
As can be seen from table 10, the composite nanocatalyst prepared in example 1 was able to efficiently catalyze the alkylation reaction of phenols with methanol.
Application example 14
The catalytic performance of the composite nano catalyst prepared in example 1 in the continuous alkylation reaction of benzene, toluene, ethylbenzene and ethanol or ethylene was evaluated by using a fixed bed reactor, and the operation procedure is as follows:
stainless steel pipe with outer diameter of 10mm, inner diameter of 6mm and length of 300mm is used as a reactor, 1g of composite nano catalyst (particle size of 20-40 meshes) is added, the reaction temperature is 230 ℃, and the mass space velocity of phenol is 0.5h -1 The molar ratio of ethanol to benzene, toluene and ethylbenzene and the molar ratio of ethylene to benzene, toluene and ethylbenzene were 3:1, and the analysis conditions were conducted in accordance with application example 9, and the results are shown in Table 11.
TABLE 11
As can be seen from table 11, the composite nanocatalyst prepared in example 1 is capable of efficiently catalyzing the alkylation of aromatic compounds with ethylene or ethanol.
Application example 15
The catalytic performance of the composite nanocatalyst prepared in example 1 in a mixed phenol (molar ratio of m-cresol to p-cresol of 2:1) and isobutylene or tert-butanol continuous alkylation reaction was evaluated using a fixed bed reactor, and the procedure was as follows:
adopts a diameter of 10mm,Stainless steel pipe with inner diameter of 6mm and length of 300mm is used as a reactor, 1g of composite nano catalyst (particle size of 20-40 meshes) is added, the reaction temperature is 250 ℃, and the mass airspeed of the mixed phenol is 0.5h -1 The molar ratio of isobutylene to mixed phenol and the molar ratio of t-butanol to mixed phenol were 2:1, and the analysis conditions were carried out in accordance with application example 9, wherein isobutylene was used as a raw material, the conversion of m-cresol was 52%, the selectivity of the target product was 85%, the conversion of p-cresol was 53%, and the selectivity of the target product was 84%. The tertiary butanol is used as a raw material, the conversion rate of m-cresol is 55%, the selectivity of a target product is 87%, the conversion rate of p-cresol is 56%, and the selectivity of the target product is 86%.
Application example 16
The catalytic performance of the composite nanocatalyst prepared in example 1 in a continuous alkylation reaction of m-cresol with propylene or isopropanol was evaluated using a fixed bed reactor, and the procedure was as follows:
stainless steel pipe with outer diameter of 10mm, inner diameter of 6mm and length of 300mm is used as a reactor, 1g of composite nano catalyst (particle size of 20-40 meshes) is added, the reaction temperature is 280 ℃, and the mass space velocity of phenol is 0.5h -1 The molar ratio of propylene to m-cresol and the molar ratio of isopropyl alcohol to m-cresol were both 2:1, and the analysis conditions were carried out in accordance with application example 9, with isopropyl alcohol as a raw material, the conversion of m-cresol was 54%, and the selectivity of the objective product was 82%. Propylene was used as a raw material, the conversion of m-cresol was 48%, and the selectivity of the target product was 83%.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. The preparation method of the composite nano catalyst is characterized by comprising the following steps:
mixing polyoxometalate, a template agent and a solvent to obtain a first configuration material;
mixing the first configuration with an alumina precursor to obtain a second configuration;
aging the second configuration material to obtain a solid mixture;
calcining the solid mixture to obtain a composite nano-catalyst, wherein the composite nano-catalyst is porous nano-alumina loaded with polyoxometallate, and the polyoxometallate is loaded on five-coordination aluminum sites of the porous nano-alumina.
2. The method for preparing the composite nano catalyst according to claim 1, wherein the mass ratio of the polyoxometallate, the template agent and the alumina precursor is 1 (2-4): 4-8.
3. The method for preparing the composite nano catalyst according to claim 1, wherein the polyoxometalate is at least one selected from the group consisting of ammonium phosphomolybdate, phosphomolybdic acid, phosphotungstic acid, silicotungstic acid, silicomolybdic acid, sodium phosphotungstate, and sodium silicotungstate;
and/or the template agent is at least one selected from polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, polyoxyethylene polyoxypropylene ether block copolymer, cetyltrimethylammonium bromide, sodium oleate, sodium dodecyl benzene sulfonate, stearic acid, sodium stearate and polyethylene glycol;
and/or the alumina precursor is at least one selected from aluminum isopropoxide, triethylaluminum, triisobutylaluminum, aluminum n-butoxide, aluminum nitrate, aluminum chloride and aluminum sulfate.
4. The method for preparing a composite nanocatalyst according to claim 1, wherein in the step of aging the second formulation, the temperature is 30 ℃ to 80 ℃ and the time is 0.5h to 96h;
and/or in the step of calcining the solid mixture, the calcining temperature is 200-500 ℃, the heating rate is 1-20 ℃/min, and the calcining time is 0.5-6 h.
5. A composite nanocatalyst obtained by the process of preparation of a composite nanocatalyst according to any of claims 1-4, characterized in that the composite nanocatalyst comprises a porous nanocapsule oxide and a polyoxometalate supported on pentadentate aluminum sites of the porous nanocapsule oxide.
6. The composite nanocatalyst of claim 5, wherein the polyoxometallate loading is 1% -60% and the specific surface area of the composite nanocatalyst is 100m 2 /g-800m 2 Per gram, total pore volume of 0.1cm 3 /g-1cm 3 And/g, the average pore diameter is 1nm-10nm.
7. A composite nanocatalyst according to claim 5 or 6 for catalyzing the selective oxidation of aldehydes.
8. A composite nanocatalyst according to claim 5 or 6 for catalyzing the selective oxidation of alcohols.
9. A composite nanocatalyst according to claim 5 or 6 for catalyzing the esterification of an acid with an alcohol or an acid with an alkene.
10. A composite nanocatalyst according to claim 5 or 6 for catalyzing an alkylation reaction of an aromatic compound.
CN202311107451.0A 2023-08-30 2023-08-30 Composite nanocatalyst and its preparation method and application Pending CN117138812A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311107451.0A CN117138812A (en) 2023-08-30 2023-08-30 Composite nanocatalyst and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311107451.0A CN117138812A (en) 2023-08-30 2023-08-30 Composite nanocatalyst and its preparation method and application

Publications (1)

Publication Number Publication Date
CN117138812A true CN117138812A (en) 2023-12-01

Family

ID=88909344

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311107451.0A Pending CN117138812A (en) 2023-08-30 2023-08-30 Composite nanocatalyst and its preparation method and application

Country Status (1)

Country Link
CN (1) CN117138812A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118616096A (en) * 2024-08-12 2024-09-10 浙江大学 Alumina-supported composite catalyst and its preparation method and application

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1235873A (en) * 1998-05-19 1999-11-24 中国石油化工总公司 Silicon dioxide carried heteropoly acid catalyst, its preparation and use
WO2005070854A1 (en) * 2004-01-19 2005-08-04 China Petroleum & Chemical Corporation Solid catalytic process for alylating aromatic hydrocarbon or isometric parafin and olefin
CN101003472A (en) * 2007-01-12 2007-07-25 扬子石油化工股份有限公司 Method for synthesizing crotonic acid by oxidizing croton aldehyde selectively
CN101108360A (en) * 2007-07-05 2008-01-23 北京服装学院 A silicon tungsten, phosphotungstic heteropolyacid supported catalyst for esterification, preparation method and application
CN102247875A (en) * 2010-05-18 2011-11-23 长江大学 Preparation method of heteropoly acid / alumina mesoporous composite material
CN105688906A (en) * 2016-01-14 2016-06-22 同济大学 Method for preparing catalyst for hydrogenolysis of biodiesel by-product glycerinum to produce 1,3-propylene glycol
CN106179321A (en) * 2016-06-24 2016-12-07 天津大学 The method of the alumina mesoporous material that solvent-induced volatilization self assembly tungsten is modified and catalytic applications
CN110841716A (en) * 2019-12-02 2020-02-28 万华化学集团股份有限公司 Catalyst for preparing citral by rearrangement reaction of dehydrolinalool and preparation method thereof, and method for preparing citral

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1235873A (en) * 1998-05-19 1999-11-24 中国石油化工总公司 Silicon dioxide carried heteropoly acid catalyst, its preparation and use
WO2005070854A1 (en) * 2004-01-19 2005-08-04 China Petroleum & Chemical Corporation Solid catalytic process for alylating aromatic hydrocarbon or isometric parafin and olefin
CN101003472A (en) * 2007-01-12 2007-07-25 扬子石油化工股份有限公司 Method for synthesizing crotonic acid by oxidizing croton aldehyde selectively
CN101108360A (en) * 2007-07-05 2008-01-23 北京服装学院 A silicon tungsten, phosphotungstic heteropolyacid supported catalyst for esterification, preparation method and application
CN102247875A (en) * 2010-05-18 2011-11-23 长江大学 Preparation method of heteropoly acid / alumina mesoporous composite material
CN105688906A (en) * 2016-01-14 2016-06-22 同济大学 Method for preparing catalyst for hydrogenolysis of biodiesel by-product glycerinum to produce 1,3-propylene glycol
CN106179321A (en) * 2016-06-24 2016-12-07 天津大学 The method of the alumina mesoporous material that solvent-induced volatilization self assembly tungsten is modified and catalytic applications
CN110841716A (en) * 2019-12-02 2020-02-28 万华化学集团股份有限公司 Catalyst for preparing citral by rearrangement reaction of dehydrolinalool and preparation method thereof, and method for preparing citral

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118616096A (en) * 2024-08-12 2024-09-10 浙江大学 Alumina-supported composite catalyst and its preparation method and application
CN118616096B (en) * 2024-08-12 2024-11-22 浙江大学 Alumina-supported composite catalyst and its preparation method and application

Similar Documents

Publication Publication Date Title
Wang et al. Pd nanoparticles encapsulated into mesoporous ionic copolymer: Efficient and recyclable catalyst for the oxidation of benzyl alcohol with O2 balloon in water
Wang et al. Selective oxidation of glycerol over Pt supported on mesoporous carbon nitride in base-free aqueous solution
Yan et al. Synergistic Pt/MgO/SBA-15 nanocatalysts for glycerol oxidation in base-free medium: Catalyst design and mechanistic study
Biffis et al. Microgel-stabilized gold nanoclusters: Powerful “quasi-homogeneous” catalysts for the aerobic oxidation of alcohols in water
Tao et al. Pd nanoparticles immobilized on sepiolite by ionic liquids: efficient catalysts for hydrogenation of alkenes and Heck reactions
Grass et al. Dependence of gas-phase crotonaldehyde hydrogenation selectivity and activity on the size of Pt nanoparticles (1.7–7.1 nm) supported on SBA-15
Hu et al. Three‐Dimensionally Hierarchical Pt/C Nanocomposite with Ultra‐High Dispersion of Pt Nanoparticles as a Highly Efficient Catalyst for Chemoselective Cinnamaldehyde Hydrogenation
Li et al. Selective aerobic oxidation of glycerol over zirconium phosphate-supported vanadium catalyst
CN117138812A (en) Composite nanocatalyst and its preparation method and application
Masuda et al. Synthesis of active, robust and cationic Au 25 cluster catalysts on double metal hydroxide by long-term oxidative aging of Au 25 (SR) 18
Wang et al. Aerobic oxidation of benzyl alcohol in water catalyzed by gold nanoparticles supported on imidazole containing crosslinked polymer
CN107876047A (en) A kind of preparation method of α, β unsaturated aldehyde/ketone hydrogenation Pd/C catalyst
CN115007184A (en) Nitrogen-doped carbon-loaded ruthenium-iron bimetallic catalyst and preparation method and application thereof
US20190054454A1 (en) Mechanically strong catalyst and catalyst carrier, its preparation, and its use
Nakato et al. Unique catalysis of an acidic salt of heteropoly acid, Cs2. 5H0. 5PW12O40, consisting of microcrystallites
CN111111774A (en) Organic phosphine-containing polymer carrier loaded rhodium and heteropoly acid catalyst, preparation and application thereof
CN118616096B (en) Alumina-supported composite catalyst and its preparation method and application
CN106391000A (en) Pd(111)/γ-Al2O3 catalyst for CO dehydrogenation purification reaction and preparation method thereof
Yang et al. Effect of organic moieties (phenyl, naphthalene, and biphenyl) in Zr-MIL-140 on the hydrogenation activity of Pd nanoparticles
CN110075835A (en) A kind of catalyst and its preparation method and application of step oxidative esterification legal system methyl methacrylate
Jiang et al. Convenient preparation of Pd/RGO catalyst for the efficient hydrodechlorination of various chlorophenols
CN115337943A (en) Catalyst for synthesizing isoprene, preparation method thereof and synthesis method of isoprene
García-Bosch et al. Tracking the paths for the sucrose transformations over bifunctional Ru-POM/AC catalysts
CN114522683B (en) Carbon-supported Pd-M bimetallic single-atom catalyst and application thereof in C2H2Application in double carbonylation reaction
CN118267997A (en) Catalyst applied to propane dehydrogenation and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination