CN116174019A - Composite catalytic material containing metal elements and molecular sieve, and preparation method and application thereof - Google Patents

Composite catalytic material containing metal elements and molecular sieve, and preparation method and application thereof Download PDF

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CN116174019A
CN116174019A CN202111424565.9A CN202111424565A CN116174019A CN 116174019 A CN116174019 A CN 116174019A CN 202111424565 A CN202111424565 A CN 202111424565A CN 116174019 A CN116174019 A CN 116174019A
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molecular sieve
catalytic material
composite catalytic
aggregate
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夏长久
厉晨豪
浦宁
彭欣欣
朱斌
林民
罗一斌
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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    • 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
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    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
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    • 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
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract

The present disclosure relates to a metal nanoparticle and molecular sieve composite catalytic material, a preparation method and application thereof, wherein the composite catalytic material comprises an all-silicon molecular sieve and metal elements M dispersed in crystals of the all-silicon molecular sieve; the metal element M is a metal element capable of forming an oxide aggregate; the composite catalytic material has the following H 2 -TPR features: the composite catalytic material is in H 2 Reduction peak temperature T in TPR test 1 The oxide aggregate is at H 2 Reduction peak temperature T in TPR test 2 Such asT defined by the following formula (1) 0 Is any value between 350 ℃ and 600 ℃; t (T) 0 ＝T 1 ‑T 2 Formula (1). The composite catalytic material has large specific surface area, pore volume and macromolecular substrate reaction activity; the metal oxide particles have uniform particle size and are uniformly dispersed in the molecular sieve pore channels.

Description

Composite catalytic material containing metal elements and molecular sieve, and preparation method and application thereof
Technical Field
The present disclosure relates to the field of catalytic materials, and in particular, to a composite catalytic material containing metal elements and molecular sieves, and a preparation method and application thereof.
Background
In recent years, nanotechnology and unique physical and chemical properties of nanoparticles have attracted widespread attention, and research involving "nano" in various fields has been rapidly progressed. It was found by research that catalytic reactions often cannot occur on Bulk (Bulk) metal surfaces, nor is the catalytic problem a single molecule or single atom problem. Early concepts considered that the catalytically active unit was a collection of clusters of several or more atoms. For example, metal supported catalysts used in petrochemical industry have about 1018 active sites per cubic centimeter, and the specific surface area of the support is 50 to 300m 2 ·g -1 The scale of the active sites should be between 1 and 10nm, another important aspect is that molecular sieves with a regular pore structure occupy very important positions in the catalyst supports used today. The effective aperture of the molecular sieve can be from a few tenths of nanometers to tens of nanometers or even can be ten nanometers according to the mixture ratio of raw materials and the different synthesis methodsModulation between hundreds of nanometers. The catalytic reactions occurring in these nanopores with specific structures have very unique properties such as regioselectivity, molecular shape selectivity, etc.
The microporous molecular sieve can only be diffused by reactants with small molecular size due to the limitation of pore channels, so that the reaction participated by a macromolecular substrate cannot be catalyzed. In order to overcome the defect, mesopores and even macropores are introduced into the microporous molecular sieve to construct the molecular sieve with multi-stage pore diameters, so that the performance of the microporous molecular sieve when the microporous molecular sieve is applied to macromolecular reactants is improved. According to different synthesis methods, the synthesis method of the hierarchical pore molecular sieve mainly comprises a skeleton atom removal method, a double-template agent synthesis method ordered micro-mesoporous composite molecular sieve, a hard template agent method, a dry gel conversion method and a silanization method. Among them, the silylation method is a relatively simple and widely used method. The silicon hydroxyl of the silanization reagent and the silicon hydroxyl of the molecular sieve precursor are hydrolyzed and condensed to generate stable Si-O-Si bond, so that the realization of the expanding effect of the support layer is ensured.
Wang Baorong et al (CN 111847471 a) prepared a hierarchical pore molecular sieve encapsulating active metals by introducing silylating agents in a direct hydrothermal synthesis process. However, since the above process is performed under strongly alkaline and high temperature hydrothermal conditions, the metal precursor is extremely prone to form hydroxide precipitates. Without solving this problem, the precursor metal ion often forms a complex with a lone pair-containing ligand (e.g., an organic amine ligand or ammonia, etc.), such as Wang, etc., using an ethylenediamine ligand with PdCl 2 Formation of [ Pd (NH) 2 CH 2 CH 2 NH 2 )]Cl 2 The complex precursor is directly synthesized into the silicalite-1 molecular sieve (Pd@silicalite-1) embedding and dispersing uniformly Pd nano particles by a hydrothermal crystallization method. In summary, the method of complexing a metal precursor with an organic ligand and then introducing the complex into the hydrothermal crystallization process of a molecular sieve is a relatively effective method for highly dispersing nano particles in crystals of the molecular sieve. While the silylation process in which the silylating agent is introduced into the molecular sieve synthesis process is an efficient and simple process for preparing a hierarchical pore molecular sieve. However, it is difficult to achieve both of the above objects at the same time in the general studies of the prior art, and to obtain a molecular sieve having both advantages, i.e., it is difficult to directly obtainThen preparing the multistage pore molecular sieve with the metal nano particles highly dispersed.
Disclosure of Invention
The purpose of the present disclosure is to provide a composite catalytic material containing metal elements and molecular sieves, and a preparation method and application thereof, wherein the composite catalytic material has a large specific surface area, a large pore volume and a large molecular substrate reaction activity; the metal oxide particles have uniform particle size and are uniformly dispersed in the molecular sieve pore channels.
To achieve the above object, a first aspect of the present disclosure provides a metal nanoparticle and molecular sieve composite catalytic material, including an all-silicon molecular sieve and a metal element M dispersed in crystals of the all-silicon molecular sieve; the metal element M is a metal element capable of forming an oxide aggregate; the composite catalytic material has the following H 2 -TPR features: the composite catalytic material is in H 2 Reduction peak temperature T in TPR test 1 The oxide aggregate is at H 2 Reduction peak temperature T in TPR test 2 T as defined by the following formula (1) 0 Is any value between 350 and 600 ℃; t (T) 0 ＝T 1 -T 2 Formula (1).
Optionally, said T 0 The value of (2) is any value between 350 and 550 ℃.
Optionally, the all-silicon molecular sieve in the composite catalytic material is at least one of an MFI structure molecular sieve, an MEL structure molecular sieve, a BEA structure molecular sieve, an MWW structure molecular sieve, a two-dimensional hexagonal structure molecular sieve, an MOR structure molecular sieve, a TUN structure molecular sieve and a silicon molecular sieve with other structures; preferably one or more selected from MFI structure molecular sieve, MEL structure molecular sieve, BEA structure molecular sieve, MCM structure molecular sieve and SBA structure molecular sieve; further preferably one or more of MFI structure molecular sieve, MEL structure molecular sieve and BEA structure molecular sieve; further preferred are MFI structure molecular sieves;
the metal M is selected from one or more of manganese, iron, cobalt, nickel, palladium, platinum, copper and gold.
Optionally, the metal M is Co, and the oxide aggregate is Co 3 O 4 An aggregate;
the metal M is Mn, and the oxide aggregate is MnO 2 An aggregate;
the metal M is Fe, and the oxide aggregate is Fe 2 O 3 An aggregate;
the metal M is Ni, and the oxide aggregate is NiO aggregate;
the metal M is Pd, and the oxide aggregate is a PdO aggregate;
the metal M is Pt, and the oxide aggregate is PtO 2 An aggregate; or alternatively
The metal M is Cu, and the oxide aggregate is CuO aggregate.
Optionally, in the composite catalytic material, the molar ratio of the metal M element to the silicon element is (0.001-0.25): 1, preferably (0.001 to 0.2): 1.
optionally, the BET specific surface area of the composite catalytic material is 400-800 m 2 And/g, wherein the total pore volume is 0.30-0.65 mL/g, the micropore volume is 0.10-0.19 mL/g, the mesopore volume is 0.18-0.46 mL/g, the metal element M in the composite catalytic material exists in the form of metal nano particles, and the average particle size of the metal nano particles is 0.5-8.0 nm.
A second aspect of the present disclosure provides a method of preparing a metal nanoparticle and molecular sieve composite catalytic material, comprising the steps of: s1, mixing a template agent, a silicon source, water, a metal M precursor, a silanization reagent and peroxide to obtain a reaction mixture, wherein the silanization reagent comprises at least one coordination group complexed with metal M ions; s2, carrying out hydrothermal crystallization treatment and roasting treatment on the reaction mixture.
Optionally, in step S1, siO is used 2 Silicon source: template agent: water: metal element M: the molar ratio of the silylating agent is 1: (0.001-1): (5-100): (0.001-0.25): (0.025 to 0.4), preferably 1: (0.005-0.5): (5-100): (0.001-0.2): (0.025-0.3); the molar ratio of the peroxide to the metal element M is (0.5-5): 1.
optionally, step S1 includes:
a. mixing a template agent, a silicon source and water to obtain a silicon hydrolysis solution;
b. adding peroxide into the aqueous solution of the metal M precursor, and mixing to obtain a first mixed material; mixing the first mixed material with the silicon hydrolysis solution to obtain a second mixed material;
c. adding a silylation reagent into the second mixed material, and mixing to obtain the reaction mixture;
preferably, the conditions of mixing in step c include: stirring at 20-80 deg.c for 0.5-2 hr.
Optionally, the silicon source is selected from at least one of silicone grease, solid silica gel, white carbon black and silica sol; preferably at least one selected from the group consisting of silicone grease, solid silica gel and white carbon black;
further preferred is a silicone grease having a structure represented by the following formula (A):
Figure BDA0003378499830000041
Wherein R is a 、R b 、R c 、R d Each independently selected from alkyl groups having 1 to 6 carbon atoms, said alkyl groups being branched or straight chain alkyl groups; preferably, R a 、R b 、R c 、R d Each independently selected from a straight chain alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms; further preferably, the R a 、R b 、R c 、R d Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl; further preferably, the organic silicone grease is selected from one or more of tetramethyl silicate, tetraethyl silicate, tetrabutyl silicate and dimethyl diethyl silicone grease.
Optionally, in step S1, the template agent is an organic base, preferably at least one selected from quaternary ammonium base, aliphatic amine and aliphatic alcohol amine; further preferably, the template is at least one selected from quaternary ammonium bases having a structure represented by the following formula (B):
Figure BDA0003378499830000051
R 1 、R 2 、R 3 and R is 4 Each selected from alkyl groups having 1 to 4 carbon atoms, preferably straight chain alkyl groups having 1 to 4 carbon atoms and branched alkyl groups having 3 to 4 carbon atoms, more preferably R 1 、R 2 、R 3 And R is 4 At least one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl;
Further preferably, the molecular sieve in the composite catalytic material is an MFI type molecular sieve, and the template agent is tetrapropylammonium hydroxide or a mixture of tetrapropylammonium hydroxide and one or more selected from tetrapropylammonium chloride and tetrapropylammonium bromide; or alternatively
The molecular sieve in the composite catalytic material is MEL type molecular sieve, and the template agent is tetrabutylammonium hydroxide or a mixture of tetrabutylammonium hydroxide and one or more selected from tetrabutylammonium chloride and tetrabutylammonium bromide; or alternatively
The molecular sieve in the composite catalytic material is Beta-type molecular sieve, and the template agent is tetraethylammonium hydroxide or a mixture of tetraethylammonium hydroxide and one or more selected from tetraethylammonium chloride and tetraethylammonium bromide.
Optionally, in the step a, the silicon source is organic silicone grease, and the step a further comprises hydrolysis alcohol removal treatment after the template agent, the organic silicone grease and water are mixed to obtain a hydrolysis solution of the silicon;
the conditions for the hydrolysis alcohol expelling treatment comprise: stirring and hydrolyzing for 2-10 hours at 0-95 ℃; preferably at 50-95 deg.C for 2-8 hr.
Optionally, in step S1, the metal M precursor is one or more of an inorganic metal compound and an organic metal compound; the inorganic metal compound is water-soluble inorganic salt of metal M; the water-soluble inorganic salt of the metal M is selected from one or more of chloride, hydrated chloride, sulfate, hydrated sulfate and nitrate of the metal M; the organic metal compound is an organic ligand compound of metal M; preferably, the metal M precursor is a water-soluble inorganic salt of metal M;
The metal M is selected from one or more of manganese, iron, cobalt, nickel, palladium, platinum, copper and gold;
preferably, the molar ratio of the metal M element to water in the aqueous solution of the metal M precursor is 1: (50-500).
Optionally, in step S1, the silylating agent has the general formula R 5 Si(R 6 )(R 7 )R 8 Wherein R is 5 、R 6 、R 7 、R 8 Each independently is halogen, alkyl, alkoxy, aryl, mercapto or amino, and R 5 、R 6 、R 7 、R 8 At least one of which is alkyl, alkoxy, aryl, mercapto or amino; the alkyl, alkoxy, mercapto and amino groups each independently have 1 to 18 carbon atoms, and the aryl group has 6 to 18 carbon atoms;
preferably, the silylating agent is selected from one or more of dimethyldichlorosilane, N-phenyl-3-aminopropyl trimethoxysilane, phenyl trimethoxysilane, 1, 7-dichlorooctanethyltetrasiloxane, hexadecyl trimethoxysilane, octyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane and-mercaptopropyl trimethoxysilane; further preferred is at least one selected from the group consisting of N-phenyl-3-aminopropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane and 3-mercaptopropyl trimethoxysilane.
Optionally, in step S1, the peroxide is one or more of hydrogen peroxide or organic peroxide; the organic peroxides include cumene hydroperoxide, ethylbenzene hydroperoxide and tert-butyl hydroperoxide.
Optionally, in step S2, the conditions of the hydrothermal crystallization treatment include: under autogenous pressure, the hydrothermal crystallization time is 0.5-10 days, and the hydrothermal crystallization temperature is 110-200 ℃; preferably, the hydrothermal crystallization time is 0.5-5 days, and the hydrothermal crystallization temperature is 150-200 ℃;
the conditions of the calcination treatment include: roasting temperature is 400-900 ℃ and roasting time is 1-16 hours; preferably, the roasting temperature is 400-800 ℃ and the roasting time is 2-8 hours.
A third aspect of the present disclosure provides a metal nanoparticle and molecular sieve composite catalytic material prepared according to the method of the second aspect of the present disclosure.
A fourth aspect of the present disclosure provides the use of the metal nanoparticle and molecular sieve composite catalytic material of the first or third aspect of the present disclosure in catalyzing a co-oxidation reaction of a macromolecular aldehyde/olefin; preferably in catalyzing the co-oxidation of cyclooctene and isobutyraldehyde.
Through the technical scheme, the disclosure provides a metal nanoparticle and molecular sieve composite catalytic material, and a preparation method and application thereof, wherein the composite catalytic material is prepared by simultaneously adding a metal precursor, a silanization reagent and peroxide into a crystallization system, and the molecular sieve of the prepared composite catalytic material has large specific surface area, pore volume and macromolecular substrate reaction activity; the molecular sieve of the prepared composite catalytic material has a multi-level pore structure, and the metal oxide nano particles have uniform particle size and are uniformly dispersed in mesoporous pore channels of the multi-level pore molecular sieve; at H 2 In the TPR test, the reduction peak temperature of the composite catalytic material is 350-600 ℃ higher than that of the oxide aggregate of the metal element M, and the composite catalytic material has higher catalytic activity in the co-oxidation reaction of cyclooctene and isobutyraldehyde.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
FIG. 1 is a metal-containing composition prepared in example 1H of hierarchical pore MFI structure molecular sieve 2 -TPR profile.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
The inventor of the present disclosure surprisingly found in experiments that, after introducing a metal precursor during the crystallization synthesis of a molecular sieve and then continuously introducing a silylating agent and peroxide, and performing hydrothermal crystallization, washing and roasting on the obtained mixture, the obtained composite catalytic material comprising the all-silicon molecular sieve and metal M-oxide nanoparticles has a larger specific surface area and pore volume, the metal oxide nanoparticles have uniform particle size and are uniformly dispersed in the pore channels of the molecular sieve, and when T is contained in the composite catalytic material 0 (i.e.T 1 -T 2 ) Has a value of 350 ℃ or higher (T) 1 Indicating that the composite catalytic material is in H 2 Reduction peak temperature, T in TPR test 2 Indicating that the oxide aggregate is at H 2 The reduction peak temperature in the TPR test), the composite catalytic material has good catalytic activity in the co-oxidation reaction of macromolecular aldehydes/olefins, for example, when used in the co-oxidation reaction of cyclooctene and isobutyraldehyde, higher cyclooctene conversion and cyclooctene oxide selectivity can be obtained.
A first aspect of the present disclosure provides a metal oxide nanoparticle and molecular sieve composite catalytic material comprising an all-silicon molecular sieve and a metal element M dispersed within crystals of the all-silicon molecular sieve; the metal element M is a metal element capable of forming an oxide aggregate;
the composite catalytic material has the following H 2 -TPR features:
the composite catalytic material is in H 2 Reduction peak temperature T in TPR test 1 ，
The oxide aggregate is at H 2 Reduction peak temperature T in TPR test 2 ，
T as defined by the following formula (1) 0 Is any value between 350 and 600 ℃;
T 0 ＝T 1 -T 2 formula (1).
The present disclosure provides a metal oxide nanoparticle and molecular sieve composite catalytic material, the molecular sieve of the composite catalytic material having a large specific surface area, pore volume and macromolecular substrate reaction activity; the metal oxide nano particles have uniform particle size and are uniformly dispersed in mesoporous pore channels of the hierarchical pore molecular sieve; the composite catalytic material has higher catalytic activity in the co-oxidation reaction of cyclooctene and isobutyraldehyde.
In the present disclosure, metal M oxide aggregates refer to the species of conventional oxides obtained after calcination treatment of metal M precursors (e.g., nitrates, chlorides, etc.) known in the art during molecular sieve synthesis, e.g., metal cobalt oxide aggregates are Co 3 O 4 The aggregate of the oxide of the metallic copper is CuO.
In the present disclosure, H 2 The TPR test refers to a hydrogen temperature programming reduction characterization method, wherein the composite catalytic material is reduced in the temperature programming process, and information of interaction between metal oxides or between the metal oxides and a carrier in the reduction process of the supported metal catalyst can be provided. In the present disclosure H 2 TPR test AutoChemII2920, test conditions include: 10% by volume H 2 90% Ar by volume, 50ml/min, 60-900 ℃.
In a preferred embodiment, said T 0 The value of (2) is any value between 350 and 550 ℃. T of composite catalytic material 0 Within this range, there is higher catalytic activity, and cyclooctene conversion and cyclooctene epoxide selectivity are higher.
In one embodiment, the all-silicon molecular sieve in the composite catalytic material is one or more of MFI structure molecular sieve (such as S-1), MEL structure molecular sieve (such as S-2), BEA structure molecular sieve (such as Beta), MWW structure molecular sieve (such as MCM-22), two-dimensional hexagonal structure molecular sieve (such as MCM-41, SBA-15), MOR structure molecular sieve (such as MOR), TUN structure molecular sieve (such as TUN) and silicon molecular sieve with other structures (such as ZSM-48, MCM-48); preferably one or more selected from MFI structure molecular sieve, MEL structure molecular sieve, BEA structure molecular sieve, MCM structure molecular sieve and SBA structure molecular sieve; further preferably one or more of MFI structure molecular sieve, MEL structure molecular sieve and BEA structure molecular sieve, such as one of S-1, S-2 and Beta; further preferred are MFI structure molecular sieves, such as S-1.
The metal M is selected from one or more of manganese, iron, cobalt, nickel, palladium, platinum, copper and gold; preferably one or more selected from manganese, iron, cobalt, nickel, palladium, platinum and copper.
In an alternative embodiment, the metal M is Co and the oxide aggregate is Co 3 O 4 An aggregate;
in an alternative embodiment, the metal M is Mn and the oxide aggregate is MnO 2 An aggregate;
in an alternative embodiment, the metal M is Fe and the oxide aggregate is Fe 2 O 3 An aggregate;
in an alternative embodiment, the metal M is Ni and the oxide aggregate is NiO aggregate;
in an alternative embodiment, the metal M is Pd and the oxide aggregates are PdO aggregates;
in an alternative embodiment, the metal M is Pt and the oxide aggregate is PtO 2 An aggregate;
in an alternative embodiment, the metal M is Cu and the oxide aggregate is CuO aggregate.
In one embodiment, in the composite catalytic material, the molar ratio of the metal M element to the silicon element is (0.001 to 0.25): 1, preferably (0.001 to 0.2): 1.
in one embodiment, the metal element M in the composite catalytic material is present in the form of metal nanoparticles having an average particle diameter of 0.5 to 8.0nm, preferably 1 to 7.5nm; BET specific surface area of 400-800 m 2 Preferably 400 to 750m 2 /g; the total pore volume is 0.3-0.65 m 2 Preferably 0.31 to 0.63m 2 /g；The micropore volume is 0.1-0.19 mL/g, preferably 0.11-0.18 mL/g; the mesoporous volume is 0.15-0.46 mL/g, preferably 0.18-0.46 mL/g. The composite catalytic material also has a multi-stage pore structure, which is beneficial to catalyzing the catalytic reaction of different sizes of reaction substrates, especially macromolecular substrates.
A second aspect of the present disclosure provides a method of preparing a metal nano-oxide particle and molecular sieve composite catalytic material, comprising the steps of:
s1, mixing a template agent, a silicon source, water, a metal M precursor, a silanization reagent and peroxide to obtain a reaction mixture, wherein the silanization reagent comprises at least one coordination group complexed with metal M ions;
s2, carrying out hydrothermal crystallization treatment and roasting treatment on the reaction mixture.
The metal precursor, the silanization reagent and the peroxide are introduced into the molecular sieve synthesis raw material, so that the effects of expanding the pores of the highly dispersed metal oxide nano particles and the molecular sieve support layer can be considered, and the multistage pore molecular sieve composite catalytic material of the highly dispersed metal oxide nano particles can be prepared.
In the method, the peroxide can play a role of complexing metal, so as to achieve the effects of dispersing and stabilizing the metal; a silanization reagent with one or more coordination groups (the coordination groups can be at least one of amino, mercapto and oxygen-containing coordination groups) is also added into the reaction mixture, the coordination groups can complex metals to achieve the effect of fixing and dispersing metals, and the layering effect of alkyl chains plays a role of expanding pores; thus preparing the hierarchical pore all-silicon molecular sieve with highly dispersed metal oxide nano particles. And the high-dispersity metal M oxide nano particles formed by the metal M introduced in the synthesis process of the molecular sieve enter the crystal of the molecular sieve, and partial metal oxide nano particles can also exist to form among crystals and on the surface (such as pore channel surface) of the molecular sieve.
In one embodiment, siO 2 Silicon source: template agent: water: metal element M: the molar ratio of the silylating agent is 1: (0.001-1): (5-100): (0.001-0.25): (0.025 to 0.4), preferably 1: (0.005 to 0.5): (5-100): (0.001-0.2): (0.025-0.3); the molar ratio of the peroxide to the metal element M is (0.5-5): 1. specifically, the water used in step S1 may be water commonly used in synthesizing molecular sieves, and deionized water is preferred in order to avoid the introduction of heteroatoms.
In a preferred embodiment, step S1 comprises:
a. mixing a template agent, a silicon source and water to obtain a silicon hydrolysis solution;
b. adding peroxide into the aqueous solution of the metal M precursor, and mixing to obtain a first mixed material; mixing the first mixed material with the silicon hydrolysis solution to obtain a second mixed material;
c. adding a silylation reagent into the second mixed material, and mixing to obtain the reaction mixture; preferably, the conditions of mixing in step c include: stirring at 20-80 deg.c for 0.5-2 hr.
In one embodiment, in step S1, the silicon source is at least one selected from the group consisting of silicone grease, solid silica gel, white carbon black, and silica sol; preferably at least one selected from the group consisting of silicone grease, solid silica gel and white carbon black; the general formula of the silicone grease is a structure shown in the following formula (A):
Figure BDA0003378499830000111
Wherein R is a 、R b 、R c 、R d Each independently selected from alkyl groups having 1 to 6 carbon atoms, said alkyl groups being branched or straight chain alkyl groups; preferably, R a 、R b 、R c 、R d Each independently selected from a straight chain alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms. For example R a 、R b 、R c 、R d Each independently is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. Further preferably R a 、R b 、R c 、R d Each independently is methyl or ethyl.
In a preferred embodiment, the silicone grease is selected from one or more of tetramethyl silicate, tetraethyl silicate, tetrabutyl silicate and dimethyl diethyl silicone grease.
According to the present disclosure, in step S1, the template agent is an organic base, preferably at least one selected from the group consisting of quaternary ammonium bases, aliphatic amines, and aliphatic alcohol amines. Wherein, the quaternary ammonium base can be organic quaternary ammonium base; the aliphatic amine may be NH 3 A compound formed by substituting at least one hydrogen of the compound with an aliphatic hydrocarbon group (e.g., an alkyl group); the aliphatic alcohol amine can be various NH 3 A compound in which at least one hydrogen is substituted with an aliphatic group having a hydroxyl group (e.g., an alkyl group).
Further preferably, the template is at least one selected from structural quaternary ammonium bases represented by the following formula (B):
Figure BDA0003378499830000121
R 1 、R 2 、R 3 And R is 4 Each selected from alkyl groups having 1 to 4 carbon atoms, preferably straight chain alkyl groups having 1 to 4 carbon atoms and branched alkyl groups having 3 to 4 carbon atoms, more preferably R 1 、R 2 、R 3 And R is 4 Each is selected from at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
The template is preferably at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide (including various isomers of tetrapropylammonium hydroxide, such as tetra-n-propylammonium hydroxide and tetraisopropylammonium hydroxide), and tetrabutylammonium hydroxide (including various isomers of tetrabutylammonium hydroxide, such as tetra-n-butylammonium hydroxide and tetraisobutylammonium hydroxide).
In a preferred embodiment, the molecular sieve in the composite catalytic material is an MFI-type molecular sieve, and the template agent is tetrapropylammonium hydroxide or a mixture of tetrapropylammonium hydroxide and one or more selected from tetrapropylammonium chloride and tetrapropylammonium bromide; or alternatively
The molecular sieve in the composite catalytic material is MEL type molecular sieve, and the template agent is tetrabutylammonium hydroxide or a mixture of tetrabutylammonium hydroxide and one or more selected from tetrabutylammonium chloride and tetrabutylammonium bromide; or alternatively
The molecular sieve in the composite catalytic material is Beta-type molecular sieve, and the template agent is tetraethylammonium hydroxide or a mixture of tetraethylammonium hydroxide and one or more selected from tetraethylammonium chloride and tetraethylammonium bromide. The molecular sieve with different structures can be prepared by selecting different templates.
In one embodiment, in step S1, the silicon source is an organosilicon grease, and the method further includes hydrolysis alcohol removal treatment after mixing the template agent, the organosilicon grease and water to obtain a hydrolysis solution of the silicon;
the conditions for the hydrolysis alcohol expelling treatment comprise: stirring and hydrolyzing for 2-10 hours at 0-95 ℃; preferably at 50-95 deg.C for 2-8 hr. Preferably, the hydrolysis alcohol-expelling treatment is performed so that the mass content of alcohol produced by hydrolysis of the obtained silicone grease in the silicon hydrolysis solution is 10ppm or less.
According to the present disclosure, the metal precursor may have a wide range of types, and any material containing the metal (e.g., a compound containing a metal element and/or a metal simple substance) may achieve the object of the present disclosure.
In one embodiment, in step S1, the metal M precursor is one or more of an inorganic metal compound and an organic metal compound; the organic metal compound is water-soluble inorganic salt of metal M; the water-soluble inorganic salt of the metal M is selected from one or more of chloride, hydrated chloride, sulfate, hydrated sulfate and nitrate of the metal M; the organic metal compound is an organic ligand compound of metal M; preferably, the metal M precursor is a water-soluble inorganic salt of metal M;
The metal M is selected from one or more of manganese, iron, cobalt, nickel, palladium, platinum, copper and gold;
preferably, the metal M precursor is an aqueous solution of metal M precursor, and the molar ratio of metal M element to water in the aqueous solution of metal M precursor is 1: (50-500).
In one embodiment, in step S1, the silylating agent has the general formula R 5 Si(R 6 )(R 7 )R 8 Wherein R is 5 、R 6 、R 7 、R 8 Each independently is halogen, alkyl, alkoxy, aryl, mercapto or amino, and R 5 、R 6 、R 7 、R 8 At least one of which is alkyl, alkoxy, aryl, mercapto or amino; the alkyl, alkoxy, mercapto and amine groups each independently have 1 to 18 carbon atoms, preferably 1 to 12; the number of carbon atoms of the aromatic group may be 6 to 18, preferably 6 to 12;
preferably, the silylating agent is selected from one or more of dimethyldichlorosilane, N-phenyl-3-aminopropyl trimethoxysilane, phenyl trimethoxysilane, 1, 7-dichlorooctanethyltetrasiloxane, hexadecyl trimethoxysilane, octyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane and 3-mercaptopropyl trimethoxysilane; further preferred is at least one selected from the group consisting of N-phenyl-3-aminopropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane and 3-mercaptopropyl trimethoxysilane.
In one embodiment, in step S1, the peroxide is one or more of hydrogen peroxide or organic peroxide; the organic peroxides include Cumene Hydroperoxide (CHP), ethylbenzene hydroperoxide (EBHP) and tert-butyl hydroperoxide (TBHP).
In one embodiment, in step S2, the conditions of the hydrothermal crystallization treatment include: under autogenous pressure, the hydrothermal crystallization time is 0.5-10 days, and the hydrothermal crystallization temperature is 110-200 ℃; preferably, the hydrothermal crystallization time is 0.5-5 days, and the hydrothermal crystallization temperature is 150-200 ℃.
In one embodiment, in step S2, the conditions of the baking process include: roasting temperature is 400-900 ℃ and roasting time is 1-16 hours; preferably, the roasting temperature is 400-800 ℃ and the roasting time is 2-8 hours.
A third aspect of the present disclosure provides a metal oxide nanoparticle and molecular sieve composite catalytic material prepared according to the method of the second aspect of the present disclosure.
A fourth aspect of the present disclosure provides the use of the metal oxide nanoparticles of the first or third aspect of the present disclosure with a molecular sieve composite catalytic material in catalyzing a co-oxidation reaction of a macromolecular aldehyde/olefin; preferably in catalyzing the co-oxidation of cyclooctene and isobutyraldehyde.
In a specific embodiment, the reaction conditions in the use of catalyzing the co-oxidation of cyclooctene and isobutyraldehyde include: the molar ratio of isobutyraldehyde to cyclooctene is 2-8: 1, taking the total weight of isobutyraldehyde and cyclooctene as a reference, wherein the weight ratio of the metal nano particles to the molecular sieve composite catalytic material is 1-20 percent; 0.1-2 MPa, the reaction temperature is 20-120 ℃ and the reaction time is 2-48 hours. Alternatively, the reaction is carried out in a slurry bed reactor.
When the composite catalytic material is used for catalyzing the co-oxidation reaction of cyclooctene and isobutyraldehyde, the conversion rate of cyclooctene is not lower than 75mol percent, the selectivity of the target product cyclooctene is not lower than 85mol percent, and the conversion rate of isobutyraldehyde is not lower than 98mol percent.
The present disclosure will be further illustrated by the following examples.
In the present disclosure, H is performed on AutoChemII2920 2 TPR experiment, experimental conditions: 10% H 2 90% Ar,50ml/min, 60-900 ℃.
Transmission electron microscopy TEM of the samples was obtained on a TecnaiG2F20S-TWIN transmission electron microscope from FEI company. The average particle diameter of the metal oxide nanoparticles was obtained according to TEM electron microscopy.
The total specific surface area and total pore volume of the samples were measured on a Micromeritics company ASAP245 static nitrogen adsorber according to the standard method of ASTMD 4222-98. The determination of adsorption isotherms and desorption isotherms for low temperature nitrogen adsorption of the samples was performed according to astm d4222-98 standard method.
In the present disclosure, the X-ray diffraction (XRD) pattern measurement of the sample was performed on a siemens d5005 type X-ray diffractometer with a source of kα (Cu) and a test range of 2θ from 0.5 ° to 70 °.
The cobalt nitrate used in the embodiments of the present disclosure is cobalt nitrate hexahydrate.
Example 1
(1) 1.6g of a water solution of tetrapropylammonium hydroxide (TPAOH, 0.002 mol) with a concentration of 25.05 wt%, 20.8g of tetraethyl silicate (0.1 mol) and 52.8g (3 mol) of water are sequentially added into a 500mL beaker, put on a magnetic stirrer with heating and stirring functions to be uniformly mixed, and stirred at 50 ℃ for 2 hours, and evaporated water is periodically supplemented to obtain a colorless transparent silica gel solution;
(2) Stirring 0.03g of cobalt nitrate hexahydrate (0.0001 mol) and 0.18g of water (0.01 mol) uniformly, and adding 0.05 mmole of H 2 O 2 Mixing the aqueous solution of cobalt with the silicon hydrolysis solution obtained in the step (1);
(3) To the mixture of step (2) was added 0.64g of N-phenyl-3-aminopropyl trimethoxysilane (PHAPTMS, 0.0025 mol) and stirred for 0.5 hours;
(4) Transferring the mixture obtained in the step (3) into a stainless steel closed reaction kettle, crystallizing at the constant temperature of 175 ℃ for 24 hours to obtain a sample, filtering and washing the obtained sample, drying at the temperature of 110 ℃ for 6 hours, and roasting in a muffle furnace at the temperature of 600 ℃ for 6 hours to obtain a metal oxide nanoparticle and multistage hole all-silicon molecular sieve composite catalytic material product which is marked as C-1. Its H 2 The TPR diagram is shown in fig. 1.
The BET specific surface area, total pore volume, micropore volume, mesopore volume and the average particle diameter of the metal nanoparticles contained in the C-1 are shown in Table 2. H of C-1 2 The TPR spectrum is shown in FIG. 1.
Comparative example 1
This comparative example was prepared as in example 1, except that no silylating agent was added, and the proportions and synthesis conditions, results are set forth in Table 1. Other conditions and operations refer to example 1. The product obtained was designated as sample DC-1.
Comparative example 2
Under the stirring condition, mixing tetraethoxysilane, tetrapropylammonium hydroxide, cobalt nitrate and deionized water to obtain SiO with the molar ratio of 2 : structure directing agent: co: h 2 O=1: 0.2:0.001: 30; stirring at 50℃for 2 hours;
then according to SiO 2 : silylating agent = 1:0.025 molar ratio, adding PHAPTMS into the first mixture, stirring for 0.5h, and transferring the second mixture into a pressure-resistant stainless steel reaction kettle; under stirring, heating to 170℃and crystallizing for 8h under autogenous pressure. After the stainless steel pressure-resistant reaction kettle is cooled to room temperature, recovering crystallized products, drying at 110 ℃ for 6 hours, and roasting at 550 ℃ for 4 hours to obtain the multi-stage pore molecular sieve for encapsulating molybdenum. The product obtained was designated as sample DC-2.
Comparative example 3
This comparative example was prepared according to the method of NingWang et al (JACS, 2016, vol.138 pages 7484-7487).
Deionized water was mixed with 10.8g of TPAOH solution and stirred continuously for 10 minutes, then 8.32g of ethyl orthosilicate (0.04 mol) was added. After stirring continuously for 6 hours, the mixture became clear after complete hydrolysis. Preparation of [ Pd (NH) by dissolving 0.012g of cobalt nitrate hexahydrate (0.041 mmol, molar ratio of metallic cobalt to silicon source 0.001) in a mixture of 0.3mL of ethylenediamine and 3mL of water 2 CH 2 CH 2 NH 2 ) 2 ]Cl 2 The solution was then added dropwise to the above mixture, and stirring was carried out for 30 minutes without precipitation occurring. The reaction mixture was transferred to a 100mL stainless steel autoclave lined with polytetrafluoroethylene and subjected to static crystallization in a conventional oven at 170 ℃ for 4 days. The obtained solid product is centrifuged, washed by water and ethanol for several times, dried overnight in an oven at 80 ℃, roasted for 8 hours in an air atmosphere at 550 ℃, and finally reduced by hydrogen to obtain the product. The product obtained was designated as sample DC-3.
Examples 2 to 9
The corresponding products C-2 to C-9 were prepared in the same manner as in example 1, the proportions and synthesis conditions and the results are shown in Table 1. Other conditions and operations refer to example 1.
Example 10
The metal-containing hierarchical pore beta molecular sieve was prepared by varying the ratio and the template agent, which was tetraethylammonium hydroxide (TEAOH), according to the procedure of example 1, and the ratio and synthesis conditions and results are shown in table 1. The product obtained was designated as sample C-10.
Example 11
Cobalt-containing hierarchical pore MEL molecular sieves were prepared in practice, and the ratio and the template were changed by the method of example 1, and the template used was tetrabutylammonium hydroxide (TBAOH), and the ratio and synthesis conditions and results are shown in Table 1. The product obtained was designated as sample C-11.
Example 12
The cobalt-containing hierarchical pore MFI molecular sieve was prepared by the method of reference example 1, and the proportions, synthesis conditions and results are shown in Table 1. Wherein the hydrothermal crystallization temperature is 130 ℃ and the hydrothermal crystallization time is 6 days; the roasting temperature is 850 ℃ and the roasting time is 9 hours. The product obtained was designated as sample C-12.
The BET specific surface areas, total pore volumes, micropore volumes, mesopore volumes, and average particle diameters of the metal nanoparticles contained therein of the products obtained in the above examples and comparative examples are listed in table 2 below.
TABLE 1
Figure BDA0003378499830000171
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Figure BDA0003378499830000181
In table 1, TPAOH is tetrapropylammonium hydroxide, TPABr is tetrapropylammonium bromide, TBAOH is tetrabutylammonium hydroxide, TEAOH is tetraethylammonium hydroxide; PHAPTMS is N-phenyl-3-aminopropyl trimethoxysilane, APTES is 3-aminopropyl triethoxysilane, KH792 is silane coupling agent KH792 (diamino functional silane, N-aminoethyl-gamma-aminopropyl trimethoxysilane); CHP is cumene hydroperoxide and TBHP is tert-butyl hydroperoxide. Reagents employed in the present disclosure may be obtained through conventional purchase channels.
TABLE 2
Figure BDA0003378499830000191
Wherein the pores with the diameter smaller than 2nm are micropore diameters; the pores with the diameter of 2-50 nm are mesoporous.
As can be seen from Table 2, compared with DC-1 (without adding silylating agent and peroxide) prepared in comparative example 1 and DC-3 (without adding silylating agent and peroxide) prepared in comparative example 3, the addition of silylating agent and peroxide to C-1-C-12 prepared in examples 1-12 of the present disclosure during the preparation process results in a product with a higher mesoporous volume, indicating that the method provided by the present disclosure is capable of effectively reaming molecular sieves.
Compared with DC-1-DC-3, the C-1-C-12 provided by the embodiment of the disclosure can simultaneously have higher BET specific surface area, total pore volume, mesoporous volume and smaller average particle diameter of nano particles, which indicates that the metal nano particles in the composite catalytic material provided by the disclosure have lower aggregation degree and good dispersibility.
Test case
This test example illustrates the reaction effect of the examples provided in this disclosure and the samples prepared in the comparative examples for the co-oxidation of cyclooctene and isobutyraldehyde.
The reagents used in this test example were all commercially available chemically pure reagents, and the concentrations of the respective substances after the reaction were quantitatively analyzed by gas chromatography. 6890 type gas chromatograph manufactured by Agilent company is used; the analytical chromatographic column used was an HP-5 column.
The conversion of cyclooctene, isobutyraldehyde conversion, and cyclooctene selectivity of the examples were calculated according to the following formulas (2) - (4), respectively:
Figure BDA0003378499830000201
Figure BDA0003378499830000202
Figure BDA0003378499830000203
the samples prepared in the above comparative examples and examples were taken, respectively, according to isobutyraldehyde: cyclooctene = 3:1 in a slurry bed, wherein a slurry bed closed system is connected with a normal pressure pure oxygen balloon as an oxygen source, the oxygen pressure is 1mmol of cyclooctene with the pressure of 0.1Mpa, the catalyst is 50mg, and the solvent acetonitrile is 2.5mL. The reaction was stable at 25℃for 6 hours, and the results of the sample analysis are shown in Table 3.
TABLE 3 Table 3
Figure BDA0003378499830000204
Figure BDA0003378499830000211
In an embodiment, oxide aggregate Co of metallic element cobalt 3 O 4 T of (2) 2 The value is 350 ℃; t of oxide aggregate NiO of metallic element nickel 2 The value is 450 ℃; oxide aggregate MnO of metal element manganese 2 T of (2) 2 The value is 300 ℃; oxide aggregate Fe of metallic element iron 2 O 3 T of (2) 2 The value is 560 ℃; t of oxide aggregate ZnO of metallic element zinc 2 The value is 390 ℃.
As can be seen from the data in Table 3, the metal oxide nanoparticles prepared in examples 1 to 12 of the present disclosure and the molecular sieve composite catalyst materials C-1 to C-12 have T compared with DC-1 to DC-3 0 The catalyst has higher catalytic activity in the co-oxidation reaction of cyclooctene and isobutyraldehyde at 350-600 ℃, and has higher cyclooctene conversion rate and cyclooctene epoxide selectivity.
Further, comparing C-1 to C-11 with C-12, it is understood that T of C-1 to C-11 0 The value of (C) is 350-550 DEG CThe composite catalytic materials C-1 to C-11 have higher catalytic activity and higher cyclooctene conversion rate, isobutyraldehyde conversion rate and cyclooctene epoxide selectivity.
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations are not described further in this disclosure in order to avoid unnecessary repetition.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.

Claims (18)

1. The composite catalytic material of the metal nano particles and the molecular sieve is characterized by comprising an all-silicon molecular sieve and metal elements M dispersed in crystals of the all-silicon molecular sieve; the metal element M is a metal element capable of forming an oxide aggregate;
The composite catalytic material has the following H 2 -TPR features:
the composite catalytic material is in H 2 Reduction peak temperature T in TPR test 1 ，
The oxide aggregate is at H 2 Reduction peak temperature T in TPR test 2 ，
T as defined by the following formula (1) 0 Is any value between 350 and 600 ℃;
T 0 ＝T 1 -T 2 formula (1).
2. The composite catalytic material of claim 1, wherein T 0 Has a value of 350-550 DEG CAny value of (2).
3. The composite catalytic material of claim 1, wherein the all-silicon molecular sieve in the composite catalytic material is at least one of MFI structure molecular sieve, MEL structure molecular sieve, BEA structure molecular sieve, MWW structure molecular sieve, two-dimensional hexagonal structure molecular sieve, MOR structure molecular sieve, TUN structure molecular sieve, and other structured silicon molecular sieves; preferably one or more selected from MFI structure molecular sieve, MEL structure molecular sieve, BEA structure molecular sieve, MCM structure molecular sieve and SBA structure molecular sieve; further preferably one or more of MFI structure molecular sieve, MEL structure molecular sieve and BEA structure molecular sieve; further preferred are MFI structure molecular sieves;
the metal M is selected from one or more of manganese, iron, cobalt, nickel, palladium, platinum, copper and gold.
4. The composite catalytic material of claim 3, wherein the metal M is Co and the oxide aggregates are Co 3 O 4 An aggregate;
the metal M is Mn, and the oxide aggregate is MnO 2 An aggregate;
the metal M is Fe, and the oxide aggregate is Fe 2 O 3 An aggregate;
the metal M is Ni, and the oxide aggregate is NiO aggregate;
the metal M is Pd, and the oxide aggregate is a PdO aggregate;
the metal M is Pt, and the oxide aggregate is PtO 2 An aggregate; or alternatively
The metal M is Cu, and the oxide aggregate is CuO aggregate.
5. The composite catalytic material according to claim 1, wherein the molar ratio of the metal M element to the silicon element is (0.001 to 0.25): 1, preferably (0.001 to 0.2): 1.
6. the composite catalytic material according to claim 1, wherein the BET specific surface area of the composite catalytic material is 400 to 800m 2 And/g, wherein the total pore volume is 0.30-0.65 mL/g, the micropore volume is 0.10-0.19 mL/g, the mesopore volume is 0.15-0.46 mL/g, the metal element M in the composite catalytic material exists in the form of metal nano particles, and the average particle size of the metal nano particles is 0.5-8.0 nm.
7. A method for preparing a composite catalytic material of metal nano-oxide particles and a molecular sieve, which is characterized by comprising the following steps:
s1, mixing a template agent, a silicon source, water, a metal M precursor, a silanization reagent and peroxide to obtain a reaction mixture, wherein the silanization reagent comprises at least one coordination group complexed with metal M ions;
s2, carrying out hydrothermal crystallization treatment and roasting treatment on the reaction mixture.
8. The method according to claim 7, wherein in step S1, siO 2 Silicon source: template agent: water: metal element M: the molar ratio of the silylating agent is 1: (0.001-1): (5-100): (0.001-0.25): (0.025 to 0.4), preferably 1: (0.005-0.5): (5-100): (0.001-0.2): (0.025-0.3); the molar ratio of the peroxide to the metal element M is (0.5-5): 1.
9. the method according to claim 7, wherein step S1 comprises:
a. mixing a template agent, a silicon source and water to obtain a silicon hydrolysis solution;
b. adding peroxide into the aqueous solution of the metal M precursor, and mixing to obtain a first mixed material; mixing the first mixed material with the silicon hydrolysis solution to obtain a second mixed material;
c. Adding a silylation reagent into the second mixed material, and mixing to obtain the reaction mixture;
preferably, the conditions of mixing in step c include: stirring at 20-80 deg.c for 0.5-2 hr.
10. The method of claim 7, wherein the silicon source is selected from at least one of silicone grease, solid silica gel, white carbon black, and silica sol; preferably at least one selected from the group consisting of silicone grease, solid silica gel and white carbon black;
further preferred is a silicone grease having a structure represented by the following formula (A):
Figure FDA0003378499820000031
wherein R is a 、R b 、R c 、R d Each independently selected from alkyl groups having 1 to 6 carbon atoms, said alkyl groups being branched or straight chain alkyl groups; preferably, R a 、R b 、R c 、R d Each independently selected from a straight chain alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms; further preferably, the R a 、R b 、R c 、R d Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl; further preferably, the organic silicone grease is selected from one or more of tetramethyl silicate, tetraethyl silicate, tetrabutyl silicate and dimethyl diethyl silicone grease.
11. The method according to claim 7, wherein in step S1, the template agent is an organic base, preferably at least one selected from the group consisting of quaternary ammonium bases, aliphatic amines and aliphatic alcohol amines; further preferably, the template is at least one selected from quaternary ammonium bases having a structure represented by the following formula (B):
Figure FDA0003378499820000041
R 1 、R 2 、R 3 And R is 4 Each selected from alkyl groups having 1 to 4 carbon atoms, preferably straight chain alkyl groups having 1 to 4 carbon atoms and branched alkyl groups having 3 to 4 carbon atoms, more preferably R 1 、R 2 、R 3 And R is 4 At least one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl;
further preferably, the molecular sieve in the composite catalytic material is an MFI type molecular sieve, and the template agent is tetrapropylammonium hydroxide or a mixture of tetrapropylammonium hydroxide and one or more selected from tetrapropylammonium chloride and tetrapropylammonium bromide; or alternatively
The molecular sieve in the composite catalytic material is MEL type molecular sieve, and the template agent is tetrabutylammonium hydroxide or a mixture of tetrabutylammonium hydroxide and one or more selected from tetrabutylammonium chloride and tetrabutylammonium bromide; or alternatively
The molecular sieve in the composite catalytic material is Beta-type molecular sieve, and the template agent is tetraethylammonium hydroxide or a mixture of tetraethylammonium hydroxide and one or more selected from tetraethylammonium chloride and tetraethylammonium bromide.
12. The method according to claim 9, wherein in step a, the silicon source is an organic silicone grease, and further comprising hydrolysis alcohol removal treatment after mixing the template agent, the organic silicone grease and water to obtain a hydrolysis solution of the silicon;
The conditions for the hydrolysis alcohol expelling treatment comprise: stirring and hydrolyzing for 2-10 hours at 0-95 ℃; preferably at 50-95 deg.C for 2-8 hr.
13. The method according to claim 7, wherein in step S1, the metal M precursor is one or more of an inorganic metal compound and an organic metal compound; the inorganic metal compound is water-soluble inorganic salt of metal M; the water-soluble inorganic salt of the metal M is selected from one or more of chloride, hydrated chloride, sulfate, hydrated sulfate and nitrate of the metal M; the organic metal compound is an organic ligand compound of metal M; preferably, the metal M precursor is a water-soluble inorganic salt of metal M;
the metal M is selected from one or more of manganese, iron, cobalt, nickel, palladium, platinum, copper and gold;
preferably, the molar ratio of the metal M element to water in the aqueous solution of the metal M precursor is 1: (50-500).
14. The method of claim 7, wherein in step S1, the silylating agent has the general formula R 5 Si(R 6 )(R 7 )R 8 Wherein R is 5 、R 6 、R 7 、R 8 Each independently is halogen, alkyl, alkoxy, aryl, mercapto or amino, and R 5 、R 6 、R 7 、R 8 At least one of which is alkyl, alkoxy, aryl, mercapto or amino; the alkyl, alkoxy, mercapto and amino groups each independently have 1 to 18 carbon atoms, and the aryl group has 6 to 18 carbon atoms;
Preferably, the silylating agent is selected from one or more of dimethyldichlorosilane, N-phenyl-3-aminopropyl trimethoxysilane, phenyl trimethoxysilane, 1, 7-dichlorooctanethyltetrasiloxane, hexadecyl trimethoxysilane, octyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane and-mercaptopropyl trimethoxysilane; further preferred is at least one selected from the group consisting of N-phenyl-3-aminopropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane and 3-mercaptopropyl trimethoxysilane.
15. The method according to claim 7, wherein in step S1, the peroxide is one or more of hydrogen peroxide or an organic peroxide; the organic peroxides include cumene hydroperoxide, ethylbenzene hydroperoxide and tert-butyl hydroperoxide.
16. The method according to claim 7, wherein in step S2, the conditions of the hydrothermal crystallization treatment include: under autogenous pressure, the hydrothermal crystallization time is 0.5-10 days, and the hydrothermal crystallization temperature is 110-200 ℃; preferably, the hydrothermal crystallization time is 0.5-5 days, and the hydrothermal crystallization temperature is 150-200 ℃;
The conditions of the calcination treatment include: roasting temperature is 400-900 ℃ and roasting time is 1-16 hours; preferably, the roasting temperature is 400-800 ℃ and the roasting time is 2-8 hours.
17. A metal nanoparticle and molecular sieve composite catalytic material prepared according to the method of any one of claims 7 to 16.
18. Use of the metal nanoparticle of any one of claims 1 to 6 or the metal nanoparticle of claim 17 in combination with a molecular sieve composite catalytic material for catalyzing the co-oxidation of macromolecular aldehydes/olefins; preferably in catalyzing the co-oxidation of cyclooctene and isobutyraldehyde.
CN202111424565.9A 2021-11-26 2021-11-26 Composite catalytic material containing metal elements and molecular sieve, and preparation method and application thereof Pending CN116174019A (en)

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