CN113559920A - ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof - Google Patents
ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 126
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 62
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 title abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 104
- 238000000227 grinding Methods 0.000 claims abstract description 55
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 33
- 239000010703 silicon Substances 0.000 claims abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 25
- 238000002425 crystallisation Methods 0.000 claims abstract description 21
- 230000008025 crystallization Effects 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 69
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 59
- 239000002105 nanoparticle Substances 0.000 claims description 34
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 17
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 17
- 229910001593 boehmite Inorganic materials 0.000 claims description 16
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 16
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 229910052573 porcelain Inorganic materials 0.000 description 28
- 239000004570 mortar (masonry) Substances 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 26
- 239000000463 material Substances 0.000 description 23
- 239000013078 crystal Substances 0.000 description 20
- 239000002245 particle Substances 0.000 description 16
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 16
- 239000011148 porous material Substances 0.000 description 15
- 235000012239 silicon dioxide Nutrition 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 229910021485 fumed silica Inorganic materials 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- -1 salt sodium chloride Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B01J35/23—
-
- B01J35/399—
-
- B01J35/643—
-
- 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)
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The invention provides a ZSM-5 molecular sieve/titanium dioxide composite material and a preparation method thereof, relating to the technical field of molecular sieve preparation. The preparation method provided by the invention comprises the following steps: silicon source, aluminum source, ammonium chloride, organic template agent, sodium hydroxide and Ti3AlC2Grinding and mixing, and carrying out crystallization reaction to obtain a composite material precursor; calcining the composite material precursor to obtain ZSM-5/TiO2A composite material. The invention is in the preparation of ZSM-5/TiO2No solvent is required to be added in the process of the composite material, the environment is protected, and the operation is performedSimple and efficient, and is suitable for industrial popularization and application.
Description
Technical Field
The invention relates to the technical field of molecular sieve preparation, in particular to a ZSM-5 molecular sieve/titanium dioxide composite material and a preparation method thereof.
Background
The ZSM-5 molecular sieve is a porous aluminosilicate, has a typical MFI type framework structure of a ten-membered ring straight channel and a ten-membered ring zigzag channel, and belongs to a high-silicon five-membered ring type molecular sieve. The ZSM-5 molecular sieve has special shape selectivity, thermal stability, chemical stability and acid strength due to the unique pore channel structure, shows excellent catalytic performance in organic catalytic reaction, and is widely applied to the field of petrochemical industry.
Currently, ZSM-5 molecular sieves are mainly synthesized under hydrothermal conditions as an important industrial material, but water occupies a large space in an autoclave, so that the pressure in the autoclave is too high, and the yield of the ZSM-5 molecular sieves is greatly influenced. In addition, the large amount of waste liquid generated after the hydrothermal reaction also causes safety and environmental problems.
Disclosure of Invention
The invention aims to provide a ZSM-5 molecular sieve/titanium dioxide composite material and a preparation method thereof, and the invention is used for preparing ZSM-5/TiO2The composite material does not need to be added with a solvent in the process, is green and environment-friendly, is simple and efficient to operate, and is suitable for industrial popularization and application.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a green solvent-free ZSM-5/TiO2The preparation method of the composite material comprises the following steps:
silicon source, aluminum source, ammonium chloride, organic template agent, sodium hydroxide and Ti3AlC2Grinding and mixing, and carrying out crystallization reaction to obtain a composite material precursor;
calcining the composite material precursor to obtain ZSM-5/TiO2A composite material.
Preferably, the silicon source and the aluminum source have a silicon-aluminum ratio of 50-90: 1.
Preferably, the silicon source comprises sodium silicate and silicon dioxide; the aluminum source comprises boehmite.
Preferably, the mass ratio of the ammonium chloride to the organic template to the aluminum source is 0.45:0.24: 0.016-0.024.
Preferably, the organic templating agent comprises tetrapropylammonium bromide.
Preferably, the mass ratio of the silicon source to the sodium hydroxide is 6-12: 1.
Preferably, the silicon source and Ti3AlC2The mass ratio of (A) to (B) is 40-120: 1.
Preferably, the temperature of the crystallization reaction is 160-200 ℃ and the time is 12-36 h.
Preferably, the calcining temperature is 500-600 ℃, and the time is 4-8 h.
The invention provides ZSM-5/TiO prepared by the preparation method in the technical scheme2The composite material comprises a ZSM-5 molecular sieve and TiO distributed on the surface of the ZSM-5 molecular sieve2And (3) nanoparticles.
The invention provides a green solvent-free ZSM-5/TiO2The preparation method of the composite material comprises the following steps: silicon source, aluminum source, ammonium chloride, organic template agent, sodium hydroxide and Ti3AlC2Grinding and mixing, and carrying out crystallization reaction to obtain a composite material precursor; calcining the composite material precursor to obtain ZSM-5/TiO2A composite material. The method comprises the steps of fully mixing materials by grinding and mixing, crystallizing a silicon source and an aluminum source under the induction of an organic template in the crystallization reaction process to form a ZSM-5 molecular sieve crystal with an MFI-type framework structure, and removing the organic template in the ZSM-5 molecular sieve crystal by calcination to obtain the ZSM-5 molecular sieve; while in the course of calcination, Ti3AlC2Is in-situ compounded with ZSM-5 molecular sieve, and titanium dioxide nano particles are introduced on the surface of the ZSM-5 molecular sieve to form ZSM-5/TiO2A composite material.
The method does not need to use a solvent in the preparation process, not only greatly reduces the generation of waste liquid, but also greatly improves the yield and the efficiency, and has very important significance for designing and preparing the zeolite with catalytic activity. The method provided by the invention has the advantages of low pressure in the kettle, high yield, low pollution rate and high safety, is a synthetic strategy which is green, environment-friendly, efficient and simple to operate, and has important significance in actual industrial production.
Drawings
FIG. 1 is a ZSM-5/TiO sample prepared in example 12An X-ray diffraction pattern of the composite;
FIG. 2 is the ZSM-5/TiO of example 12Scanning electron micrographs of the composite;
FIG. 3 is the ZSM-5/TiO of example 12High magnification transmission electron microscopy images of the composite;
FIG. 4 is the ZSM-5/TiO of example 12A medium-magnification transmission electron microscope image of the composite material;
FIG. 5 is the ZSM-5/TiO of example 12Low magnification transmission electron microscopy images of the composite;
FIG. 6 is a ZSM-5/TiO sample prepared in example 12An X-ray photoelectron energy spectrum of the composite;
FIG. 7 is a ZSM-5/TiO sample prepared in example 12Electron microscopy energy spectrum of the composite material;
FIG. 8 shows ZSM-5/TiO compounds prepared in examples 1 to 32An X-ray diffraction pattern of the composite;
FIG. 9 shows ZSM-5/TiO blends prepared in examples 1, 4 and 52An X-ray diffraction pattern of the composite;
FIG. 10 shows ZSM-5/TiO zeolite prepared in example 1, example 6 and example 72An X-ray diffraction pattern of the composite;
FIG. 11 shows ZSM-5/TiO zeolite prepared in example 1, example 8 and example 92An X-ray diffraction pattern of the composite;
FIG. 12 shows ZSM-5/TiO prepared in example 1, example 10 and example 112X-ray diffraction pattern of the composite.
Detailed Description
The invention provides a green solvent-free ZSM-5/TiO2The preparation method of the composite material comprises the following steps:
silicon source, aluminum source, ammonium chloride, organic template agent, sodium hydroxide and Ti3AlC2Grinding and mixing, and carrying out crystallization reaction to obtain a composite material precursor;
calcining the composite material precursor to obtain ZSM-5/TiO2A composite material.
In the present invention, unless otherwise specified, the starting materials used are all commercially available products well known to those skilled in the art.
The invention comprises silicon source, aluminum source, ammonium chloride, organic template agent, sodium hydroxide and Ti3AlC2Grinding, mixing and carrying out crystallization reaction to obtain the composite material precursor. In the present invention, the silicon source preferably comprises sodium silicate and silica; the sodium silicate is preferably sodium silicate nonahydrate; the silica is preferably fumed silica, the fumed silica preferably having a specific surface area of 400m2(ii) in terms of/g. In the invention, the molar ratio of the sodium silicate to the silicon dioxide is preferably 0.5-0.8: 1, and more preferably 0.6-0.7: 1.
In the present invention, the aluminum source preferably comprises boehmite.
In the invention, the silicon-aluminum ratio of the silicon source to the aluminum source is preferably 50-90: 1, and more preferably 70-80: 1. In the present invention, the silicon-aluminum ratio of the silicon source and the aluminum source refers to SiO2And Al2O3The mass ratio of (a).
In the present invention, the organic templating agent preferably comprises tetrapropylammonium bromide.
In the invention, the mass ratio of the ammonium chloride to the organic template to the aluminum source is preferably 0.45:0.24: 0.016-0.024, and more preferably 0.45:0.24: 0.019-0.021.
In the invention, the mass ratio of the silicon source to the sodium hydroxide is preferably 6-12: 1, and more preferably 8-10: 1. In a specific embodiment of the invention, the mass ratio of the silicon dioxide to the sodium hydroxide is preferably 6-12: 1, and more preferably 8-10: 1.
In the present invention, the silicon source and Ti3AlC2The mass ratio of (A) to (B) is preferably 40 to 120:1, more preferably 60 to 100: 1. In a specific embodiment of the invention, the silica and Ti3AlC2The mass ratio of (A) to (B) is preferably 40 to 120:1, more preferably 60 to 100: 1.
The invention limits the raw materials to synthesize the ZSM-5/TiO within the range2The composite material can improve the crystallinity of the ZSM-5 molecular sieve. Preferably, the interaction between sodium silicate nonahydrate and ammonium chloride displaces sodium ions in the sodium silicate nonahydrate to form the solid salt sodium chloride, resulting in spontaneous dispersion of the solid salt on the amorphous support, greatly reducing TPA+Bands of species; fumed silica facilitates the formation of framework silicon tetrahedra; the tetrapropylammonium bromide serving as an organic template agent is added to induce crystallization, so that a ZSM-5 molecular sieve crystal with an MFI type framework structure can be formed; the pH value of the system can be adjusted by adding a proper amount of sodium hydroxide, and a proper alkaline environment is provided for ZSM-5 molecular sieve crystallization; by using Ti3AlC2As a titanium source, titanium element can be introduced into a ZSM-5 molecular sieve to form a two-dimensional transition metal carbide Ti3AlC2In-situ compounding with ZSM-5 molecular sieve to form ZSM-5/TiO2A composite material.
In the invention, the silicon source, the aluminum source, the ammonium chloride, the organic template, the sodium hydroxide and the Ti3AlC2The method of mill mixing preferably comprises the steps of: carrying out first grinding and mixing on a silicon source and an aluminum source to obtain a first mixed material; carrying out second grinding and mixing on the first mixed material, ammonium chloride, an organic template and sodium hydroxide to obtain a second mixed material; mixing the second mixed material with Ti3AlC2And carrying out third grinding and mixing to obtain a third mixed material. In the present invention, the time for the first milling mixing is preferably 3 min. In the present invention, the time for the second milling mixing is preferably 3 min. In the present invention, the time for the third milling mixing is preferably 10 min. The invention mixes the first grindingThe rotation speeds of the second mill mixing and the third mill mixing are not particularly required, and it is preferable to use hand milling.
According to the invention, the silicon source and the aluminum source can be more fully mixed by utilizing the first grinding and mixing; the second grinding and mixing can provide substances such as an organic template agent and the like to induce further crystallization; the third grinding and mixing can mix Ti3AlC2More uniformly mixed with the above materials. The grinding and mixing method can fully mix the raw materials, and is more favorable for forming the ZSM-5 molecular sieve crystal with the MFI type framework structure.
In the present invention, the grinding and mixing are preferably carried out in an agate mortar.
After the grinding and mixing, the crystallization reaction is preferably carried out on the obtained third mixed material to obtain the composite material precursor. In the present invention, the crystallization reaction is preferably carried out in a high-pressure reaction vessel. In the invention, the temperature of the crystallization reaction is preferably 160-200 ℃, and more preferably 180-190 ℃; the time of the crystallization reaction is preferably 12-36 hours, and more preferably 24-30 hours.
In the crystallization reaction process, a silicon source and an aluminum source are crystallized under the induction of an organic template agent, so that an amorphous phase is completely converted into a ZSM-5 molecular sieve crystal with an MFI type framework structure.
After the crystallization reaction, the obtained crystal is preferably cooled to room temperature, and is sequentially washed and dried to obtain the composite material precursor. In the invention, the washing method preferably comprises suction filtration by using deionized water; the temperature of the drying is preferably 80 ℃, and the time of the drying is preferably 12 h.
After obtaining the composite material precursor, the invention calcines the composite material precursor to obtain ZSM-5/TiO2A composite material. In the present invention, the calcination is preferably carried out in a muffle furnace. In the invention, the calcining temperature is preferably 500-600 ℃, and more preferably 550 ℃; the calcination time is preferably 4-8 h, and more preferably 5-6 h. In the present invention, the calcination is preferably performed in an air atmosphere. In the present invention, the rate of temperature rise from room temperature to the temperature of calcination is excellentThe temperature is selected to be 2-5 ℃/min, and more preferably 3 ℃/min.
In the calcining process, the structure of a ZSM-5 molecular sieve crystal can be destroyed, and an organic template agent in a hole is fully removed to obtain the ZSM-5 molecular sieve; while in the course of calcination, Ti3AlC2Is in-situ compounded with ZSM-5 molecular sieve, and titanium dioxide nano particles are introduced on the surface of the ZSM-5 molecular sieve to form ZSM-5/TiO2A composite material.
The invention provides ZSM-5/TiO prepared by the preparation method in the technical scheme2The composite material comprises a ZSM-5 molecular sieve and TiO distributed on the surface of the ZSM-5 molecular sieve2And (3) nanoparticles. In the invention, the specific surface area of the ZSM-5 molecular sieve is preferably 447-451 m2(ii)/g; the preferable micropore volume is 0.218-0.232 cm3(ii)/g; the average pore diameter is preferably 0.95 to 0.96 nm.
In the present invention, the TiO is2The average particle diameter of the nanoparticles is preferably 8 to 10nm, and more preferably 9 nm.
The invention introduces TiO with uniform particles on the surface of the ZSM-5 molecular sieve2The nano particles are beneficial to improving the catalytic activity of the composite material.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing sodium silicate nonahydrate, fumed silica and boehmite according to the silicon-aluminum ratio (SiO)2And Al2O3Mass ratio of) 70 in an agate mortar, and primarily grinding for three minutes; 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (SiO in mass ratio)2NaOH 8) and grinding for three minutes; finally 0.01g Ti3AlC2(mass ratio of SiO)2:Ti3AlC260) in agateIn a mortar, uniformly mixing and fully grinding for ten minutes; transferring the obtained mixed material into a high-pressure reaction kettle, reacting for 24 hours at 180 ℃, cooling to room temperature after the reaction is finished, performing suction filtration on the obtained crystal by using deionized water, and drying the suction-filtered sample for 12 hours at 80 ℃ to obtain a composite material precursor; placing the composite material precursor into a porcelain boat, placing the porcelain boat into a muffle furnace, heating from normal temperature to 550 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and keeping at the temperature of 550 ℃ for 6 hours to obtain ZSM-5/TiO2A composite material.
ZSM-5/TiO prepared in this example2In the composite material, TiO2The nano particles are uniformly distributed on the surface of the ZSM-5 molecular sieve; wherein the average pore diameter of the ZSM-5 molecular sieve is 0.96 nm; TiO 22The average particle size of the nanoparticles was 9 nm.
Example 2
Putting sodium silicate nonahydrate, gas-phase silicon dioxide and boehmite into an agate mortar according to the silicon-aluminum ratio of 50, and primarily grinding for three minutes; 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (SiO in mass ratio)2NaOH 8) and grinding for three minutes; finally 0.01g Ti3AlC2(mass ratio of SiO)2:Ti3AlC260) placing in an agate mortar, mixing uniformly and fully grinding for ten minutes; transferring the obtained mixed material into a high-pressure reaction kettle, reacting for 24 hours at 180 ℃, performing suction filtration on the obtained crystal by using deionized water after the reaction is cooled to room temperature, and drying the suction-filtered sample for 12 hours at 80 ℃ to obtain a composite material precursor; placing the composite material precursor into a porcelain boat, placing the porcelain boat into a muffle furnace, heating from normal temperature to 550 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and keeping at the temperature of 550 ℃ for 6 hours to obtain ZSM-5/TiO2A composite material.
ZSM-5/TiO prepared in this example2In the composite material, TiO2The nano particles are uniformly distributed on the surface of the ZSM-5 molecular sieve; wherein the average pore diameter of the ZSM-5 molecular sieve is 0.95 nm; TiO 22The average particle diameter of the nanoparticles was 9nm。
Example 3
Putting sodium silicate nonahydrate, gas-phase silicon dioxide and boehmite into an agate mortar according to the silicon-aluminum ratio of 90, and primarily grinding for three minutes; 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (SiO in mass ratio)2NaOH 8) and grinding for three minutes; finally 0.01g Ti3AlC2(mass ratio of SiO)2:Ti3AlC260) placing in an agate mortar, mixing uniformly and fully grinding for ten minutes; transferring the obtained mixed material into a high-pressure reaction kettle, reacting for 24 hours at 180 ℃, performing suction filtration on the obtained crystal by using deionized water after the reaction is cooled to room temperature, and drying the suction-filtered sample for 12 hours at 80 ℃ to obtain a composite material precursor; placing the composite material precursor into a porcelain boat, placing the porcelain boat into a muffle furnace, heating from normal temperature to 550 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and keeping at the temperature of 550 ℃ for 6 hours to obtain ZSM-5/TiO2A composite material.
ZSM-5/TiO prepared in this example2In the composite material, TiO2The nano particles are uniformly distributed on the surface of the ZSM-5 molecular sieve; wherein the average pore diameter of the ZSM-5 molecular sieve is 0.96 nm; TiO 22The average particle size of the nanoparticles was 9 nm.
Example 4
Putting sodium silicate nonahydrate, gas-phase silicon dioxide and boehmite into an agate mortar according to the silicon-aluminum ratio of 70, and primarily grinding for three minutes; 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.1g of sodium hydroxide (mass ratio SiO)2NaOH 6) and grinding for three minutes; finally 0.01g Ti3AlC2(mass ratio of SiO)2:Ti3AlC260) placing in an agate mortar, mixing uniformly and fully grinding for ten minutes; transferring the obtained mixed material into a high-pressure reaction kettle, reacting for 24 hours at 180 ℃, performing suction filtration on the obtained crystal by using deionized water after the reaction is cooled to room temperature, and drying the suction-filtered sample for 12 hours at 80 ℃ to obtain a composite material precursor; placing the composite material precursor in a porcelain boatPutting the porcelain boat into a muffle furnace, heating the porcelain boat from normal temperature to 550 ℃ at a heating rate of 2 ℃/min in the air atmosphere, and keeping the porcelain boat at the temperature of 550 ℃ for 6 hours to obtain ZSM-5/TiO2A composite material.
ZSM-5/TiO prepared in this example2In the composite material, TiO2The nano particles are uniformly distributed on the surface of the ZSM-5 molecular sieve; wherein the average pore diameter of the ZSM-5 molecular sieve is 0.96 nm; TiO 22The average particle size of the nanoparticles was 9 nm.
Example 5
Putting sodium silicate nonahydrate, gas-phase silicon dioxide and boehmite into an agate mortar according to the silicon-aluminum ratio of 70, and primarily grinding for three minutes; 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.05g of sodium hydroxide (mass ratio SiO)2NaOH 12) and grinding for three minutes; finally 0.01g Ti3AlC2(mass ratio of SiO)2:Ti3AlC260) placing in an agate mortar, mixing uniformly and fully grinding for ten minutes; transferring the obtained mixed material into a high-pressure reaction kettle, reacting for 24 hours at 180 ℃, performing suction filtration on the obtained crystal by using deionized water after the reaction is cooled to room temperature, and drying the suction-filtered sample for 12 hours at 80 ℃ to obtain a composite material precursor; placing the composite material precursor into a porcelain boat, placing the porcelain boat into a muffle furnace, heating from normal temperature to 550 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and keeping at the temperature of 550 ℃ for 6 hours to obtain ZSM-5/TiO2A composite material.
ZSM-5/TiO prepared in this example2In the composite material, TiO2The nano particles are uniformly distributed on the surface of the ZSM-5 molecular sieve; wherein the average pore diameter of the ZSM-5 molecular sieve is 0.96 nm; TiO 22The average particle size of the nanoparticles was 9 nm.
Example 6
Putting sodium silicate nonahydrate, gas-phase silicon dioxide and boehmite into an agate mortar according to the silicon-aluminum ratio of 70, and primarily grinding for three minutes; 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (SiO in mass ratio)2NaOH 8) and grinding for three minutes; and finally 0.015g Ti3AlC2(mass ratio of SiO)2:Ti3AlC240) placing in an agate mortar, mixing uniformly and fully grinding for ten minutes; transferring the obtained mixed material into a high-pressure reaction kettle, reacting for 24 hours at 180 ℃, performing suction filtration on the obtained crystal by using deionized water after the reaction is cooled to room temperature, and drying the suction-filtered sample for 12 hours at 80 ℃ to obtain a composite material precursor; placing the composite material precursor into a porcelain boat, placing the porcelain boat into a muffle furnace, heating from normal temperature to 550 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and keeping at the temperature of 550 ℃ for 6 hours to obtain ZSM-5/TiO2A composite material.
ZSM-5/TiO prepared in this example2In the composite material, TiO2The nano particles are uniformly distributed on the surface of the ZSM-5 molecular sieve; wherein the average pore diameter of the ZSM-5 molecular sieve is 0.96 nm; TiO 22The average particle size of the nanoparticles was 9 nm.
Example 7
Putting sodium silicate nonahydrate, gas-phase silicon dioxide and boehmite into an agate mortar according to the silicon-aluminum ratio of 70, and primarily grinding for three minutes; 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (SiO in mass ratio)2NaOH 8) and grinding for three minutes; finally 0.005g Ti3AlC2(mass ratio of SiO)2:Ti3AlC2120) in an agate mortar, uniformly mixing and fully grinding for ten minutes; transferring the obtained mixed material into a high-pressure reaction kettle, reacting for 24 hours at 180 ℃, performing suction filtration on the obtained crystal by using deionized water after the reaction is cooled to room temperature, and drying the suction-filtered sample for 12 hours at 80 ℃ to obtain a composite material precursor; placing the composite material precursor into a porcelain boat, placing the porcelain boat into a muffle furnace, heating from normal temperature to 550 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and keeping at the temperature of 550 ℃ for 6 hours to obtain ZSM-5/TiO2A composite material.
ZSM-5/TiO prepared in this example2In the composite material, TiO2The nano particles are uniformly distributed on the surface of the ZSM-5 molecular sieve;wherein the average pore diameter of the ZSM-5 molecular sieve is 0.96 nm; TiO 22The average particle size of the nanoparticles was 9 nm.
Example 8
Putting sodium silicate nonahydrate, gas-phase silicon dioxide and boehmite into an agate mortar according to the silicon-aluminum ratio of 70, and primarily grinding for three minutes; 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (SiO in mass ratio)2NaOH 8) and grinding for three minutes; finally 0.01g Ti3AlC2(mass ratio of SiO)2:Ti3AlC260) placing in an agate mortar, mixing uniformly and fully grinding for ten minutes; transferring the obtained mixed material into a high-pressure reaction kettle, reacting for 24 hours at 160 ℃, performing suction filtration on the obtained crystal by using deionized water after the reaction is cooled to room temperature, and drying the suction-filtered sample for 12 hours at 80 ℃ to obtain a composite material precursor; placing the composite material precursor into a porcelain boat, placing the porcelain boat into a muffle furnace, heating from normal temperature to 550 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and keeping at the temperature of 550 ℃ for 6 hours to obtain ZSM-5/TiO2A composite material.
ZSM-5/TiO prepared in this example2In the composite material, TiO2The nano particles are uniformly distributed on the surface of the ZSM-5 molecular sieve; wherein the average pore diameter of the ZSM-5 molecular sieve is 0.96 nm; TiO 22The average particle size of the nanoparticles was 9 nm.
Example 9
Putting sodium silicate nonahydrate, gas-phase silicon dioxide and boehmite into an agate mortar according to the silicon-aluminum ratio of 70, and primarily grinding for three minutes; 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (SiO in mass ratio)2NaOH 8) and grinding for three minutes; finally 0.01g Ti3AlC2(mass ratio of SiO)2:Ti3AlC260) placing in an agate mortar, mixing uniformly and fully grinding for ten minutes; transferring the obtained mixed material into a high-pressure reaction kettle, reacting for 24 hours at 200 ℃, performing suction filtration on the obtained crystal by using deionized water after the reaction is cooled to room temperature, and then performing suction filtration on the sample at 80 DEG CDrying at the temperature of 12 hours to obtain a composite material precursor; placing the composite material precursor into a porcelain boat, placing the porcelain boat into a muffle furnace, heating from normal temperature to 550 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and keeping at the temperature of 550 ℃ for 6 hours to obtain ZSM-5/TiO2A composite material.
ZSM-5/TiO prepared in this example2In the composite material, TiO2The nano particles are uniformly distributed on the surface of the ZSM-5 molecular sieve; wherein the average pore diameter of the ZSM-5 molecular sieve is 0.96 nm; TiO 22The average particle size of the nanoparticles was 9 nm.
Example 10
Putting sodium silicate nonahydrate, gas-phase silicon dioxide and boehmite into an agate mortar according to the silicon-aluminum ratio of 70, and primarily grinding for three minutes; 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (SiO in mass ratio)2NaOH 8) and grinding for three minutes; finally 0.010g Ti3AlC2(mass ratio of SiO)2:Ti3AlC260) placing in an agate mortar, mixing uniformly and fully grinding for ten minutes; transferring the obtained mixed material into a high-pressure reaction kettle, reacting for 12 hours at 180 ℃, after the reaction is cooled to room temperature, carrying out suction filtration on the obtained crystal by using deionized water, and drying the suction-filtered sample for 12 hours at 80 ℃ to obtain a composite material precursor; placing the composite material precursor into a porcelain boat, placing the porcelain boat into a muffle furnace, heating from normal temperature to 550 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and keeping at the temperature of 550 ℃ for 6 hours to obtain ZSM-5/TiO2A composite material.
ZSM-5/TiO prepared in this example2In the composite material, TiO2The nano particles are uniformly distributed on the surface of the ZSM-5 molecular sieve; wherein the average pore diameter of the ZSM-5 molecular sieve is 0.96 nm; TiO 22The average particle size of the nanoparticles was 9 nm.
Example 11
Putting sodium silicate nonahydrate, gas-phase silicon dioxide and boehmite into an agate mortar according to the silicon-aluminum ratio of 70, and primarily grinding for three minutes; 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and0.075g of sodium hydroxide (mass ratio SiO)2NaOH 8) and grinding for three minutes; finally 0.01g Ti3AlC2(mass ratio of SiO)2:Ti3AlC260) placing in an agate mortar, mixing uniformly and fully grinding for ten minutes; transferring the obtained mixed material into a high-pressure reaction kettle, reacting for 36h at 180 ℃, performing suction filtration on the obtained crystal by using deionized water after the reaction is cooled to room temperature, and drying the suction-filtered sample for 12h at 80 ℃ to obtain a composite material precursor; placing the composite material precursor into a porcelain boat, placing the porcelain boat into a muffle furnace, heating from normal temperature to 550 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and keeping at the temperature of 550 ℃ for 6 hours to obtain ZSM-5/TiO2A composite material.
ZSM-5/TiO prepared in this example2In the composite material, TiO2The nano particles are uniformly distributed on the surface of the ZSM-5 molecular sieve; wherein the average pore diameter of the ZSM-5 molecular sieve is 0.96 nm; TiO 22The average particle size of the nanoparticles was 9 nm.
Example 12
Putting sodium silicate nonahydrate, gas-phase silicon dioxide and boehmite into an agate mortar according to the silicon-aluminum ratio of 70, and primarily grinding for three minutes; 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (SiO in mass ratio)2NaOH 8) and grinding for three minutes; finally 0.01g Ti3AlC2(mass ratio of SiO)2:Ti3AlC260) placing in an agate mortar, mixing uniformly and fully grinding for ten minutes; transferring the obtained mixed material into a high-pressure reaction kettle, reacting for 24 hours at 180 ℃, performing suction filtration on the obtained crystal by using deionized water after the reaction is cooled to room temperature, and drying the suction-filtered sample for 12 hours at 80 ℃ to obtain a composite material precursor; placing the composite material precursor into a porcelain boat, placing the porcelain boat into a muffle furnace, heating from normal temperature to 550 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and keeping at the temperature of 550 ℃ for 4h to obtain ZSM-5/TiO2A composite material.
Z prepared in this exampleSM-5/TiO2In the composite material, TiO2The nano particles are uniformly distributed on the surface of the ZSM-5 molecular sieve; wherein the average pore diameter of the ZSM-5 molecular sieve is 0.96 nm; TiO 22The average particle size of the nanoparticles was 9 nm.
Example 13
Putting sodium silicate nonahydrate, gas-phase silicon dioxide and boehmite into an agate mortar according to the silicon-aluminum ratio of 70, and primarily grinding for three minutes; 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (SiO in mass ratio)2NaOH 8) and grinding for three minutes; finally 0.010g Ti3AlC2(mass ratio of SiO)2:Ti3AlC260) placing in an agate mortar, mixing uniformly and fully grinding for ten minutes; transferring the obtained mixed material into a high-pressure reaction kettle, reacting for 24 hours at 180 ℃, performing suction filtration on the obtained crystal by using deionized water after the reaction is cooled to room temperature, and drying the suction-filtered sample for 12 hours at 80 ℃ to obtain a composite material precursor; placing the composite material precursor into a porcelain boat, placing the porcelain boat into a muffle furnace, heating from normal temperature to 550 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and keeping at the temperature of 550 ℃ for 8h to obtain ZSM-5/TiO2A composite material.
ZSM-5/TiO prepared in this example2In the composite material, TiO2The nano particles are uniformly distributed on the surface of the ZSM-5 molecular sieve; wherein the average pore diameter of the ZSM-5 molecular sieve is 0.96 nm; TiO 22The average particle size of the nanoparticles was 9 nm.
Test example
ZSM-5/TiO prepared in example 12The X-ray powder diffraction pattern of the composite material is shown in fig. 1. As can be seen from FIG. 1, the ZSM-5/TiO prepared by the present invention2The composite material belongs to a typical zeolite of the MFI-type structure.
ZSM-5/TiO prepared in example 12The scanning electron micrograph of the composite is shown in FIG. 2. As can be seen from FIG. 2, the ZSM-5/TiO prepared by the present invention2The composite material exhibits a rough and irregular surface dough-like morphology.
ZSM prepared in example 1-5/TiO2The transmission electron microscope images of the composite material are shown in FIGS. 3-5. As can be seen from FIGS. 3 to 5, TiO having a uniform particle size2The nano particles are uniformly distributed on the surface of the material.
ZSM-5/TiO prepared in example 12The X-ray photoelectron spectrum of the composite material is shown in fig. 6. As can be seen from FIG. 6, the ZSM-5/TiO prepared by the present invention2The composite material contains elements such as Si, Al, Ti, C, O and the like.
ZSM-5/TiO prepared in example 12The electron microscopic energy spectrum of the composite material is shown in FIG. 7. It can be seen from FIG. 7 that the four elements C, Si, Al and Ti are uniformly distributed on the surface of the material.
ZSM-5/TiO prepared in examples 1 to 32The X-ray diffraction pattern of the composite material is shown in fig. 8. It can be seen from fig. 8 that the crystallinity of the composite material can be changed by adjusting the ratio of the raw materials to the silicon to the aluminum, and within the range of the ratio of the raw materials to the silicon to the aluminum adopted by the invention, the crystallinity of the composite material is higher as the ratio of the raw materials to the silicon to the aluminum is increased.
ZSM-5/TiO prepared in example 1, example 4 and example 52The X-ray diffraction pattern of the composite material is shown in fig. 9. As can be seen from FIG. 9, the crystallinity of the composite material can be changed by adjusting the ratio of sodium to silicon, and within the range of the ratio of sodium to silicon adopted by the invention, the crystallinity of the composite material is lower as the ratio of sodium to aluminum of the raw material is increased.
ZSM-5/TiO prepared in example 1, example 6 and example 72The X-ray diffraction pattern of the composite material is shown in fig. 10. As can be seen from FIG. 10, Ti was added3AlC2The amount of (A) affects the crystallinity of the composite material, and in the present invention, Ti is added with the raw material3AlC2The more the amount of (b), the lower the crystallinity of the composite material.
ZSM-5/TiO prepared in example 1, example 8 and example 92The X-ray diffraction pattern of the composite material is shown in fig. 11. As can be seen from FIG. 11, the crystallization temperature affects the crystallinity of the composite material, which is highest at 180 ℃ in the present invention.
ZSM-5/TiO prepared in example 1, example 10 and example 112The X-ray diffraction pattern of the composite material is shown in figure 12, respectively. As can be seen from fig. 12, the crystallization time affects the crystallinity of the composite material, and in this experiment, the crystallization time is more than 24 hours at 180 ℃, and the composite material exhibits better crystallinity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. Green solvent-free ZSM-5/TiO2The preparation method of the composite material is characterized by comprising the following steps:
silicon source, aluminum source, ammonium chloride, organic template agent, sodium hydroxide and Ti3AlC2Grinding and mixing, and carrying out crystallization reaction to obtain a composite material precursor;
calcining the composite material precursor to obtain ZSM-5/TiO2A composite material.
2. The preparation method according to claim 1, wherein the silicon source and the aluminum source have a silicon-aluminum ratio of 50 to 90: 1.
3. The method of claim 1 or 2, wherein the silicon source comprises sodium silicate and silica; the aluminum source comprises boehmite.
4. The preparation method according to claim 1, wherein the mass ratio of the ammonium chloride to the organic template to the aluminum source is 0.45:0.24:0.016 to 0.024.
5. The method of claim 1 or 4, wherein the organic template comprises tetrapropylammonium bromide.
6. The preparation method according to claim 1, wherein the mass ratio of the silicon source to the sodium hydroxide is 6-12: 1.
7. The method of claim 1, wherein the silicon source and Ti are3AlC2The mass ratio of (A) to (B) is 40-120: 1.
8. The method according to claim 1, wherein the temperature of the crystallization reaction is 160-200 ℃ and the time is 12-36 h.
9. The preparation method according to claim 1, wherein the calcining temperature is 500-600 ℃ and the calcining time is 4-8 h.
10. ZSM-5/TiO prepared by the preparation method of any one of claims 1 to 92The composite material comprises a ZSM-5 molecular sieve and TiO distributed on the surface of the ZSM-5 molecular sieve2And (3) nanoparticles.
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