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 PDF

Info

Publication number
CN113559920A
CN113559920A CN202110756320.XA CN202110756320A CN113559920A CN 113559920 A CN113559920 A CN 113559920A CN 202110756320 A CN202110756320 A CN 202110756320A CN 113559920 A CN113559920 A CN 113559920A
Authority
CN
China
Prior art keywords
zsm
composite material
tio
molecular sieve
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110756320.XA
Other languages
Chinese (zh)
Inventor
王磊
王福鹏
刘佳
傅梓淇
郭自洋
冯守华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Frontier Research Institute Of Nano And Micro Sciences Qingdao Co ltd
Qingdao University of Science and Technology
Original Assignee
Frontier Research Institute Of Nano And Micro Sciences Qingdao Co ltd
Qingdao University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Frontier Research Institute Of Nano And Micro Sciences Qingdao Co ltd, Qingdao University of Science and Technology filed Critical Frontier Research Institute Of Nano And Micro Sciences Qingdao Co ltd
Priority to CN202110756320.XA priority Critical patent/CN113559920A/en
Publication of CN113559920A publication Critical patent/CN113559920A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

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

ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof
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.
CN202110756320.XA 2021-07-05 2021-07-05 ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof Pending CN113559920A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110756320.XA CN113559920A (en) 2021-07-05 2021-07-05 ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110756320.XA CN113559920A (en) 2021-07-05 2021-07-05 ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113559920A true CN113559920A (en) 2021-10-29

Family

ID=78163618

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110756320.XA Pending CN113559920A (en) 2021-07-05 2021-07-05 ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113559920A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114210364A (en) * 2021-11-17 2022-03-22 青岛科技大学 Iron-loaded functionalized SAPO-34 molecular sieve and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2298445A1 (en) * 2009-08-19 2011-03-23 King Abdulaziz City for Science and Technology Hydroconversion process and catalyst used therein
CN107640775A (en) * 2017-10-17 2018-01-30 北京科技大学 A kind of method that the molecular sieves of ZSM 5 are prepared using solid waste
CN108238614A (en) * 2018-03-16 2018-07-03 淮阴工学院 The method that ZSM-5 zeolite is prepared as raw material slightly soluble agent using clay
CN108264057A (en) * 2016-12-30 2018-07-10 中国石油天然气股份有限公司 Method for solid-phase synthesis of wettability-controllable ZSM-5 zeolite
CN112599762A (en) * 2020-12-15 2021-04-02 南京国轩电池有限公司 TiO 22Negative electrode material of CNF battery and preparation method thereof
CN112875717A (en) * 2021-01-28 2021-06-01 青岛科技大学 Method for synthesizing TS-1 zeolite by solvent-free method with adjustable size

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2298445A1 (en) * 2009-08-19 2011-03-23 King Abdulaziz City for Science and Technology Hydroconversion process and catalyst used therein
CN108264057A (en) * 2016-12-30 2018-07-10 中国石油天然气股份有限公司 Method for solid-phase synthesis of wettability-controllable ZSM-5 zeolite
CN107640775A (en) * 2017-10-17 2018-01-30 北京科技大学 A kind of method that the molecular sieves of ZSM 5 are prepared using solid waste
CN108238614A (en) * 2018-03-16 2018-07-03 淮阴工学院 The method that ZSM-5 zeolite is prepared as raw material slightly soluble agent using clay
CN112599762A (en) * 2020-12-15 2021-04-02 南京国轩电池有限公司 TiO 22Negative electrode material of CNF battery and preparation method thereof
CN112875717A (en) * 2021-01-28 2021-06-01 青岛科技大学 Method for synthesizing TS-1 zeolite by solvent-free method with adjustable size

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MAJID H. NADA ET AL.: "Mechanochemical reaction pathways in solvent-free synthesis of ZSM-5" *
XIAO HUI WANG ET AL.: "Oxidation behavior of TiC-containing Ti3AlC2 based material at 500–900 ℃ in air" *
孙家伟等: "纳米TiO2/ZSM-5 型催化剂的制备及其光催化应用研究进展" *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114210364A (en) * 2021-11-17 2022-03-22 青岛科技大学 Iron-loaded functionalized SAPO-34 molecular sieve and preparation method and application thereof

Similar Documents

Publication Publication Date Title
WO2019144253A1 (en) Preparation method for hollow single crystal beta molecular sieve
WO2015161630A1 (en) Fezsm-5 molecular sieve and synthesis process therefor
CN102666385A (en) Method of preparing zsm-5 zeolite using nanocrystalline zsm-5 seeds
CN112678842B (en) Synthesis method of nano Sn-Beta molecular sieve
CN103318911A (en) Preparation method of beta zeolite with multilevel pore canals
CN107777700A (en) Stepped hole HZSM-5 molecular sieve and preparation method thereof
JP6423729B2 (en) Method for producing beta-type zeolite
CN111115651B (en) Nano molecular sieve, synthesis method and application thereof
CN113149026A (en) Preparation method of molecular sieve with stepped pore structure
US10287172B2 (en) Preparation method for beta zeolite
JP2016506903A (en) Method for producing boron-containing zeolitic material having MWW framework structure
CN113135578B (en) Preparation method of silicon-germanium ISV zeolite molecular sieve
CN110156040A (en) ZSM-5 molecular sieve and preparation method thereof
CN113559920A (en) ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof
CN114804136B (en) Preparation method and application of nano SSZ-13 molecular sieve
CN112624146B (en) Molecular sieve and preparation method and application thereof
CN112645346B (en) Method for preparing nanoscale Sn-Beta molecular sieve by using double templates
CN110844919B (en) Preparation method of NaY molecular sieve and NaY molecular sieve prepared by preparation method
CN109694086B (en) Preparation method of nano ZSM-5 zeolite molecular sieve aggregate
KR101208224B1 (en) Manufacturing method of crystalline zeolite
AU2021105922A4 (en) ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof
SG194087A1 (en) Process for producing molecular sieve materials
CN107686119B (en) hierarchical porous silicon-aluminum molecular sieve nanoclusters and preparation method thereof
WO2017217424A1 (en) Method for producing beta zeolite
CN117800357B (en) IM-5 molecular sieve synthesis method and modification method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20211029