AU2021105922A4 - 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
- Publication number
- AU2021105922A4 AU2021105922A4 AU2021105922A AU2021105922A AU2021105922A4 AU 2021105922 A4 AU2021105922 A4 AU 2021105922A4 AU 2021105922 A AU2021105922 A AU 2021105922A AU 2021105922 A AU2021105922 A AU 2021105922A AU 2021105922 A4 AU2021105922 A4 AU 2021105922A4
- Authority
- AU
- Australia
- Prior art keywords
- zsm
- composite material
- tio2
- preparation
- molecular sieve
- 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.)
- Ceased
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 239000002131 composite material Substances 0.000 title claims abstract description 117
- 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 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 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 117
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000227 grinding Methods 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 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
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 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 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 112
- 239000000377 silicon dioxide Substances 0.000 claims description 35
- 239000002105 nanoparticle Substances 0.000 claims description 34
- 235000012239 silicon dioxide Nutrition 0.000 claims description 32
- 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
- 239000010936 titanium Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 description 27
- 229910052906 cristobalite Inorganic materials 0.000 description 27
- 239000004570 mortar (masonry) Substances 0.000 description 27
- 229910052682 stishovite Inorganic materials 0.000 description 27
- 229910052905 tridymite Inorganic materials 0.000 description 27
- 229910052573 porcelain Inorganic materials 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
- 238000001035 drying Methods 0.000 description 15
- 229910021485 fumed silica Inorganic materials 0.000 description 15
- 239000011148 porous material Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 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
- 230000009286 beneficial effect Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 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
- 239000012071 phase Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000035484 reaction time Effects 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
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention provides a ZSM-5 molecular sieve/titanium dioxide composite
material and preparation method thereof, and relates to the technical field of molecular
sieve preparation. The preparation method provided by the invention comprises the
following steps: grinding and mixing a silicon source, an aluminum source, ammonium
chloride, an organic template agent, sodium hydroxide and Ti3AlC 2 , and performing
crystallization reaction to obtain a precursor of the composite material. And calcining
the composite precursor to obtain the ZSM-5/TiO 2 composite material. The method
does not need to add solvent in the process of preparing the ZSM-5/TiO2 composite
material, is green and environment-friendly, is simple and efficient to operate, and is
suitable for industrial popularization and application.
1/6
FIGURES
)C
10 20 30 40
2 Theta (degree)
Figure
Figure2
Description
1/6
10 20 30 40 2 Theta (degree)
Figure
Figure2
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 ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof.
BACKGROUND ZSM-5 molecular sieve is a kind of porous aluminosilicate, which has typical MFI framework structure with straight channels and zigzag channels of ten-membered rings, and belongs to high-silicon five-membered ring molecular sieve. ZSM-5 molecular sieve is widely used in petrochemical industry because of its unique pore structure, special shape selectivity, thermal stability, chemical stability and acid strength. As an important industrial material, ZSM-5 molecular sieve is mainly synthesized under hydrothermal conditions at present, but water occupies a large space in the autoclave, resulting in high pressure in the autoclave, which greatly affects the yield of ZSM-5 molecular sieve. In addition, a large amount of waste liquid produced after hydrothermal reaction also leads to safety and environmental problems.
SUMMARY The purpose of the invention is to provide a ZSM-5 molecular sieve/titanium dioxide composite material and a preparation method thereof. in the preparation process of the ZSM-5/TiO2 composite material, no solvent is added, which is green and environment friendly, simple and efficient to operate, and suitable for industrial popularization and application. In order to achieve the above object of the invention, the present invention provides the following technical scheme: The invention provides a preparation method of a green solvent-free ZSM-5/TiO2 composite material, which comprises the following steps:
Grinding and mixing a silicon source, an aluminum source, ammonium chloride, an organic template agent, sodium hydroxide and TiAIC2, and performing crystallization reaction to obtain a precursor of the composite material. Calcining the composite precursor to obtain the ZSM-5/TiO2 composite material. Preferably, the ratio of silicon to aluminum is 50-90:1. Preferably, the silicon source comprises sodium silicate and silicon dioxide. The aluminum source comprises boehmite. Preferably, the mass ratio of ammonium chloride, organic template agent and aluminum source is 0.45:0.24:0.016-0.024. Preferably, the organic template agent comprises tetrapropylammonium bromide. Preferably, the mass ratio of the silicon source to the sodium hydroxide is 6-12:1. Preferably, the mass ratio of the silicon source to TiAIC2 is 40-120:1. Preferably, the temperature of the crystallization reaction is 160-200°C,and the time is 12-36 h. Preferably, the calcination temperature is 500-600 0C and the calcination time is 4 8h. The ZSM-5/TiO2 composite material prepared by the preparation method in the technical scheme comprises a ZSM-5 molecular sieve and TiO2 nanoparticles distributed on the surface of the ZSM-5 molecular sieve. The invention provides a preparation method of a green solvent-free ZSM-5/TiO2 composite material, which comprises the following steps: grinding and mixing a silicon source, an aluminum source, ammonium chloride, an organic template agent, sodium hydroxide and Ti3AIC2, and performing crystallization reaction to obtain a composite material precursor. And calcining the composite precursor to obtain the ZSM-5/TiO2 composite material. According to the invention, all materials are fully mixed by grinding and mixing. in the crystallization reaction process, a silicon source and an aluminum source are crystallized under the induction of an organic template agent to form a ZSM molecular sieve crystal with an MFI framework structure. and the organic template agent in the ZSM-5 molecular sieve crystal is removed by calcination to obtain the ZSM molecular sieve. Meanwhile, in the calcination process, TiAIC2 and ZSM-5 molecular sieve are compounded in situ, and titanium dioxide nanoparticles are introduced on the surface of ZSM-5 molecular sieve to form ZSM-5/TiO2 composite material. According to the invention, no solvent is needed in the preparation process, so that the generation of waste liquid is greatly reduced, the yield and efficiency are greatly improved, and the method has very important significance for designing and preparing zeolite with catalytic activity. Furthermore, the method provided by the invention has the advantages of small pressure in the kettle, high yield, low pollution rate and high safety, is a green, environment-friendly, efficient and simple-to-operate synthesis strategy, and has important significance in actual industrial production.
BRIEF DESCRIPTION OF THE FIGURES Fig. 1 is X-ray diffraction pattern of ZSM-5/TiO2 composite prepared in embodiment 1 Fig. 2 is scanning electron micrograph of ZSM-5/TiO2 composite prepared in embodiment 1. Fig. 3 is high magnification transmission electron micrograph of ZSM-5/TiO2 composite prepared in embodiment 1 Fig. 4 is medium magnification transmission electron micrograph of ZSM-5/TiO2 composite prepared in embodiment 1 Fig. 5 is low magnification transmission electron micrograph of ZSM-5/TiO2 composite prepared in embodiment 1. Fig. 6 is X- ray photoelectron spectroscopy of ZSM-5/TiO2 composite prepared in embodiment 1 Fig. 7 is electron microscope energy spectrum of ZSM-5/TiO2 composite prepared in embodiment 1 Fig. 8 is X-ray diffraction diagram of ZSM-5/TiO2 composites prepared in embodiments 1-3 Fig. 9 is X-ray diffraction diagram of ZSM-5/TiO2 composites prepared in embodiments 1, 4 and 5. Fig. 10 is X-ray diffraction diagram of ZSM-5/TiO2 composites prepared in embodiments 1, 6 and 7.
Fig. 11 is X-ray diffraction diagram of ZSM-5/TiO2 composites prepared in embodiments 1, 8 and 9. Fig. 12 is X-ray diffraction diagram of ZSM-5/TiO2 composites prepared in embodiments 1, 10 and 11.
DESCRIPTION OF THE INVENTION The invention provides a preparation method of a green solvent-free ZSM-5/TiO2 composite material, which comprises the following steps: Grinding and mixing a silicon source, an aluminum source, ammonium chloride, an organic template agent, sodium hydroxide and TiAIC2, and performing crystallization reaction to obtain a precursor of the composite material. Calcining the composite precursor to obtain the ZSM-5/TiO2 composite material. In the present invention, unless otherwise specified, the adopted raw materials are all commercially available products well known to those skilled in the art. The method comprises the following steps: grinding and mixing a silicon source, an aluminum source, ammonium chloride, an organic template agent, sodium hydroxide and Ti3AIC2, and performing crystallization reaction to obtain a precursor of the composite material. In the present invention, the silicon source preferably includes sodium silicate and silicon dioxide. The sodium silicate is preferably sodium silicate nonahydrate. The silica is preferably fumed silica, and the specific surface area of the fumed silica is preferably 400 m 2/g. In the present invention, the molar ratio of sodium silicate to silicon dioxide is preferably 0.5-0.8:1, more preferably 0.6-0.7:1. In the present invention, the aluminum source preferably comprises boehmite. In the present invention, the ratio of silicon to aluminum is preferably 50-90: 1, more preferably 70-80:1. In the present invention, the silicon-aluminum ratio of the silicon source and the aluminum source refers to the mass ratioof SiO2 and A1203. In the present invention, the organic template agent preferably comprises tetrapropylammoniumbromide.
In the present invention, the mass ratio of the ammonium chloride, the organic template agent and the aluminum source is preferably 0.45:0.24:0.016-0.024, more preferably 0.45:0.24:0.019-0.021. In the present invention, the mass ratio of the silicon source to sodium hydroxide is preferably 6-12:1, more preferably 8-10:1. In a specific embodiment of the present invention, the mass ratio of silica to sodium hydroxide is preferably 6-12:1, and more preferably 8-10:1. In the present invention, the mass ratio of the silicon source to Ti3AIC2 is preferably 40-120:1, more preferably 60 100:1. In a specific embodiment of the present invention, the mass ratio of the silicon dioxide to Ti3AIC2 is preferably 40-120:1, and more preferably 60-100:1. According to the invention, the ZSM-5/TiO2 composite material is synthesized from raw materials within the above range, and the crystallinity of the ZSM-5 molecular sieve can be improved. Preferably, the interaction between sodium silicate nonahydrate and ammonium chloride displaces sodium ions in sodium silicate nonahydrate to form solid salt sodium chloride, which leads to the spontaneous dispersion of the solid salt on the amorphous carrier and greatly reduces the spectral band of TPA' species. Vapor phase silica is beneficial to form skeleton silicon tetrahedron. The addition of organic template tetrapropylammonium bromide can induce crystallization, which is beneficial to the formation of ZSM-5 molecular sieve crystals with MF1 skeleton structure. Adding a proper amount of sodium hydroxide can adjust the pH value of the system and provide a suitable alkaline environment for the crystallization of ZSM-5 molecular sieve. With Ti3AIC2 as titanium source, titanium can be introduced into ZSM-5 molecular sieve, and two-dimensional transition metal carbide Ti3AIC2 and ZSM-5 molecular sieve are compounded in situ, finally forming ZSM-5/TiO2 composite material. In the present invention, the grinding and mixing method of silicon source, aluminum source, ammonium chloride, organic template agent, sodium hydroxide and Ti3AIC2 preferably comprises the following steps: firstly grinding and mixing the silicon source and the aluminum source to obtain a first mixed material. Grinding and mixing the first mixed material with ammonium chloride, organic template agent and sodium hydroxide for the second time to obtain a second mixed material. Grinding and mixing the second mixed material and Ti3AIC2 for the third time to obtain a third mixed material. In the present invention, the first grinding and mixing time is preferably 3min. In the present invention, the second grinding and mixing time is preferably 3min. In the present invention, the third grinding and mixing time is preferably 10min. In the present invention, there is no special requirement on the rotation speed of the first grinding mixing, the second grinding mixing and the third grinding mixing, and manual grinding is preferred. According to the invention, the silicon source and the aluminum source can be fully mixed by utilizing the first grinding mixing. The second grinding and mixing can provide organic template agent and other substances to induce further crystallization. And the third grinding mixing can mix Ti3AIC2 with the above materials more uniformly. According to the invention, by adopting the grinding and mixing method, the raw materials can be mixed more fully, and the ZSM-5 molecular sieve crystal with MFI framework structure can be formed more favorably. In the present invention, the grinding mixing is preferably carried out in an agate mortar. After the grinding and mixing, the invention preferably carries out crystallization reaction on the obtained third mixed material to obtain the precursor of the composite material. In the present invention, the crystallization reaction is preferably carried out in a high-pressure reaction kettle. In the present invention, the temperature of the crystallization reaction is preferably 160-200 °C , more preferably 180-190. The crystallization reaction time is preferably 12-36h, more preferably 24-30h. In the crystallization reaction process of this invention, 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 ZSM-5 molecular sieve crystals with an MFI framework structure. After the crystallization reaction, the invention preferably cools the obtained crystal to room temperature, and sequentially washes and dries to obtain the precursor of the composite material. In the present invention, the washing method preferably includes suction filtration with deionized water; The drying temperature is preferably 80°C and the drying time is preferably 12h. The ZSM-5/TiO2 composite material is obtained by calcining the composite material precursor after obtaining the composite material precursor. In the present invention, the calcination is preferably carried out in a muffle furnace. In the present invention, the calcination temperature is preferably 500-600°C, more preferably 550°C. The calcination time is preferably 4-8h, more preferably 5-6h. In the present invention, the calcination is preferably carried out in an air atmosphere. In the present invention, the heating rate from room temperature to the calcination temperature is preferably 2 to 5C./min, more preferably 3C./min. In the calcination process, the structure of the ZSM-5 molecular sieve crystal is destroyed, and the organic template agent in the hole is fully removed to obtain the ZSM molecular sieve; Meanwhile, in the calcination process, TiAIC2 and ZSM-5 molecular sieve are compounded in situ, and titanium dioxide nanoparticles are introduced on the surface of ZSM-5 molecular sieve to form ZSM-5/TiO2 composite material. The ZSM-5/TiO2 composite material prepared by the preparation method in the technical scheme comprises a ZSM-5 molecular sieve and TiO2 nanoparticles distributed on the surface of the ZSM-5 molecular sieve. In the present invention, the specific surface area of the ZSM-5 molecular sieve is preferably 447-451m2/g; The micropore volume is preferably 0.218-0.232cm3/g.The average pore diameter is preferably 0.95-0.96nm. In the present invention, the average particle size of the TiO2 nanoparticles is preferably 8-1Onm, more preferably 9nm. According to the invention, TiO2 nanoparticles with uniform particles are introduced on the surface of the ZSM-5 molecular sieve, which is beneficial to improving the catalytic activity of the composite material. In the following, the technical scheme of the present invention will be described clearly and completely in combination with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without creative labor belong to the scope of protection of the present invention. Embodiment 1 Putting sodium silicate nonahydrate, fumed silica and boehmite in an agate mortar according to a silicon-aluminum ratio (mass ratioof SiO2 to A1203) of 70, and preliminarily grinding for 3mins. Then, 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (mass ratio of SiO2:NaOH=8) are added into the mixture, and grinding is continued for 3mins. At last, 0.01g of Ti3AIC2 (the mass ratio of SiO2:Ti3AIC2=60) is placed in an agate mortar, mixed evenly and ground fully for 10 min. Transferring the obtained mixed materials to a high-pressure reaction kettle, reacting at 180°C for 24h, after the reaction is finished, cooling to room temperature, filtering the obtained crystals with deionized water, and drying the filtered samples at °C for 12h to obtain the precursor of the composite material. And placing the precursor of the composite material in a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature from normal temperature to 550°C at a speed of 2°C /min in an air atmosphere, and keeping the temperature at 55 0 °Cfor 6h to obtain the ZSM-5/TiO2 composite material. In the ZSM-5/TiO2 composite prepared In this embodiment, TiO2 nanoparticles are uniformly distributed on the surface of ZSM-5 molecular sieve. The average pore diameter of ZSM-5 molecular sieve is 0.96nm. The mean particle size of TiO2 nanoparticles is 9nm. Embodiment 2 Putting sodium silicate nonahydrate, fumed silica and boehmite in an agate mortar according to a silicon-aluminum ratio of 50, and preliminarily grinding for 3mins; Then, 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (mass ratio of SiO2:NaOH=8) are added into the mixture, and grinding is continued for 3mins. At last, 0.01g of Ti3AIC2 (the mass ratioof SiO2:Ti3AIC2=60) is placed in an agate mortar, mixed evenly and ground fully for 10 min. Transferring the obtained mixed materials to a high-pressure reaction kettle, reacting at 180°C for 24h, filtering the obtained crystals with deionized water after the reaction is cooled to room temperature, and drying the filtered samples at 80°C for 12h to obtain a composite precursor. And placing the precursor of the composite material in a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature from normal temperature to 550°C at a speed of 2C/min in an air atmosphere, and keeping the temperature at 550°C for 6h to obtain the ZSM-5/TiO2 composite material. In the ZSM /TiO2 composite prepared in this embodiment, TiO2 nanoparticles are uniformly distributed on the surface of ZSM-5 molecular sieve. The average pore diameter of ZSM molecular sieve is 0.95nm. The mean particle size of TiO2 nanoparticles is 9nm. embodiment 3 Putting sodium silicate nonahydrate, fumed silica and boehmite in an agate mortar according to a silicon-aluminum ratio of 90, and preliminarily grinding for 3mins; Then, 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (mass ratio of SiO2:NaOH=8) are added into the mixture, and grinding is continued for 3mins. At last, 0.01g Ti3AIC2 (the mass ratio of SiO2:Ti3AIC2=60) is placed in an agate mortar, mixed evenly and ground fully for 10 min. Transferring the obtained mixed materials to a high-pressure reaction kettle, reacting at 180°C for 24h, filtering the obtained crystals with deionized water after the reaction is cooled to room temperature, and drying the filtered samples at 80°C for 12h to obtain a composite precursor. And placing the precursor of the composite material in a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature from normal temperature to 550°C at a speed of 2C/min in an air atmosphere, and keeping the temperature at 550 °C for 6h to obtain the ZSM-5/TiO2 composite material. In the ZSM-5/TiO2 composite prepared in this embodiment, TiO2 nanoparticles are uniformly distributed on the surface of ZSM-5 molecular sieve. The average pore diameter of ZSM-5 molecular sieve is 0.96nm. The mean particle size of TiO2 nanoparticles is 9nm. embodiment 4 Putting sodium silicate nonahydrate, fumed silica and boehmite in an agate mortar according to a silicon-aluminum ratio of 70, and preliminarily grinding for 3mins; Then, 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.1g of sodium hydroxide (mass ratio of SiO2:NaOH=6) are added into the mixture, and grinding is continued for 3mins; At last, 0.01g Ti3AIC2 (the mass ratioof SiO2:Ti3AC2=60) is placed in an agate mortar, mixed evenly and ground fully for 10min; Transferring the obtained mixed materials to a high-pressure reaction kettle, reacting at 180°C for 24h, filtering the obtained crystals with deionized water after the reaction is cooled to room temperature, and drying the filtered samples at 80 °C for 12h to obtain composite precursor. And placing the precursor of the composite material in a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature from normal temperature to 550°C at a speed of 2 °C/min in an air atmosphere, and keeping the temperature at 55 0 °Cfor 6h to obtain the ZSM-5/TiO2 composite material. In the ZSM-5/TiO2 composite prepared in this embodiment, TiO2 nanoparticles are uniformly distributed on the surface of ZSM-5 molecular sieve. The average pore diameter of ZSM-5 molecular sieve is 0.96n. The mean particle size of TiO2 nanoparticles is 9nm. Embodiment 5 Putting sodium silicate nonahydrate, fumed silica and boehmite in an agate mortar according to a silicon-aluminum ratio of 70, and preliminarily grinding for 3mins; Then, 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.05g of sodium hydroxide (mass ratio of SiO2:NaOH=12) are added into the mixture, and grinding is continued for 3mins. At last, 0.01g of Ti3AIC2 (the mass ratio of SiO2:Ti3AIC2=60) is placed in an agate mortar, mixed evenly and ground fully for ten minutes; Transferring the obtained mixed materials to a high-pressure reaction kettle, reacting at 180°Cfor 24h, filtering the obtained crystals with deionized water after the reaction is cooled to room temperature, and drying the filtered samples at 8 0 °Cfor 12h to obtain a composite precursor. And placing the precursor of the composite material in a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature from normal temperature to 550°Cat a speed of 2C/min in an air atmosphere, and keeping the temperature at 550 °C for 6h to obtain the ZSM-5/TiO2 composite material. In the ZSM-5/TiO2 composite prepared. In this embodiment, TiO2 nanoparticles are uniformly distributed on the surface of ZSM-5 molecular sieve. The average pore diameter of ZSM-5 molecular sieve is 0.96nm. The mean particle size of TiO2 nanoparticles is 9nm. Embodiment 6 Putting sodium silicate nonahydrate, fumed silica and boehmite in an agate mortar according to a silicon-aluminum ratio of 70, and preliminarily grinding for 3mins; Then, 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (mass ratio of SiO2:NaOH=8) are added into the mixture, and grinding is continued for 3mins; At last, 0.015g of Ti3AIC2 (mass ratio SiO2:Ti3AIC2=40) was put into agate mortar, mixed evenly and ground for ten minutes. Transferring the obtained mixed materials to a high-pressure reaction kettle, reacting at 180°C for 24h, filtering the obtained crystals with deionized water after the reaction is cooled to room temperature, and drying the filtered samples at 80°C for 12h to obtain a composite precursor. And placing the precursor of the composite material in a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature from normal temperature to 550°C at a speed of 2C/min in an air atmosphere, and keeping the temperature at 550°C for 6h to obtain the ZSM-5/TiO2 composite material. In the ZSM-5/TiO2 composite prepared in this embodiment, TiO2 nanoparticles are uniformly distributed on the surface of ZSM-5 molecular sieve. The average pore diameter of ZSM-5 molecular sieve is 0.96nm. The mean particle size of TiO2 nanoparticles is 9nm. embodiment 7 Putting sodium silicate nonahydrate, fumed silica and boehmite in an agate mortar according to a silicon-aluminum ratio of 70, and preliminarily grinding for 3mins, Then, 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (mass ratio of SiO2:NaOH=8) are added into the mixture, and grinding is continued for 3mins. At last, 0.005g Ti3AIC2 (mass ratio SiO2:Ti3AIC2=120) was put into agate mortar, mixed evenly and ground for ten minutes. Transferring the obtained mixed materials to a high-pressure reaction kettle, reacting at 180°Cfor 24h, filtering the obtained crystals with deionized water after the reaction is cooled to room temperature, and drying the filtered samples at 80°C for 12h to obtain a composite precursor. And placing the precursor of the composite material in a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature from normal temperature to 550'Cat a speed of 2C/min in an air atmosphere, and keeping the temperature at 55 0 °Cfor 6h to obtain the ZSM-5/TiO2 composite material. In the ZSM-5/TiO2 composite prepared in this embodiment, TiO2 nanoparticles are uniformly distributed on the surface of ZSM-5 molecular sieve. The average pore diameter of ZSM-5 molecular sieve is 0.96nm. The mean particle size of TiO2 nanoparticles is 9nm. embodiment 8 Putting sodium silicate nonahydrate, fumed silica and boehmite in an agate mortar according to a silicon-aluminum ratio of 70, and preliminarily grinding for 3mins; Then, 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (mass ratio of SiO2:NaOH=8) are added into the mixture, and grinding is continued for 3mins. At last, 0.01g of Ti3AIC2(the mass ratioof SiO2:Ti3AIC2=60) is placed in an agate mortar, mixed evenly and ground fully for ten minutes. Transferring the obtained mixed materials to a high-pressure reaction kettle, reacting at 16 0 °Cfor 24h, filtering the obtained crystals with deionized water after the reaction is cooled to room temperature, and drying the filtered samples at 80 °Cfor 12h to obtain a composite precursor. And placing the precursor of the composite material in a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature from normal temperature to 550 0C at a speed of 2C/min in an air atmosphere, and keeping the temperature at 5500 C for 6h to obtain the ZSM-5/TiO2 composite material. In the ZSM-5/TiO2 composite prepared in this embodiment, TiO2 nanoparticles are uniformly distributed on the surface of ZSM-5 molecular sieve. The average pore diameter of ZSM-5 molecular sieve is 0.96nm. The mean particle size of TiO2 nanoparticles is 9nm. Embodiment 9 Putting sodium silicate nonahydrate, fumed silica and boehmite in an agate mortar according to a silicon-aluminum ratio of 70, and preliminarily grinding for 3mins; Then, 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (mass ratio of SiO2:NaOH=8) are added into the mixture, and grinding is continued for 3mins. At last, 0.01g Ti3AIC2 (the mass ratioof SiO2:Ti3AIC2=60) is placed in an agate mortar, mixed evenly and ground fully for ten minutes; Transferring the obtained mixed materials to a high-pressure reaction kettle, reacting at 200°Cfor 24h, filtering the obtained crystals with deionized water after the reaction is cooled to room temperature, and drying the filtered samples at 80 0C for 12h to obtain a composite precursor. And placing the precursor of the composite material in a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature from normal temperature to 550°Cat a speed of 2 °C/min in an air atmosphere, and keeping the temperature at 55 0 °Cfor 6h to obtain the ZSM-5/TiO2 composite material. In the ZSM-5/TiO2 composite prepared in this embodiment, TiO2 nanoparticles are uniformly distributed on the surface of ZSM-5 molecular sieve. The average pore diameter of ZSM-5 molecular sieve is 0.96nm. The mean particle size of TiO2 nanoparticles is 9nm. Embodiment 10 Putting sodium silicate nonahydrate, fumed silica and boehmite in an agate mortar according to a silicon-aluminum ratio of 70, and preliminarily grinding for 3mins. Then, 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (mass ratio of SiO2:NaOH=8) are added into the mixture, and grinding is continued for 3mins. At last, 0.01Og of Ti3AIC2((the mass ratioof SiO2:Ti3AIC2=60) is placed in an agate mortar, mixed evenly and ground fully for ten minutes. Transferring the obtained mixed materials to a high-pressure reaction kettle, reacting at 180 °Cfor 12h, filtering the obtained crystals with deionized water after the reaction is cooled to room temperature, and drying the filtered samples at 800 C for 12h to obtain a composite precursor. And placing the precursor of the composite material in a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature from normal temperature to 550°Cat a speed of 20 C/min in an air atmosphere, and keeping the temperature at 550°Cfor 6h to obtain the ZSM-5/TiO2 composite material. In the ZSM-5/TiO2 composite prepared in this embodiment, TiO2 nanoparticles are uniformly distributed on the surface of ZSM-5 molecular sieve. The average pore diameter of ZSM-5 molecular sieve is 0.96nm. The mean particle size of TiO2 nanoparticles is 9nm. Embodiment 11 Putting sodium silicate nonahydrate, fumed silica and boehmite in an agate mortar according to a silicon-aluminum ratio of 70, and preliminarily grinding for 3mins. Then, 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (mass ratio of SiO2:NaOH=8) are added into the mixture, and grinding is continued for 3mins; At last, 0.01g of TiAIC2 (the mass ratio of Si2:Ti3AIC2=60) is placed in an agate mortar, mixed evenly and ground fully for ten minutes; Transferring the obtained mixed materials to a high-pressure reaction kettle, reacting at 180 °Cfor 36h, filtering the obtained crystals with deionized water after the reaction is cooled to room temperature, and drying the filtered samples at 80 °Cfor 12h to obtain a composite precursor; And placing the precursor of the composite material in a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature from normal temperature to 550 °Cat a speed of 2 °C/min in an air atmosphere, and keeping the temperature at 550 °Cfor 6h to obtain the ZSM-5/TiO2 composite material. In the ZSM-5/TiO2 composite prepared in this embodiment, TiO2 nanoparticles are uniformly distributed on the surface of ZSM-5 molecular sieve. The average pore diameter of ZSM-5 molecular sieve is 0.96nm. The mean particle size of TiO2 nanoparticles is 9nm. Embodiment 12 Putting sodium silicate nonahydrate, fumed silica and boehmite in an agate mortar according to a silicon-aluminum ratio of 70, and preliminarily grinding for three minutes; Then, 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (mass ratio of SiO2:NaOH=8) are added into the mixture, and grinding is continued for three minutes. At last, 0.01g of Ti3AIC2 (the mass ratio of SiO2:Ti3AIC2=60) is placed in an agate mortar, mixed evenly and ground fully for ten minutes; Transferring the obtained mixed materials to a high-pressure reaction kettle, reacting at 180 °C for 24h, filtering the obtained crystals with deionized water after the reaction is cooled to room temperature, and drying the filtered samples at 800 C for 12h to obtain a composite precursor. And placing the precursor of the composite material in a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature from normal temperature to 550 0C at a speed of 20 C/min in an air atmosphere, and keeping the temperature at 5500 C for 4h to obtain the ZSM-5/TiO2 composite material. In the ZSM-5/TiO2 composite prepared in this embodiment, TiO2 nanoparticles are uniformly distributed on the surface of ZSM-5 molecular sieve. The average pore diameter of ZSM-5 molecular sieve is 0.96nm. The mean particle size of TiO2 nanoparticles is 9nm. Embodiment 13
Putting sodium silicate nonahydrate, fumed silica and boehmite in an agate mortar according to a silicon-aluminum ratio of 70, and preliminarily grinding for three minutes; Then, 0.45g of ammonium chloride, 0.24g of tetrapropylammonium bromide and 0.075g of sodium hydroxide (mass ratio of SiO2:NaOH=8) are added into the mixture, and grinding is continued for three minutes. At last, 0.010g of Ti3AIC2( (the mass ratio of SiO2:Ti3AIC2=60) is placed in an agate mortar, mixed evenly and ground fully for ten minutes. Transferring the obtained mixed materials to a high-pressure reaction kettle, reacting at 180 0C for 24h, filtering the obtained crystals with deionized water after the reaction is cooled to room temperature, and drying the filtered samples at 800 C for 12h to obtain a composite precursor. And placing the precursor of the composite material in a porcelain boat, placing the porcelain boat in a muffle furnace, raising the temperature from normal temperature to 550 0C at a speed of 20 C/min in an air atmosphere, and keeping the temperature at 5500 C for 8 hours to obtain the ZSM-5/TiO2 composite material. In the ZSM-5/TiO2 composite prepared in this embodiment, TiO2 nanoparticles are uniformly distributed on the surface of ZSM-5 molecular sieve. The average pore diameter of ZSM-5 molecular sieve is 0.96nm. The mean particle size of TiO2 nanoparticles is 9nm. Test case The X-ray powder diffraction pattern of ZSM-5/TiO2 composite prepared in embodiment 1 is shown in Fig. 1. It can be seen from Fig.1 that the ZSM-5/TiO2 composite material prepared by the present invention belongs to zeolite with typical MFI structure. The SEM image of ZSM-5/TiO2 composite prepared in embodiment 1 is shown in Fig. 2. It can be seen from Fig. 2 that the ZSM-5/TiO2 composite material prepared by the present invention has a rough and irregular dough shape. The transmission electron micrographs of ZSM-5/TiO2 composite prepared in embodiment 1 are shown in Figs.3-5. It can be seen from Figs.3-5 that TiO2 nanoparticles with uniform particle size are uniformly distributed on the material surface. X-ray photoelectron spectroscopy of ZSM-5/TiO2 composite prepared in embodiment 1 is shown in Fig.6. It can be seen from Fig.6 that the ZSM-5/TiO2 composite prepared by the present invenTion contains Si, Al, Ti, C, 0 and other elements inside. The energy spectrum of the ZSM-5/TiO2 composite prepared in embodiment 1 is shown in Fig. 7. It can be seen from Fig. 7 that the four elements C, Si, Al and Ti are evenly distributed on the material surface. X-ray diffraction patterns of ZSM-5/TiO2 composites prepared in embodiments 1-3 are 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 raw material silicon to aluminum. within the range of the ratio of raw material silicon to aluminum adopted in the present invention, the crystallinity of the composite material increases with the increase of the ratio of raw material silicon to aluminum. X-ray diffraction patterns of ZSM-5/TiO2 composites prepared in embodiment 1, 4 and 5 are shown in Fig.9. It can be seen from Fig.9 that the crystallinity of the composite material can be changed by adjusting the ratio of raw materials to silicon and sodium, and the crystallinity of the composite material decreases with the increase of the ratio of raw materials to sodium and aluminum within the range of the ratio of silicon and sodium adopted in the present invention. X-ray diffraction patterns of ZSM-5/TiO2 composites prepared in embodiment 1, 6 and 7 are shown in Fig.10. It can be seen from Fig.10 that the amount of TiAIC2 added will affect the crystallinity of the composite material. in the present invention, the crystallinity of the composite material will be lower as the amount of Ti3AIC2 added to the raw material increases. X-ray diffraction patterns of ZSM-5/TiO2 composites prepared in embodiment 1, 8 and 9 are shown in Fig.11. It can be seen from Fig. 11 that the crystallization temperature will affect the crystallinity of the composite material, and the crystallinity of the composite material is the highest at 1800 C. X-ray diffraction patterns of ZSM-5/TiO2 composites prepared in embodiment 1, 10 and 11 are shown in Fig. 12. It can be seen from Fig. 12 that the crystallization time will affect the crystallinity of the composite material. in this experiment, the crystallization time is more than 24h at 1800 C, and the composite material shows good crystallinity.
The above is only the preferred embodiment of the present invention, and it should be pointed out that for ordinary people in the technical field, without departing from the principle of the present invention, several improvements and embellishments can be made, and these improvements and embellishments should also be regarded as the protection scope of the present invention.
Claims (10)
- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. Preparation method of a green solvent-free ZSM-5/TiO 2 composite material, which is characterized by comprising the following steps: Grinding and mixing a silicon source, an aluminum source, ammonium chloride, an organic template agent, sodium hydroxide and Ti 3AlC 2 , and performing crystallization reaction to obtain a precursor ofthe composite material. And calcining the composite precursor to obtain the ZSM/TiO 2 composite material.
- 2. The preparation method according to claim 1, wherein the ratio of silicon to aluminum is 50-90:1.
- 3. The preparation method according to claim 1, wherein the silicon source comprises sodium silicate and silicon dioxide. The aluminum source comprises boehmite.
- 4. The preparation method according to claim 1, is characterized in that the mass ratio of the ammonium chloride, the organic template agent and the aluminum source is 0.45:0.24:0.016-0.024.
- 5. The preparation method according to claim 1, is characterized in that the organic template agent comprises tetrapropylammonium bromide.
- 6. The preparation method according to claim 1, is characterized in that the mass ratio of the silicon source to the sodium hydroxide is 6-12: 1.
- 7. The preparation method according to claim 1, is characterized in that the mass ratio of the silicon source to Ti 3AlC 2 is 40-120: 1.
- 8. The preparation method according to claim 1, wherein the temperature of thecrystallization reaction is 160-200C and the time is 12-36h.
- 9. The preparation method according to claim 1, wherein the calcination temperature is 500-600°C and the calcination time is 4-8h.
- 10. The ZSM-5/TiO2 composite material prepared by the preparation method according to any one of claims 1 to 9 comprises a ZSM-5 molecular sieve and TiO2 nanoparticles distributed on the surface of the ZSM-5 molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2021105922A AU2021105922A4 (en) | 2021-08-19 | 2021-08-19 | ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2021105922A AU2021105922A4 (en) | 2021-08-19 | 2021-08-19 | ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2021105922A4 true AU2021105922A4 (en) | 2021-10-21 |
Family
ID=78177109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2021105922A Ceased AU2021105922A4 (en) | 2021-08-19 | 2021-08-19 | ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| AU (1) | AU2021105922A4 (en) |
-
2021
- 2021-08-19 AU AU2021105922A patent/AU2021105922A4/en not_active Ceased
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103848439B (en) | Synthetic method of ZSM-5 type molecular sieve | |
| WO2018000660A1 (en) | Environment-friendly method for synthesizing zsm-5 molecular sieve | |
| WO2015161630A1 (en) | Fezsm-5 molecular sieve and synthesis process therefor | |
| CN101643219A (en) | Preparation method of nano-ZSM-5 molecular sieve | |
| CN111592011A (en) | Method for directly synthesizing SSZ-13 zeolite molecular sieve by using TEAOH as organic template agent | |
| CN111495421A (en) | Method for directly preparing M-HZSM-5 molecular sieve | |
| US10287172B2 (en) | Preparation method for beta zeolite | |
| CN113135578B (en) | Preparation method of silicon-germanium ISV zeolite molecular sieve | |
| CN110860307A (en) | Beta molecular sieve catalyst, preparation method and application thereof in preparation of aromatic ketone by acylation method | |
| CN114655966A (en) | Preparation and modification method of sodium-free synthetic multi-stage pore ZSM-5 molecular sieve | |
| CN110745864A (en) | Perovskite type lanthanum titanate material and preparation method and application thereof | |
| CN105293520A (en) | Synthesis method for ZSM-5 molecular sieve of special morphology | |
| CN112499644B (en) | Low SiO2/Al2O3Cu-CHA molecular sieve and preparation method thereof | |
| AU2021105922A4 (en) | ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof | |
| CN113559920A (en) | ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof | |
| CN114014335B (en) | Silicon germanium UTL type macroporous molecular sieve and preparation method thereof | |
| CN112591764B (en) | Single crystal aluminum-rich cascade hole HZSM-5 molecular sieve and green preparation method thereof | |
| WO2018218736A1 (en) | Aluminosilicate zeolite molecular sieve having bog structure and preparation method therefor | |
| CN114804136B (en) | Preparation method and application of nano SSZ-13 molecular sieve | |
| CN111186846B (en) | ITH structure silicon-aluminum molecular sieve and preparation method thereof | |
| CN110589848B (en) | Clinoptilolite synthesis method with columnar morphology | |
| CN104556105B (en) | Aerosol-assisted synthesis method of Beta molecular sieve | |
| CN112357932A (en) | Method for preparing ZSM-5 molecular sieve by solid phase method | |
| CN113181954A (en) | ZSM-5 molecular sieve nanosheet/LDHs composite catalytic material and preparation method thereof | |
| CN108996517B (en) | Hierarchical-pore wide-silica-alumina-ratio EU-1 molecular sieve and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FGI | Letters patent sealed or granted (innovation patent) | ||
| MK22 | Patent ceased section 143a(d), or expired - non payment of renewal fee or expiry |