CN114853029A - Preparation method of titanium silicalite molecular sieve and preparation method of transition metal loaded titanium silicalite molecular sieve - Google Patents
Preparation method of titanium silicalite molecular sieve and preparation method of transition metal loaded titanium silicalite molecular sieve Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 101
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 101
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 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 92
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 41
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 261
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 130
- 239000002699 waste material Substances 0.000 claims abstract description 128
- 238000000227 grinding Methods 0.000 claims abstract description 79
- 239000007788 liquid Substances 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 53
- 238000002156 mixing Methods 0.000 claims abstract description 45
- 238000002425 crystallisation Methods 0.000 claims abstract description 43
- 230000008025 crystallization Effects 0.000 claims abstract description 43
- 239000013078 crystal Substances 0.000 claims abstract description 38
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 37
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010457 zeolite Substances 0.000 claims abstract description 37
- 230000002378 acidificating effect Effects 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 150000003608 titanium Chemical class 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000008139 complexing agent Substances 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 29
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 26
- 229910052710 silicon Inorganic materials 0.000 description 25
- 239000010703 silicon Substances 0.000 description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- 230000032683 aging Effects 0.000 description 13
- 239000012264 purified product Substances 0.000 description 13
- 229910017052 cobalt Inorganic materials 0.000 description 12
- 239000010941 cobalt Substances 0.000 description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 12
- -1 titanium ions Chemical class 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 8
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 8
- 229910000348 titanium sulfate Inorganic materials 0.000 description 8
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- 230000006698 induction Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000013507 mapping Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- 239000002910 solid waste Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
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- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910002001 transition metal nitrate Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
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- 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
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
-
- 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
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- 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
- C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
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- 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
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- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to the technical field of molecular sieve preparation, in particular to a preparation method of a titanium silicalite molecular sieve and a preparation method of a transition metal loaded titanium silicalite molecular sieve. The invention provides a preparation method of a titanium-silicon molecular sieve, which comprises the following steps: mixing and grinding silicon dioxide waste, an organic alkaline template agent, water, zeolite seed crystals and a titanium source to obtain grinding material liquid; the silica waste comprises alkaline silica waste or acidic silica waste; the titanium source is inorganic titanium salt; carrying out crystallization reaction on the grinding material liquid to obtain a solid precursor; and calcining the solid precursor to obtain the titanium silicalite molecular sieve. The invention utilizes the industrial silicon dioxide waste to prepare the titanium silicalite molecular sieve and the transition metal loaded titanium silicalite molecular sieve, and the preparation process does not need to use a large amount of organic solvent, thereby greatly reducing the cost for treating the silicon dioxide waste and generating higher practical economic value.
Description
Technical Field
The invention relates to the technical field of molecular sieve preparation, in particular to a preparation method of a titanium silicalite molecular sieve and a preparation method of a transition metal loaded titanium silicalite molecular sieve.
Background
Titanium silicalite molecular sieve (TS-1) is a breakthrough in the technical field of green chemistry as a new generation of shape-selective oxidation catalytic material. Currently, the TS-1 zeolite molecular sieve is applied to the fields of olefin epoxidation, cyclohexanone ammoxidation, alcohol oxidation, saturated hydrocarbon oxidation, aromatic hydrocarbon hydroxylation and the like. Researches show that the addition of the transition metal has the effect of improving the catalytic performance of the TS-1 zeolite molecular sieve, so that the molecular sieve catalyst has an active site which is easier to expose, the TS-1 zeolite molecular sieve containing ultra-particle size and excellent thermal stability can be obtained, and the method has a great application prospect in a plurality of catalytic reactions.
In the actual industrial production, a large amount of solid waste rich in silicon dioxide is generated every year, the open-air stacking of the solid waste rich in silicon dioxide not only occupies a huge space, but also has great harm to the environment, but the recovery and treatment of the solid waste rich in silicon dioxide are difficult, the solid waste rich in silicon dioxide is generally purified and reused by the steps of calcining, acid treatment, acid-base combined treatment and the like at present, the treatment cost is high, the requirement on equipment is strict, and therefore, the efficient energy-saving recovery and utilization of the silicon dioxide waste generated in the production are problems which need to be solved urgently.
Disclosure of Invention
The invention aims to provide a preparation method of a titanium silicalite molecular sieve and a preparation method of a transition metal loaded titanium silicalite molecular sieve. The invention utilizes the industrial silicon dioxide waste to prepare the titanium silicalite molecular sieve and the transition metal loaded titanium silicalite molecular sieve, and the preparation process does not need to use a large amount of organic solvent, thereby greatly reducing the cost for treating the silicon dioxide waste and generating higher practical economic value.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a titanium silicalite molecular sieve, which comprises the following steps:
mixing and grinding the silicon dioxide waste, the organic alkaline template agent, water, zeolite seed crystals and a titanium source to obtain grinding material liquid; the silica waste comprises alkaline silica waste and/or acidic silica waste; the titanium source is inorganic titanium salt;
carrying out crystallization reaction on the grinding material liquid to obtain a solid precursor;
and calcining the solid precursor to obtain the titanium-silicon molecular sieve.
Preferably, the pH value of the alkaline silicon dioxide waste is more than or equal to 7.7, the pH value of the acidic silicon dioxide waste is less than or equal to 3.8, and SiO in the silicon dioxide waste 2 The mass content of the compound is more than or equal to 98 percent.
Preferably, the alkaline silica waste is SiO 2 The titanium source is calculated as TiO 2 The mass ratio of the alkaline silicon dioxide waste to the organic alkaline template is 1 (0.34-0.86), and the mass ratio of the alkaline silicon dioxide waste to water to the titanium source is 1 (0.51-1.65) to 0.04-0.08.
Preferably, the alkaline silica waste is SiO 2 And the mass ratio of the zeolite seed crystals to the alkaline silicon dioxide waste is (0.0125-0.1): 1.
Preferably, the acidic silica waste is SiO 2 The titanium source is calculated as TiO 2 The mass ratio of the acidic silicon dioxide waste to the organic alkaline template is (1.5-2) to 0.34; the mass ratio of the acidic silicon dioxide waste material to the water to the titanium source is (1.5-2): (0.41-1.5): 0.04-0.08.
Preferably, the acidic silica waste is SiO 2 The mass ratio of the zeolite seed crystal to the acidic silica waste is (0.007-0.05): 1.
Preferably, the temperature of the crystallization reaction is 150-200 ℃, and the heat preservation time of the crystallization reaction is 24-48 h.
Preferably, the calcining temperature is 500-600 ℃; and the heat preservation time of the calcination is 6-8 h.
The invention provides a preparation method of a transition metal loaded titanium silicalite molecular sieve, which comprises the following steps:
mixing and grinding silicon dioxide waste, an organic alkaline template agent, water, zeolite seed crystals, a titanium source, transition metal inorganic salt and an organic amine complexing agent to obtain grinding material liquid; the silica waste comprises alkaline silica waste or acidic silica waste;
carrying out crystallization reaction on the grinding material liquid to obtain a solid precursor;
and calcining the solid precursor to obtain the transition metal loaded titanium silicalite molecular sieve.
Preferably, the mass percentage of the transition metal in the transition metal-loaded titanium silicalite molecular sieve is 0.1-5 wt%.
The invention provides a preparation method of a titanium silicalite molecular sieve, which comprises the following steps: mixing and grinding the silicon dioxide waste, the organic alkaline template agent, water, zeolite seed crystals and a titanium source to obtain grinding material liquid; the silica waste comprises alkaline silica waste or acidic silica waste; carrying out crystallization reaction on the grinding material liquid to obtain a solid precursor; and calcining the solid precursor to obtain the titanium silicalite molecular sieve. The preparation method provided by the invention takes silicon dioxide waste as a silicon source, when the silicon dioxide waste is mixed and ground, the silicon source is subjected to framework depolymerization under the alkaline condition brought by an organic alkaline template agent and is uniformly mixed with a titanium source, in the crystallization reaction process, the silicon source is condensed under the induction action of zeolite seed crystals and the organic alkaline template to obtain a silicon framework, meanwhile, titanium ions in the titanium source enter the silicon framework to replace part of silicon atoms in the silicon framework, and finally, the titanium ions gradually grow into a titanium-silicon molecular sieve under the induction of the zeolite seed crystals and the organic alkaline template.
The invention provides a preparation method of a transition metal loaded titanium silicalite molecular sieve, which comprises the following steps: mixing and grinding silicon dioxide waste, an organic alkaline template agent, water, zeolite seed crystals, a titanium source, transition metal inorganic salt and an organic amine complexing agent to obtain grinding material liquid; the silica waste comprises alkaline silica waste or acidic silica waste; the titanium source is inorganic titanium salt; carrying out crystallization reaction on the grinding material liquid to obtain a solid precursor; and calcining the solid precursor to obtain the transition metal loaded titanium silicalite molecular sieve. The preparation method provided by the invention takes the silicon dioxide waste as the silicon source, when the silicon dioxide waste is mixed and ground, the silicon source is subjected to skeleton depolymerization under the alkaline condition brought by the organic alkaline template agent and is uniformly mixed with the titanium source and the transition metal inorganic salt, in the crystallization reaction process, a silicon source is condensed under the induction action of zeolite seed crystals and an organic alkaline template to obtain a silicon framework, meanwhile, titanium ions in the titanium source enter the silicon framework to replace part of silicon atoms in the silicon framework, and then gradually grow into the titanium-silicon molecular sieve under the induction of the zeolite seed crystal and the organic alkaline template, in the growth process of the titanium silicalite molecular sieve, metal ions in the transition metal inorganic salt enter the pore channels of the titanium silicalite molecular sieve in the presence of the organic amine complexing agent, and can be stably loaded in the molecular sieve structure to obtain the transition metal loaded titanium-silicon molecular sieve with stable structure.
The preparation method of the titanium-silicon molecular sieve and the preparation method of the transition metal loaded titanium-silicon molecular sieve provided by the invention directly utilize industrial silicon dioxide waste to prepare the TS-1 molecular sieve or the transition metal loaded titanium-silicon molecular sieve, overcome the defect that the conventional process of recycling and treating the silicon dioxide waste needs complex treatment, and directly use the silicon dioxide waste to synthesize the TS-1 zeolite molecular sieve, thereby greatly reducing the cost for treating the silicon dioxide waste, providing an economic and environment-friendly way to utilize the silicon dioxide waste and generating higher actual economic value. Meanwhile, the invention takes water as solvent, and does not need to use other organic solvents, thereby avoiding the use of a large amount of organic solvents and further avoiding the waste liquid treatment.
The relative crystallinity of the TS-1 zeolite molecular sieve prepared by the preparation method provided by the invention is 87-95%, the appearance is uniform, and the TS-1 zeolite molecular sieve has a stable crystal structure, is a green and sustainable synthesis strategy, and is suitable for industrial large-scale production.
According to the preparation method of the transition metal loaded titanium silicalite molecular sieve, the TS-1 molecular sieve can increase reaction active sites through transition metal loading, the service life of the TS-1 molecular sieve serving as a catalyst is prolonged, the cost is low, and the TS-1 molecular sieve can play an important role in a plurality of catalytic reactions.
Drawings
FIG. 1 is a TEM image of example 1 synthesis of Ni @ TS-1 using alkaline silica waste;
FIG. 2 is a TEM image of example 3 synthesis of Fe @ TS-1 using basic silica waste;
FIG. 3 is a TEM image of the synthesis of Co @ TS-1 using acidic silica waste of example 5;
FIG. 4 is a mapping chart of example 1 synthesis of Ni @ TS-1 using alkaline silica waste;
FIG. 5 is a mapping chart for the synthesis of Fe @ TS-1 using alkaline silica waste of example 3;
FIG. 6 is a mapping chart of example 7 synthesis of Co/Ni @ TS-1 using alkaline silica waste;
FIG. 7 is an SEM image of Ni @ TS-1 synthesized in example 1 using alkaline silica waste.
Detailed Description
The invention provides a preparation method of a titanium silicalite molecular sieve, which comprises the following steps:
mixing and grinding the silica waste, the organic alkaline template, water, the zeolite seed crystal and the titanium source (hereinafter referred to as first mixed grinding) to obtain an abrasive liquid (hereinafter referred to as first abrasive liquid); the silica waste comprises alkaline silica waste or acidic silica waste; the titanium source is inorganic titanium salt;
subjecting the abrasive liquid to a crystallization reaction (hereinafter referred to as a first crystallization reaction) to obtain a solid precursor (hereinafter referred to as a first solid precursor);
and calcining the first solid precursor (hereinafter referred to as first calcination) to obtain the titanium-silicon molecular sieve.
In the present invention, the starting materials are all commercially available products well known to those skilled in the art, unless otherwise specified.
Firstly mixing and grinding silicon dioxide waste, an organic alkaline template, water, zeolite seed crystals and a titanium source to obtain first grinding material liquid; the silica waste comprises alkaline silica waste or acidic silica waste.
In the invention, the silicon dioxide waste is industrial silicon dioxide waste, and is derived from waste silicon dioxide-rich waste which is discarded when different pore size types of silica gel are produced by Qingdao American college.
In the present invention, the silica waste includes an alkaline silica waste or an acidic silica waste. In the invention, the acidity and alkalinity of the silicon dioxide waste are respectively from the soaking process of silica gel chambering sulfuric acid and ammonia water in the process.
In the present invention, the alkaline silica waste has a pH of 7.7 or more, more preferably 7.7.
In the present invention, the acidic silica waste has a pH of 3.8 or less, more preferably 3.8.
In the present invention, SiO in the silica waste 2 The mass content of (B) is preferably not less than 98%.
In the present invention, SiO in the alkaline silica waste 2 The mass content of (b) is preferably 98.1%.
In the invention, SiO in the acidic silicon dioxide waste material 2 The mass content of (A) is preferably 98.1-98.5%.
In the present invention, the organic basic template is particularly preferably tetrapropylammonium hydroxide.
In the present invention, the zeolite seeds are preferably MFI-type zeolite seeds.
In the present invention, the zeolite seeds are preferably all-silica molecular sieve (Silicalite-1) seeds or titanium Silicalite (TS-1) seeds.
In the invention, the particle size of the zeolite seed crystal is preferably 200-800 nm.
In the present invention, the titanium source is an inorganic titanium salt, and particularly preferably titanium sulfate.
In the invention, the particle size of the titanium source is preferably 0.5-5 mm.
In the present invention, the basic silica waste is SiO 2 The titanium source is calculated as TiO 2 The mass ratio of the alkaline silica waste to the organic alkaline template is preferably 1 (0)34 to 0.86), more preferably 1: 0.34. The mass ratio of the alkaline silicon dioxide waste material to water to the titanium source is 1 (0.51-1.65): 0.04-0.08), and more preferably 1 (0.55-1.6): 0.05-0.07.
In the present invention, the basic silica waste is SiO 2 The mass ratio of the zeolite seed crystals to the alkaline silica waste is preferably (0.0125-0.1): 1, and more preferably (0.013-0.8): 1.
In the invention, the acidic silica waste is SiO 2 The titanium source is calculated as TiO 2 The mass ratio of the acidic silica waste to the organic basic template is (1.5-2): 0.34, and more preferably (1.55-1.95): 0.34. The mass ratio of the acidic silicon dioxide waste material to water to the titanium source is (1.5-2): (0.41-1.5): 0.04-0.08), and more preferably (1.55-1.95): 0.42-1.45): 0.05-0.075.
In the invention, the acidic silica waste is SiO 2 The mass ratio of the zeolite seed crystals to the acidic silica waste is preferably (0.007-0.05): 1, and more preferably (0.0075-0.045): 1.
In the present invention, the first mixed grinding preferably includes the steps of:
putting the organic alkaline template solution into water to obtain an organic alkaline template solution;
mixing and grinding the silicon dioxide waste and the organic alkaline template solution for the second time to obtain a second grinding material liquid;
and thirdly, mixing and grinding the second grinding material liquid, the zeolite seed crystal and the titanium source to obtain the first grinding material liquid.
In the present invention, the time for the second mixed grinding is preferably 5 min.
In the present invention, the particle size of the second abrasive liquid is preferably 9 ten thousand mesh.
In the present invention, the time for the third mixed grinding is preferably 10 min.
After the first abrasive liquid is obtained, the first abrasive liquid is subjected to a first crystallization reaction to obtain a first solid precursor.
In the present invention, before the first crystallization reaction is performed, the first abrasive liquid is preferably subjected to a first aging treatment.
In the present invention, the temperature of the first aging treatment is preferably room temperature.
In the present invention, the heat-retaining time of the first aging treatment is preferably 30 min.
In the present invention, the first crystallization reaction is preferably performed in a crystallization reaction vessel.
In the invention, the temperature of the first crystallization reaction is preferably 150-200 ℃, and more preferably 180 ℃.
In the invention, the heat preservation time of the first crystallization reaction is preferably 24-48 h, and more preferably 25-45 h.
In the invention, the first crystallization reaction is performed to obtain a first crystallization reaction liquid, and in the invention, the first crystallization reaction liquid is preferably subjected to post-treatment to obtain the first solid precursor. In the present invention, the post-treatment preferably comprises: and sequentially carrying out solid-liquid separation and drying. In the present invention, the solid-liquid separation is particularly preferably filtration. The invention preferably dries the solid product after solid-liquid separation, has no special care requirement on the drying temperature, and can remove the moisture in the solid product.
After the first solid precursor is obtained, the first solid precursor is subjected to first calcination to obtain the titanium-silicon molecular sieve.
In the present invention, the temperature of the first calcination is preferably 500 to 600 ℃, and more preferably 550 ℃.
In the invention, the heat preservation time of the first calcination is preferably 6-8 h, and more preferably 6.5-7.5 h.
The preparation method provided by the invention takes silicon dioxide waste as a silicon source, when the silicon dioxide waste is mixed and ground, the silicon source is subjected to framework depolymerization under the alkaline condition brought by an organic alkaline template agent and is uniformly mixed with a titanium source, in the crystallization reaction process, the silicon source is condensed under the induction action of zeolite seed crystals and the organic alkaline template to obtain a silicon framework, meanwhile, titanium ions in the titanium source enter the silicon framework to replace part of silicon atoms in the silicon framework, and finally, the titanium ions gradually grow into a titanium-silicon molecular sieve under the induction of the zeolite seed crystals and the organic alkaline template.
The invention provides a preparation method of a transition metal loaded titanium silicalite molecular sieve, which comprises the following steps:
mixing and grinding the silicon dioxide waste, the organic alkaline template agent, water, zeolite seed crystals, a titanium source, a transition metal inorganic salt and an organic amine complexing agent (hereinafter referred to as fourth mixed grinding) to obtain an abrasive liquid (hereinafter referred to as third abrasive liquid); the silica waste comprises alkaline silica waste or acidic silica waste;
subjecting the abrasive liquid to a crystallization reaction (hereinafter referred to as a second crystallization reaction) to obtain a solid precursor (hereinafter referred to as a second solid precursor);
and calcining the second solid precursor (hereinafter referred to as second calcination) to obtain the transition metal supported titanium silicalite molecular sieve.
Mixing and grinding silicon dioxide waste, an organic alkaline template agent, water, zeolite seed crystals, a titanium source, a transition metal inorganic salt and an organic amine complexing agent (hereinafter referred to as fourth mixed grinding) to obtain an abrasive material liquid (hereinafter referred to as third abrasive material liquid); the silica waste comprises alkaline silica waste or acidic silica waste.
In the present invention, the protection ranges of the silica waste, the organic alkaline template, the water, the zeolite seed crystal and the titanium source are the same as the protection ranges in the preparation of the titanium-silicon molecular sieve, and are not repeated again.
In the present invention, the transition metal inorganic salt preferably includes one or more of an inorganic iron salt, an inorganic nickel salt and an inorganic cobalt salt, and more preferably includes one or two of an inorganic iron salt, an inorganic nickel salt and an inorganic cobalt salt.
In the present invention, the transition metal inorganic salt is preferably a transition metal nitrate, more preferably a hydrated transition metal nitrate.
In the present invention, the organic amine complexing agent is particularly preferably ethylenediamine.
In the invention, the molar ratio of the transition metal inorganic salt to the organic amine complexing agent is preferably 1 (10-20), and more preferably 1 (12.5-18).
In the present invention, the organic amine complexing agent is preferably used in the form of an aqueous solution of an organic amine complexing agent.
In the invention, the molar ratio of the organic amine complexing agent to water in the organic amine complexing agent aqueous solution is preferably (1-2): (13-15), more preferably (1.2-1.8): (13.5-14.8).
In the present invention, the fourth mixed grinding preferably includes the steps of:
putting the organic alkaline template solution into water to obtain an organic alkaline template solution;
mixing and grinding the silicon dioxide waste and the organic alkaline template solution for the second time to obtain a second grinding material liquid;
thirdly, mixing and grinding the second grinding material liquid, the zeolite seed crystal and a titanium source to obtain a first grinding material liquid;
mixing the transition metal inorganic salt and the organic amine complexing agent to perform a complexing reaction to obtain a metal salt precursor;
and fifthly, grinding the first grinding material liquid and the metal salt precursor to obtain a third grinding material liquid.
In the present invention, the protection ranges of the second mixed grinding liquid and the third mixed grinding liquid are the same as the protection ranges of the titanium silicalite molecular sieves prepared by the second mixed grinding liquid and the third mixed grinding liquid, and are not described herein again.
In the present invention, the mixing of the transition metal inorganic salt and the organic amine complexing agent is preferably a mixing of the transition metal inorganic salt and an aqueous solution of the organic amine complexing agent.
In the present invention, the complexation reaction results in a metal complex salt solution.
In the invention, the metal complex salt solution is a metal salt precursor.
In the present invention, the time for the fifth grinding is preferably 10 min.
After the third abrasive liquid is obtained, the third abrasive liquid is subjected to a second crystallization reaction to obtain a second solid precursor.
In the present invention, it is preferable that the third slurry is subjected to a second aging treatment before the second crystallization reaction.
In the present invention, the temperature of the second aging treatment is preferably room temperature.
In the present invention, the heat-retaining time of the second aging treatment is preferably 30 min.
In the present invention, the second crystallization reaction is preferably performed in a crystallization reaction vessel.
In the invention, the temperature of the second crystallization reaction is preferably 150-200 ℃, and more preferably 180 ℃.
In the invention, the heat preservation time of the second crystallization reaction is preferably 24-48 h, and more preferably 25-45 h.
In the present invention, the second crystallization reaction is performed to obtain a second crystallization reaction solution, and in the present invention, the second crystallization reaction solution is preferably post-processed to obtain the second solid precursor. In the present invention, the post-treatment preferably comprises: and sequentially carrying out solid-liquid separation and drying. In the present invention, the solid-liquid separation is particularly preferably filtration. The invention preferably dries the solid product after solid-liquid separation, has no special care requirement on the drying temperature, and can remove the moisture in the solid product.
After a second solid precursor is obtained, the second solid precursor is subjected to second calcination to obtain the transition metal-loaded titanium-silicon molecular sieve.
In the present invention, the temperature of the second calcination is preferably 500 to 600 ℃, and more preferably 550 ℃.
In the invention, the heat preservation time of the second calcination is preferably 6-8 h, and more preferably 6.5-7.5 h.
In the invention, the mass percentage of the transition metal in the transition metal-supported titanium silicalite molecular sieve is preferably 0.1-5 wt%, and more preferably 2.5 wt% or 5 wt%.
The load of the transition metal in the zeolite increases the active sites of TS-1, improves the oxidation performance of TS-1, and increases the stability of the TS-1 molecular sieve as a catalyst. Meanwhile, the invention adopts water as the synthesis solvent, has simple preparation process, improves the yield of the transition metal loaded titanium silicalite molecular sieve product and reduces the discharge of waste solvent. In addition, the preparation method provided by the invention does not need to treat the silicon dioxide waste in advance, not only reduces the synthesis cost, but also saves resources, has practical economic value, and is suitable for industrial large-scale production.
The following examples are provided to illustrate the water-soluble photosensitizer with broad-spectrum antibacterial activity and its preparation method and application, but they should not be construed as limiting the scope of the present invention.
Example 1
0.6g of basic silica waste (pH 7.7, 98.1% SiO) was charged 2 ) Mixing and grinding the mixture and 0.81g of tetrapropylammonium hydroxide solution (25%) for 5min, and then adding 0.024g of titanium sulfate and 0.015g of MFI type all-silicon molecular sieve seed crystal for grinding for 10min to obtain grinding material liquid; mixing Ni (NO) 3 ) 2 Mixing with ethylenediamine aqueous solution to perform complex reaction to obtain [ Ni (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Aqueous solution of Ni (NO) 3 ) 2 And ethylenediamine at a molar ratio of 1:10, and the ethylenediamine/water aqueous solution at a molar ratio of 1:13, and mixing the above abrasive solution with [ Ni (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Grinding the water solution in a mortar for 10min, and aging at room temperature for 30 min; and putting the aged mixed raw materials into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing crystallization reaction for 24 hours at 180 ℃, filtering and drying the purified product, and calcining the purified product at 550 ℃ for 6 hours to obtain a nickel-loaded titanium silicalite molecular sieve product, wherein the mass percentage of nickel in the nickel-loaded titanium silicalite molecular sieve is 2.5 wt%. The TEM image of the product obtained in this example, denoted as Ni @ TS-1, is shown in FIG. 1, the mapping image is shown in FIG. 4,the SEM image is shown in FIG. 7. As can be seen from the figures 1, 4 and 7, the Ni @ TS-1 prepared by the preparation method provided by the invention has the relative crystallinity of 87-95%, uniform appearance and stable crystal structure.
Example 2
1.4g of acidic silica waste (pH 3.8, 98.1% SiO) was charged 2 ) Mixing and grinding the mixture and 0.81g of tetrapropylammonium hydroxide solution (25%) for 5min, and then adding 0.024g of titanium sulfate and 0.015g of MFI type all-silicon molecular sieve seed crystal for grinding for 10min to obtain grinding material liquid; mixing Ni (NO) 3 ) 2 Mixing with ethylenediamine aqueous solution to perform complex reaction to obtain [ Ni (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Aqueous solution of Ni (NO) 3 ) 2 And ethylenediamine at a molar ratio of 1:20, and the ethylenediamine/water aqueous solution at a molar ratio of 1:15, and mixing the above abrasive solution with [ Ni (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Grinding the water solution in a mortar for 10min, and aging at room temperature for 30 min; and putting the aged mixed raw materials into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing crystallization reaction for 24 hours at 180 ℃, filtering and drying the purified product, and calcining the purified product at 550 ℃ for 6 hours to obtain a nickel-loaded titanium silicalite molecular sieve product, wherein the mass percentage of nickel in the nickel-loaded titanium silicalite molecular sieve is 5 wt%. The product prepared in this example was similar to the test results of example 1.
Example 3
0.6g of basic silica waste (pH 7.7, 98.1% SiO) was charged 2 ) Mixing and grinding the mixture and 0.81g of tetrapropylammonium hydroxide solution (25%) for 5min, and then adding 0.024g of titanium sulfate and 0.015g of MFI type all-silicon molecular sieve seed crystal for grinding for 10min to obtain grinding material liquid; mixing Fe (NO) 3 ) 2 Mixing with ethylenediamine aqueous solution to perform complex reaction to obtain [ Fe (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Aqueous solution of Ni (NO) 3 ) 2 And ethylenediamine at a molar ratio of 1:10, and ethylenediamine and water in the aqueous solution of ethylenediamine at a molar ratio of 1:13, and grindingAbrasive liquid and [ Fe (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Grinding the water solution in a mortar for 10min, and aging at room temperature for 30 min; and putting the aged mixed raw materials into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing crystallization reaction for 24 hours at 180 ℃, filtering and drying the purified product, and calcining the purified product at 550 ℃ for 6 hours to obtain an iron-loaded titanium silicalite molecular sieve product, wherein the mass percentage of iron in the iron-loaded titanium silicalite molecular sieve is 2.5 wt%. The product obtained in the example is marked as Fe @ TS-1, the TEM image of the Fe @ TS-1 is shown in the attached figure 2, and the mapping image is shown in the figure 5. As can be seen from the graphs in FIGS. 2 and 5, the relative crystallinity of Fe @ TS-1 obtained by the preparation method provided by the invention is 87-95%, the appearance is uniform, and the crystal form structure is stable.
Example 4
1.4g of acidic silica waste (pH 3.8, 98.1% SiO) was charged 2 ) Mixing and grinding the mixture and 0.81g of tetrapropylammonium hydroxide solution (25%) for 5min, and then adding 0.024g of titanium sulfate and 0.015g of MFI type all-silicon molecular sieve seed crystal for grinding for 10min to obtain grinding material liquid; mixing Fe (NO) 3 ) 2 Mixing with ethylenediamine aqueous solution to perform complex reaction to obtain [ Fe (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Aqueous solution of Fe (NO) 3 ) 2 And ethylenediamine at a molar ratio of 1:20, and the ethylenediamine/water aqueous solution at a molar ratio of 1:15, and mixing the above abrasive solution with [ Fe (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Grinding the water solution in a mortar for 10min, and aging at room temperature for 30 min; and putting the aged mixed raw materials into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing crystallization reaction for 24 hours at 180 ℃, filtering and drying the purified product, and calcining the purified product at 550 ℃ for 6 hours to obtain an iron-loaded titanium silicalite molecular sieve product, wherein the mass percentage of iron in the iron-loaded titanium silicalite molecular sieve is 2.5 wt%. The product prepared in this example was similar to the test results of example 3.
Example 5
1.4g of an acidSilica waste (pH 3.8, 98.5% SiO 2 ) Mixing and grinding the mixture and 0.81g of tetrapropylammonium hydroxide solution (25%) for 5min, and then adding 0.024g of titanium sulfate and 0.015g of MFI type all-silicon molecular sieve seed crystal for grinding for 10min to obtain grinding material liquid; mixing Co (NO) 3 ) 2 Mixing with ethylenediamine aqueous solution to perform complex reaction to obtain [ Co (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Aqueous solution of Co (NO) 3 ) 2 And ethylenediamine at a molar ratio of 1:10, and the molar ratio of ethylenediamine to water in the aqueous ethylenediamine solution at a molar ratio of 1:13, and mixing the above-mentioned abrasive liquid with [ Co (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Grinding the water solution in a mortar for 10min, and aging at room temperature for 30 min; and putting the aged mixed raw materials into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing crystallization reaction for 24 hours at 180 ℃, filtering and drying the purified product, and calcining the purified product at 550 ℃ for 6 hours to obtain a cobalt-loaded titanium silicalite molecular sieve product, wherein the cobalt in the cobalt-loaded titanium silicalite molecular sieve accounts for 2.5 wt% of the cobalt-loaded titanium silicalite molecular sieve. The TEM image of the product obtained in this example, denoted as Co @ TS-1, is shown in FIG. 3. As can be seen from FIG. 3, the Co @ TS-1 prepared by the preparation method provided by the invention is uniform in appearance.
Example 6
1.4g of acidic silica waste (pH 3.8, 98.5% SiO) was charged 2 ) Mixing and grinding the mixture and 0.81g of tetrapropylammonium hydroxide solution (25%) for 5min, and then adding 0.024g of titanium sulfate and 0.015g of MFI type all-silicon molecular sieve seed crystal for grinding for 10min to obtain grinding material liquid; mixing Co (NO) 3 ) 2 Mixing with ethylenediamine aqueous solution to perform complex reaction to obtain [ Co (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Aqueous solution of Co (NO) 3 ) 2 And ethylenediamine at a molar ratio of 1:10, and the molar ratio of ethylenediamine to water in the aqueous ethylenediamine solution at a molar ratio of 1:13, and mixing the above-mentioned abrasive liquid with [ Co (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Grinding the water solution in a mortar for 10min, and aging at room temperature for 30 min; placing the aged mixed raw materials inAnd (3) carrying out crystallization reaction for 24 hours at 180 ℃ in a stainless steel reaction kettle with a polytetrafluoroethylene lining, filtering and drying the purified product, and calcining for 6 hours at 550 ℃ to obtain a cobalt-loaded titanium silicalite molecular sieve product, wherein the cobalt in the cobalt-loaded titanium silicalite molecular sieve accounts for 5 wt% of the cobalt-loaded titanium silicalite molecular sieve. The product obtained in this example was similar to the test results of example 5.
Example 7
0.6g of basic silica waste (pH 7.7, 98.1% SiO) was charged 2 ) Mixing and grinding the mixture and 0.81g of tetrapropylammonium hydroxide solution (25%) for 5min, and then adding 0.024g of titanium sulfate and 0.015g of MFI type all-silicon molecular sieve seed crystal for grinding for 10min to obtain grinding material liquid; mixing Co (NO) 3 ) 2 Mixing with ethylenediamine aqueous solution to make complexation reaction to obtain [ Co (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Aqueous solution of Co (NO) 3 ) 2 And ethylenediamine at a molar ratio of 1:10, and the molar ratio of ethylenediamine to water in the aqueous ethylenediamine solution at a molar ratio of 1:13, and mixing the above-mentioned abrasive liquid with [ Co (NH) 2 CH 2 CH 2 NH 2 ) 3 ](NO 3 ) 2 Grinding the water solution in a mortar for 10min, and aging at room temperature for 30 min; and putting the aged mixed raw materials into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing crystallization reaction for 24 hours at 180 ℃, filtering and drying the purified product, and calcining the purified product at 550 ℃ for 6 hours to obtain a cobalt-loaded titanium silicalite molecular sieve product, wherein the cobalt in the cobalt-loaded titanium silicalite molecular sieve accounts for 2.5 wt% of the cobalt-loaded titanium silicalite molecular sieve. The product obtained in this example was designated as Co @ TS-1, and the mapping chart is shown in FIG. 6. As can be seen from FIG. 6, the relative crystallinity of Co @ TS-1 obtained by the preparation method provided by the invention is 87-95%, and the Co @ TS-1 has a stable crystal structure.
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. The preparation method of the titanium silicalite molecular sieve is characterized by comprising the following steps:
mixing and grinding the silicon dioxide waste, the organic alkaline template agent, water, zeolite seed crystals and a titanium source to obtain grinding material liquid; the silica waste comprises alkaline silica waste and/or acidic silica waste; the titanium source is inorganic titanium salt;
carrying out crystallization reaction on the grinding material liquid to obtain a solid precursor;
and calcining the solid precursor to obtain the titanium silicalite molecular sieve.
2. The method according to claim 1, wherein the alkaline silica waste has a pH of 7.7 or more, the acidic silica waste has a pH of 3.8 or less, and SiO is contained in the silica waste 2 The mass content of the compound is more than or equal to 98 percent.
3. Method for preparing according to claim 1 or 2, characterized in that the waste alkaline silica is in the form of SiO 2 The titanium source is calculated as TiO 2 The mass ratio of the alkaline silicon dioxide waste to the organic alkaline template is 1 (0.34-0.86), and the mass ratio of the alkaline silicon dioxide waste to water to the titanium source is 1 (0.51-1.65) to 0.04-0.08.
4. Method for preparing according to claim 1 or 2, characterized in that said basic silica waste is in the form of SiO 2 And the mass ratio of the zeolite seed crystals to the alkaline silicon dioxide waste is (0.0125-0.1): 1.
5. Method for preparing according to claim 1 or 2, characterized in that the acidic silica waste is in SiO 2 The titanium source is calculated as TiO 2 The mass ratio of the acidic silicon dioxide waste to the organic alkaline template is (1.5-2) to 0.34; the mass ratio of the acidic silicon dioxide waste material to the water to the titanium source is (1.5-2): (0.41-1.5): 0.04-0.08.
6. Method for preparing according to claim 1 or 2, characterized in that the acidic silica waste is in SiO 2 The mass ratio of the zeolite seed crystal to the acidic silica waste is (0.007-0.05): 1.
7. The preparation method according to claim 1, wherein the temperature of the crystallization reaction is 150-200 ℃, and the holding time of the crystallization reaction is 24-48 h.
8. The preparation method according to claim 1, wherein the temperature of the calcination is 500 to 600 ℃; and the calcining heat preservation time is 6-8 h.
9. A preparation method of a transition metal supported titanium silicalite molecular sieve is characterized by comprising the following steps:
mixing and grinding silicon dioxide waste, an organic alkaline template agent, water, zeolite seed crystals, a titanium source, transition metal inorganic salt and an organic amine complexing agent to obtain grinding material liquid; the silica waste comprises alkaline silica waste or acidic silica waste;
carrying out crystallization reaction on the grinding material liquid to obtain a solid precursor;
and calcining the solid precursor to obtain the transition metal loaded titanium silicalite molecular sieve.
10. The preparation method of claim 9, wherein the transition metal in the transition metal-supported titanium silicalite molecular sieve accounts for 0.1-5 wt% of the transition metal-supported titanium silicalite molecular sieve.
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