CN113751067A - Hierarchical pore titanium silicalite molecular sieve coating, preparation method and application thereof - Google Patents
Hierarchical pore titanium silicalite molecular sieve coating, preparation method and application thereof Download PDFInfo
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- CN113751067A CN113751067A CN202111091988.3A CN202111091988A CN113751067A CN 113751067 A CN113751067 A CN 113751067A CN 202111091988 A CN202111091988 A CN 202111091988A CN 113751067 A CN113751067 A CN 113751067A
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- molecular sieve
- coating
- titanium silicalite
- silicalite molecular
- hierarchical pore
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- 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 179
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 178
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000000576 coating method Methods 0.000 title claims abstract description 95
- 239000011248 coating agent Substances 0.000 title claims abstract description 94
- 239000010936 titanium Substances 0.000 title claims abstract description 80
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 80
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 23
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- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 23
- 239000006255 coating slurry Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 10
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
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- 239000010949 copper Substances 0.000 claims description 5
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
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- 238000006555 catalytic reaction Methods 0.000 claims description 4
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- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
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- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
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- 239000011574 phosphorus Substances 0.000 claims description 4
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 3
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- 239000010703 silicon Substances 0.000 claims description 2
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- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- 230000001131 transforming effect Effects 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims 1
- 150000003608 titanium Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 28
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 229910052878 cordierite Inorganic materials 0.000 description 14
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 9
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000006735 epoxidation reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
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- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a hierarchical porous titanium silicalite molecular sieve coating, a preparation method and application thereof, belonging to the technical field of catalytic materials. The preparation method of the invention utilizes the mixed solution or steam of organic amine or inorganic base and organic amine to promote the binder in the coating to dissolve and recrystallize under the conditions of high temperature and high pressure to be converted into the molecular sieve, thereby realizing the chemical combination between the pre-coated molecular sieve crystals and the firm combination with the carrier, and obtaining the hierarchical pore titanium silicalite molecular sieve coating.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a hierarchical pore titanium silicalite molecular sieve coating, a preparation method and application thereof.
Background
Compared with the conventional microporous molecular sieve, the molecular sieve with the hierarchical pore structure can reduce the diffusion resistance of macromolecules in the micropores of the molecular sieve, improve the utilization rate of active sites of the molecular sieve and reduce the formation of coke substances, thereby providing high utilization efficiency, prolonged catalytic life and improved catalytic performance of the molecular sieve catalyst. Various methods have been developed to date for the synthesis of molecular sieve catalysts having hierarchical pore channel structures, such as nano-assembly, templating and post-processing. These synthetic strategies provide for adjustable hierarchical pore molecular sieve characteristics, such as, distribution, size, connectivity, uniform arrangement of secondary channels, to enhance the diffusivity of macromolecules and the accessibility of substrates to catalyst active sites. The hierarchical pore molecular sieve is widely applied to the fields of petrochemical industry, biomass conversion, environmental catalysis and the like.
However, if the molecular sieve raw powder of nanometer or micrometer scale is directly used, a large bed pressure drop is caused and the catalyst is easily lost. Therefore, it is necessary to add an inorganic inert binder to form a strip or granular industrial catalyst on a millimeter to centimeter scale. The above process brings with it a series of problems: 1. the addition of the adhesive covers the active site and blocks secondary pore channels and micropores of the molecular sieve; 2. the diffusion distance of the molecular sieve catalyst will increase after the molding, which will bring about a significant internal diffusion effect of the molded particle catalyst, resulting in low catalyst utilization, poor product selectivity, and easy coking and deactivation of the catalyst. Third, the low thermal conductivity of molecular sieve molecular sieves results in a non-uniform temperature field distribution across the catalyst bed, leading to localized hot spots that result in sintering deactivation of the catalyst (especially for metal-supported catalysts). The above problems in the formation of molecular sieve catalysts not only offset the efforts of people to enhance molecular sieve diffusion, but also bring about a tremendous amplification effect in the engineering application process.
The molecular sieve is loaded on a porous catalyst carrier, such as foamed ceramic, foamed metal, honeycomb ceramic, a metal wire mesh and the like, and the prepared coating type regular structure catalyst provides a feasible method for solving the problems. The concrete expression is as follows: 1. the pressure drop of the catalyst bed is obviously reduced, which is beneficial to the high space velocity reaction; 2. the porous structure optimizes the flow field, eliminates external diffusion and obviously enhances the radial quality and heat transfer; 3. the active component of the molecular sieve exists in the form of a film coating, so that the utilization rate of the molecular sieve is greatly improved. However, it has recently been found that although structured catalysts can optimize flow field distribution, reduce bed pressure drop and eliminate external diffusion, internal mass transfer of the molecular sieve coating is still limited by internal diffusion and the effective utilization of the catalyst is high. The molecular sieve coating needs to be further improved, and the preparation of the molecular sieve coating taking the hierarchical pore molecular sieve as an active element is an effective means for strengthening the mass transfer in the coating, but the preparation method of the hierarchical pore molecular sieve is limited to the preparation of molecular sieve powder at present, and how to prepare the molecular sieve coating taking the hierarchical pore molecular sieve as an element is still a challenging subject.
Disclosure of Invention
In order to solve the limitation of large diffusion resistance in a coating type molecular sieve coating with a regular structure, the invention provides a graded porous titanium silicalite molecular sieve coating, a preparation method and application thereof.
The invention is realized by the following technical scheme:
a preparation method of a hierarchical pore titanium silicalite molecular sieve coating comprises the following specific steps: the method comprises the steps of taking a titanium silicalite molecular sieve with a hierarchical pore structure as an active element, adding deionized water, preparing a coating slurry together with a binder and a plasticizer, coating the coating slurry on the surface of a carrier with a porous structure, drying, carrying out crystal transformation treatment on the porous carrier coated with a molecular sieve coating in a mixed solution of water vapor, organic amine vapor or an organic amine solution, organic amine and inorganic base, transforming the binder into a molecular sieve in the crystal transformation process, and simultaneously dissolving and recrystallizing the coated titanium silicalite molecular sieve to form the hierarchical pore titanium silicalite molecular sieve coating, thereby obtaining the hierarchical pore titanium silicalite molecular sieve coating.
Preferably, the titanium silicalite molecular sieve with the hierarchical pore structure is a TS-1 type titanium silicalite molecular sieve or a hollow TS-1 type titanium silicalite molecular sieve with an open mesoporous structure.
Preferably, the titanium silicalite molecular sieve with hierarchical pore structure is a titanium silicalite molecular sieve or a titanium silicalite molecular sieve modified by metal nanoparticles; wherein, the metal nano-particles are one or more of manganese, copper, boron, phosphorus, tungsten, molybdenum, platinum, palladium or gold.
Preferably, the plasticizer is polyethylene glycol, methyl cellulose or glycerol; the binder is silica sol, silica-alumina sol or a molecular sieve precursor.
Preferably, the active elements account for 5-50 wt%, and the deionized water accounts for 50-95 wt%; the binder in the coating slurry accounts for 1-50% of the total mass fraction of the solid phase of the slurry; the plasticizer accounts for 1-10% of the total mass of the slurry.
Preferably, the porous carrier is honeycomb ceramic, foamed ceramic, metal wire mesh or metal rolling plate.
Preferably, the drying temperature is 20-120 ℃, and the drying time is 0.5-12 hours; the treatment temperature of the crystal transformation treatment is 50-300 ℃, and the treatment time is 2-120 hours.
Preferably, the inorganic alkali solution is one or a mixture of sodium hydroxide, potassium hydroxide and lithium hydroxide; the organic amine is one or more of ammonia water, methylamine, ethylamine, ethylenediamine, tetramethylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide or tetrapropylammonium hydroxide; wherein the concentration of the inorganic alkali liquor is 0.1-5 mol/L; the concentration of the organic amine is 0.01-5 mol/L.
Preferably, the thickness of the prepared hierarchical pore titanium silicalite molecular sieve coating is 200 nanometers to 100 micrometers, wherein the size of the hierarchical pore titanium silicalite molecular sieve is 100 nanometers to 2 micrometers, and mesopores and macropores in the hierarchical pore molecular sieve coating account for more than 50% of the volume of the total pores; the titanium element in the hierarchical pore titanium silicalite molecular sieve is distributed in a gradient way, the titanium element content in the molecular sieve crystal is high, and the titanium element content on the outer surface is low, so that a crystal surface hydrophobic structure is formed; the atomic ratio of titanium and silicon is 6-infinity, and the mass fraction of the titanium of the four-coordination framework in the total titanium element is more than 95 percent.
The invention also aims to provide an application of the hierarchical pore titanium silicalite molecular sieve coating in catalytic reaction, in particular to an application of a regular structure catalyst taking the hierarchical pore molecular sieve coating as an active component in a green catalytic process taking hydrogen peroxide as an oxidant, such as ketoammoximation, olefin epoxidation, phenol hydroxylation and the like.
Compared with the prior art, the invention has the following advantages:
(1) from the preparation process perspective, the organic amine or the mixed solution or steam of the organic amine or the inorganic base and the organic amine is adopted to promote the coating to be dissolved and recrystallized under the conditions of high temperature and high pressure, the bonding and hierarchical porogenesis of the coating and the limited-area rivet of the nano metal particles are realized in one step, and the preparation efficiency is greatly improved. Meanwhile, because the raw materials in the coating are dissolved and recrystallized in situ under the action of organic amine, more than 95 percent of the raw materials in the coating are converted into molecular sieves;
(2) from the viewpoint of obtaining material properties: in the organic amine dissolving and recrystallizing process, the adhesive silica sol or alumina sol participates in the recrystallization process to form the molecular sieve. If the silica sol is used as a binder, the obtained hierarchical pore molecular sieve coating has high content of internal titanium element, low content of external titanium and hydrophobic surface of molecular sieve crystal, which is beneficial to the reaction under the condition of aqueous medium; is advantageous for some reactions that require participation of a solid acid; if titanium sol is adopted, the content of titanium element on the surface layer of the molecular sieve crystal can be increased after dissolution and recrystallization, the hydrophilicity is enhanced, and the reaction activity is increased; if the aluminum sol is adopted, the surface of the formed molecular sieve crystal is hydrophilic and has certain solid acid characteristics; the adjustable modification of the process provides a way for adjusting the surface property of the molecular sieve coating by taking the function as guidance;
(3) from the perspective of catalytic reaction effect, the hierarchical pore molecular sieve coating layer obviously reduces the internal diffusion resistance, is beneficial to mass transfer and improves the catalytic efficiency, and particularly shows higher activity, target product selectivity and oxidant utilization rate in gas phase or liquid phase reaction with participation of macromolecules. The reactions involved include: macromolecular catalytic cracking, olefin epoxidation, phenol oxidation, aromatic hydrocarbon hydroxylation, ketone ammoxidation, alkane partial oxidation, alcohol partial oxidation and the like.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is a scanning electron microscope image of a cross section of a honeycomb cordierite surface hierarchical pore TS-1 type molecular sieve coating;
wherein a is the macro morphology of the honeycomb cordierite load hierarchical pore TS-1 titanium silicalite molecular sieve; and b is a scanning electron microscope image of the hierarchical pore molecular sieve coating.
FIG. 2 is a transmission electron microscope image before organic amine treatment of the coating slurry;
FIG. 3 is a transmission electron microscope image of a molecular sieve coating layer with hollow TS-1 as a basic element obtained after organic amine treatment of the coating slurry;
FIG. 4 is a transmission electron microscope image of a molecular sieve coating with open mesoporous TS-1 as a primitive after organic amine treatment of the coating slurry;
FIG. 5 is a transmission electron microscope image of hollow TS-1 molecular sieve confinement anchoring nano nickel particles.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
In the specific implementation process, the method takes materials with porous structures, such as honeycomb ceramics, foamed ceramics, metal wire meshes and metal rolling plates, as carriers. Firstly, adding molecular sieve powder or molecular sieve powder modified by metal salt into deionized water; then, silica sol, silica-alumina sol or molecular sieve precursor is added as a binder, and polyethylene glycol, methyl cellulose or glycerol and the like are added as plasticizers to prepare the coating slurry. Coating the slurry on a porous structure carrier, and after drying or drying and roasting, treating the porous carrier loaded with the coating in an inorganic alkali solution, an organic amine solution or an acid solution or in water vapor or organic amine vapor to obtain the hierarchical pore molecular sieve coating.
Example 1
In this example, honeycomb cordierite was used as a carrier: the pore diameter is 1 mm, and the straight channels of the cordierite carrier account for 90 percent of the total volume fraction of the material.
The preparation method of the hierarchical pore TS-1 type molecular sieve coating comprises the following steps: (1) 20 g of TS-1 type molecular sieve is added into 90 g of deionized water, and 20 g of silica sol and 2 g of carboxymethyl cellulose are added to prepare coating slurry. (2) After honeycomb cordierite ceramic having a diameter of 20 mm and a height of 20 mm was coated 3 times in the above coating slurry, it was treated in a 100 ℃ oven for 12 hours. (3) The above materials were treated in tetrapropylammonium hydroxide vapor at 180 ℃ for 48 hours. (4) The tetrapropylammonium hydroxide vapor-treated sample was calcined at 550 ℃ for 6 hours after 12 hours at 100 ℃. Thereby obtaining the titanium-silicon molecular sieve coating taking the hollow TS-1 type molecular sieve as an active element.
The technical parameters of the hierarchical pore TS-1 type molecular sieve coating prepared by the embodiment are as follows: the TS-1 type titanium silicalite molecular sieve coating does not contain a binder. The thickness of the molecular sieve coating is 30 micrometers, and the load capacity on the surface of the honeycomb cordierite carrier is 30 wt%; the interface bonding strength between the molecular sieve coating and the carrier is more than 4 MPa; the specific surface area of the integral TS-1 type molecular sieve is 166m2g-1WhereinMicropore area of 86m2g-1Mesoporous area 80m2g-1(ii) a Total pore volume 0.24cm3g-1Wherein the volume of the micro pores is 0.06cm3g-1The volume of the mesopore and the macropore is 0.18cm3g-1. The titanium element content of the hierarchical pore titanium silicalite molecular sieve crystal has gradient distribution, the silicon-titanium atomic ratio of the inner layer is 6, the silicon-titanium atomic ratio of the outer layer is 100, and the mass fraction of the four-coordination framework titanium in the total titanium element is more than 95%.
The application of the hierarchical pore TS-1 type molecular sieve coating prepared in the embodiment in the aspect of preparing benzenediol by phenol hydroxylation is as follows:
the integral TS-1 type molecular sieve is used as a catalyst, water is used as a solvent in the reaction of preparing the benzenediol by phenol hydroxylation in a fixed bed, the molar ratio of phenol to hydrogen peroxide is 3:1, the mass ratio of phenol to titanium silicalite is 20:1, and the reaction temperature is 80 ℃. The reaction was continued for 1000 hours, during which time the phenol conversion was 85%, the catechol selectivity was 20%, the hydroquinone selectivity was 80%, and no by-product was produced.
Example 2
In this example, a stainless steel wire mesh is used as a carrier: the pore diameter is 100 microns, and the pore accounts for 95 percent of the total volume of the material.
The preparation method of the hierarchical pore TS-1 type molecular sieve coating comprises the following steps: (1) 20 g of TS-1 type molecular sieve is added into 90 g of deionized water, and 20 g of titanium sol and 2 g of carboxymethyl cellulose are added to prepare coating slurry. (2) After a stainless steel wire mesh disk having a thickness of 5 mm and a diameter of 20 mm was coated 1 time in the above coating slurry, it was treated in a 100 ℃ oven for 12 hours and baked at 550 ℃ for 6 hours. (3) The above material was treated in a mixed solution of 0.5 mol/l tetrapropylammonium hydroxide and 0.1 mol/l sodium hydroxide at 160 ℃ for 12 hours. (4) The sample treated with the tetrapropylammonium hydroxide solution was calcined at 550 ℃ for 6 hours after 12 hours at 100 ℃. Thereby obtaining the molecular sieve coating taking the open mesoporous TS-1 type titanium silicalite molecular sieve as an active element.
The technical parameters of the coating of the hierarchical pore TS-1 molecular sieve of the embodiment are as follows: the open mesoporous TS-1 type titanium silicalite molecular sieve coating does not contain a binder. Hierarchical pore moleculesThe thickness of the sieve coating is 20 microns, and the loading capacity on the surface of the metal wire mesh carrier is 50 wt%; the specific surface area of the integral TS-1 type molecular sieve is 290m2g-1Wherein the area of the micropores is 150m2g-1Mesoporous area 140m2g-1(ii) a Total pore volume 0.54cm3g-1Wherein the volume of the micro pores is 0.09cm3g-1The volume of the mesopore and the macropore is 0.45cm3g-1. The titanium element content of the hierarchical pore titanium silicalite molecular sieve crystal has gradient distribution, the silicon-titanium atomic ratio of the inner layer is 25, the silicon-titanium atomic ratio of the outer layer is 12, and the mass fraction of the four-coordination framework titanium in the total titanium element is more than 95%.
The application of the hierarchical pore TS-1 type molecular sieve coating prepared in the embodiment in the aspect of preparing benzenediol by phenol hydroxylation is as follows:
the integral TS-1 type molecular sieve is used as a catalyst, water is used as a solvent in the reaction of preparing the benzenediol by phenol hydroxylation in a fixed bed, the molar ratio of phenol to hydrogen peroxide is 3:1, the mass ratio of phenol to titanium silicalite is 20:1, and the reaction temperature is 80 ℃. The reaction was continued for 1000 hours, during which time the phenol conversion was 95%, catechol selectivity 35%, hydroquinone selectivity 63%, benzoquinone selectivity 2%.
Example 3
In this example, the foamed alumina ceramic was used as a carrier: the pore diameter is 2 mm, and the pore accounts for 80 percent of the total volume of the material.
The preparation method of the hierarchical pore TS-1 type titanium silicalite molecular sieve coating comprises the following steps: (1) 20 g of TS-1 molecular sieve modified by copper element is added into 80 g of deionized water, and 30 g of silica sol and 5 g of polyethylene glycol are added to prepare coating slurry. (2) After the foamed alumina ceramics having a diameter of 20 mm and a height of 20 mm was coated 5 times in the above coating slurry, it was treated in a 100-degree oven for 12 hours and baked at 550 degrees for 6 hours. (3) The above material was treated in a mixed solution of 0.2 mol/l tetrapropylammonium hydroxide and 0.1 mol/l sodium hydroxide at 160 ℃ for 12 hours. (4) The sample treated with the tetrapropylammonium hydroxide solution was calcined at 550 ℃ for 6 hours after 12 hours at 100 ℃. Thereby obtaining the open mesoporous structure TS-1 type titanium silicalite molecular sieve coating.
The technical parameters of the coating of the hierarchical pore TS-1 molecular sieve of the embodiment are as follows: the coating of the hierarchical pore TS-1 type molecular sieve does not contain a binder. The thickness of the hierarchical pore molecular sieve coating is 50 microns, and the loading amount on the surface of the honeycomb cordierite carrier is 30 wt%; the specific surface area of the integral ZSM-5 type molecular sieve is 189m2g-1Wherein the area of the micropores is 109m2g-1Mesoporous area 80m2g-1(ii) a Total pore volume 0.18cm3g-1Wherein the volume of the micro pores is 0.06cm3g-1The volume of the mesopore and the macropore is 0.12cm3g-1. The titanium element content of the hierarchical pore TS-1 molecular sieve crystal has gradient distribution, the silicon-titanium atomic ratio of the inner layer is 7, the silicon-titanium atomic ratio of the outer layer is 120, and the mass fraction of the four-coordination framework titanium in the total titanium element is more than 95%.
The application of the hierarchical pore TS-1 type molecular sieve coating prepared in the embodiment in preparing cyclohexanone oxime through cyclohexanone ammoximation is specifically as follows:
the monolithic TS-1 molecular sieve is used as a catalyst, the usage amount of the hierarchical pore titanium-silicon molecular sieve is 1 g in the fixed bed cyclohexanone ammoximation reaction, and the weight ratio of cyclohexanone: hydrogen peroxide: ammonia 1: 1: 2 (molar ratio), the feeding rate of cyclohexanone is 1mol/h, the reaction temperature is 70 ℃, and the solvent is tert-butanol aqueous solution with the mass fraction of 85 percent. The reaction is continued for 100 hours, during which the cyclohexanone conversion is greater than 90% and the cyclohexanone oxime selectivity is greater than 99.9%.
Example 4
In this example, honeycomb cordierite was used as a carrier: the pore diameter is 1 mm, and the straight channels of the cordierite carrier account for 90 percent of the total volume fraction of the material.
The preparation method of the hierarchical pore ZSM-5 type molecular sieve coating comprises the following steps: (1) 20 g of TS-1 type molecular sieve is added into 80 g of deionized water, and 15 g of aluminum sol and 2 g of carboxymethyl cellulose are added to prepare coating slurry. (2) After honeycomb cordierite ceramic having a diameter of 20 mm and a height of 50 mm was coated 3 times in the above coating slurry, it was treated in a 100-degree oven for 12 hours and fired at 550 degrees for 6 hours. (3) The materials are treated in steam of ethylenediamine and triethylamine for 12 hours at 160 ℃. (4) The sample treated by the ethylene diamine and triethylamine steam is roasted for 6 hours at 550 ℃ after being treated for 12 hours at 100 ℃. Thereby obtaining the molecular sieve coating taking the hollow TS-1 type titanium silicalite molecular sieve as an active element.
The technical parameters of the hierarchical pore TS-1 type titanium silicalite molecular sieve coating of the embodiment are as follows: the molecular sieve coating taking the hollow TS-1 type titanium silicalite molecular sieve as an active element does not contain a binder. The thickness of the hierarchical pore molecular sieve coating is 30 microns, and the loading amount on the surface of the honeycomb cordierite carrier is 50 wt%; the specific surface area of the integral TS-1 type titanium silicalite molecular sieve is 296m2g-1Wherein the area of the micro-holes is 146m2g-1Mesoporous area 150m2g-1(ii) a Total pore volume 0.45cm3g-1Wherein the volume of the micro pores is 0.10cm3g-1The volume of the mesopore and the macropore is 0.35cm3g-1. The content of aluminum element in the hierarchical pore TS-1 type titanium silicalite molecular sieve crystal has gradient distribution, the silicon-titanium atomic ratio of an inner layer is 30, the silicon-titanium atomic ratio of an outer layer is 25, and the mass fraction of titanium of a four-coordination framework in the total titanium element is more than 90%.
Example 5
In this example, a stainless steel wire mesh is used as a carrier: the pore diameter is 60 microns, and the pore accounts for 90 percent of the volume fraction of the total volume of the material.
The preparation method of the hierarchical pore TS-1 type molecular sieve coating comprises the following steps: (1) 20 g of TS-1 type titanium silicalite molecular sieve which is dipped by nickel nitrate is added into 90 g of deionized water, and 20 g of silica sol and 2 g of carboxymethyl cellulose are added to prepare coating slurry. (2) After a stainless steel wire mesh disk having a thickness of 5 mm and a diameter of 20 mm was coated 1 time in the above coating slurry, it was treated in a 100 ℃ oven for 12 hours and baked at 550 ℃ for 6 hours. (3) The above material was treated in 0.5 mol/l tetrapropylammonium hydroxide solution at 160 ℃ for 12 hours. (4) The sample treated with the tetrapropylammonium hydroxide solution was calcined at 550 ℃ for 6 hours after 12 hours at 100 ℃. Thereby obtaining the molecular sieve coating taking the nickel nano-grade hole TS-1 type titanium silicalite molecular sieve as an active element.
The technical parameters of the hierarchical pore TS-1 type titanium silicalite molecular sieve coating of the embodiment are as follows: the TS-1 type titanium silicalite molecular sieve does not contain a binder. Coating thickness of the hierarchical pore molecular sieve is 20 micronsRice, wherein the loading amount on the surface of the metal wire mesh carrier is 50 wt%; the specific surface area of the integral TS-1 type titanium silicalite molecular sieve is 282m2g-1Wherein the area of the micropores is 140m2g-1Mesoporous area 142m2g-1(ii) a Total pore volume 0.56cm3g-1Wherein the volume of the micro pores is 0.10cm3g-1The volume of the mesopore and the macropore is 0.46cm3g-1. The loading of the nano nickel particles in the molecular sieve coating is 5 wt%.
The application of the hierarchical pore TS-1 type molecular sieve coating prepared in the embodiment in preparation of propylene oxide through propylene epoxidation is as follows:
the integral type Ni @ TS-1 type titanium silicalite molecular sieve is used as a catalyst, and in the reaction of preparing propylene oxide by epoxidation of propylene in a fixed bed, the integral type TS-1 molecular sieve catalyst is 20 ml, the feeding speed of the propylene is 50ml/h, the feeding speed of hydrogen peroxide acetonitrile solution is 180ml/h, the reaction pressure is 2MPa, and the reaction temperature is 70 ℃. Within 1000 hours of reaction time, the conversion rate of the hydrogen peroxide is 98 percent, and the yield of the propylene oxide is more than 95 percent.
The hierarchical porous titanium silicalite molecular sieve coating can improve the characteristics of high active site utilization rate and high framework titanium content, can be modified by other heteroatoms such as elements of manganese, copper, boron, phosphorus, tungsten, molybdenum, platinum, palladium, gold and the like, is favorable for mass transfer and improvement of catalytic efficiency, and particularly shows higher activity, target product selectivity and oxidant utilization rate in gas-phase or liquid-phase reactions involving macromolecules. The reactions involved include: olefin epoxidation, phenol oxidation, aromatic hydrocarbon hydroxylation, ketone ammoxidation and the like.
As shown in FIG. 1, the coating of the TS-1 type molecular sieve is tightly bonded on the surface of the cordierite carrier, and TS-1 type molecular sieve crystals are grown alternately and on the surface of the cordierite carrier.
In FIG. 1, a is a macro morphology of a honeycomb cordierite-loaded hierarchical pore TS-1 titanium silicalite molecular sieve coating; and b is a scanning electron microscope image of the hierarchical pore molecular sieve coating.
As shown in fig. 2, the projection electron microscope morphology of the coating before the TS-1 type titanium silicalite molecular sieve organic amine treatment is coated with silica sol as a binder, and it can be seen that dozens of nanometers of silica sol particles are coated on the surface of hundreds of nanometers of titanium silicalite molecular sieve.
As shown in fig. 3, the appearance of the coating obtained in example 1 under a transmission electron microscope shows that after organic amine treatment, silica sol serving as a binder is converted into a molecular sieve, so that a molecular sieve coating with a hollow TS-1 type molecular sieve as an active element is prepared.
As shown in fig. 4, the morphology of the transmission electron microscope of the coating obtained in example 2 shows that after the treatment with the mixed solution of organic amine and inorganic base, the silica sol serving as the binder is converted into the molecular sieve, so as to prepare the molecular sieve coating using the open mesoporous TS-1 type molecular sieve as the active element.
As shown in fig. 5, the transmission microscopic morphology of the molecular sieve coating obtained in example 5 shows that the nano nickel particles are anchored in the hollow TS-1 type titanium silicalite molecular sieve by confinement, which also illustrates that the nano nickel metal particles are coated in the molecular sieve crystals by the dissolution and recrystallization of the molecular sieve and the silica sol.
The preparation method of the hierarchical pore titanium silicalite molecular sieve coating has the following principle:
the method utilizes organic amine or mixed solution or steam of inorganic base and organic amine to promote the binder in the coating to dissolve and recrystallize under the conditions of high temperature and high pressure to convert into the molecular sieve, thereby realizing the chemical combination between the pre-coated molecular sieve crystals and the firm combination with the carrier. During the process, selective desilication and recrystallization of molecular sieve crystals can also occur to form a hierarchical pore structure. Modified particles of manganese, copper, boron, phosphorus, tungsten, molybdenum, platinum, palladium, gold and the like in the slurry can be encapsulated into the pore channels of the hierarchical pore molecular sieve along with the recrystallization process.
The titanium silicalite molecular sieve in the coating has a hierarchical pore structure, so that the internal diffusion resistance of reactant molecules in the coating can be remarkably reduced, and the regular structure catalyst based on the hierarchical pore titanium silicalite molecular sieve coating is suitable for a fixed bed system and has the characteristics of high activity, high selectivity and long service life in an oxidation reaction taking hydrogen peroxide as an oxidant.
The embodiment result shows that compared with the titanium silicalite molecular sieve coating prepared by the conventional coating method and the hydrothermal synthesis method, the titanium silicalite molecular sieve coating takes open mesoporous and hollow TS-1 type molecular sieves as active elements, eliminates the influence of internal diffusion in the reaction process on the activity and product selectivity of the catalyst, and improves the effective utilization rate of the catalyst. In the catalyst synthesis process, silica sol, titanium sol or aluminum sol is converted into the molecular sieve, and the elementary crystals of the molecular sieve form an interface with gradient distribution of titanium element. The gradient distribution of the titanium element is beneficial to the use of the catalyst in an aqueous solvent system, and the safety of the reaction is improved. The integral titanium-silicon molecular sieve catalyst is used for fixed bed reaction processes of phenol hydroxylation to prepare benzenediol, olefin epoxidation, ketone ammoximation and the like.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method of a hierarchical pore titanium silicalite molecular sieve coating is characterized by comprising the following specific steps: the method comprises the steps of taking a titanium silicalite molecular sieve with a hierarchical pore structure as an active element, adding deionized water, preparing a coating slurry together with a binder and a plasticizer, coating the coating slurry on the surface of a carrier with a porous structure, drying, carrying out crystal transformation treatment on the porous carrier coated with a molecular sieve coating in a mixed solution of water vapor, organic amine vapor or an organic amine solution, organic amine and inorganic base, transforming the binder into a molecular sieve in the crystal transformation process, and simultaneously dissolving and recrystallizing the coated titanium silicalite molecular sieve to form the hierarchical pore titanium silicalite molecular sieve coating, thereby obtaining the hierarchical pore titanium silicalite molecular sieve coating.
2. The method of claim 1, wherein the hierarchical pore titanium silicalite molecular sieve is a TS-1 type titanium silicalite molecular sieve with an open mesoporous structure or a hollow TS-1 type titanium silicalite molecular sieve.
3. The method of claim 1, wherein the hierarchical pore titanium silicalite molecular sieve is a titanium silicalite molecular sieve or a metal nanoparticle modified titanium silicalite molecular sieve; wherein, the metal nano-particles are one or more of manganese, copper, boron, phosphorus, tungsten, molybdenum, platinum, palladium or gold.
4. The method of claim 1, wherein the plasticizer is polyethylene glycol, methyl cellulose, or glycerol; the binder is silica sol, silicon-aluminum sol or a molecular sieve precursor; the porous carrier is honeycomb ceramics, foamed ceramics, a metal wire mesh or a metal rolling plate.
5. The method of claim 1, wherein the active moiety comprises 5-50 wt%, and the deionized water comprises 50-95 wt%; the binder in the coating slurry accounts for 1-50% of the total mass fraction of the solid phase of the slurry; the plasticizer accounts for 1-10% of the total mass of the slurry.
6. The method of claim 1, wherein the drying is at a temperature of 20 to 120 ℃ for 0.5 to 12 hours; the treatment temperature of the crystal transformation treatment is 50-300 ℃, and the treatment time is 2-120 hours.
7. The method for preparing a graded pore titanium silicalite molecular sieve coating of claim 1, wherein the inorganic alkali solution is one or a mixture of sodium hydroxide, potassium hydroxide and lithium hydroxide; the organic amine is one or more of ammonia water, methylamine, ethylamine, ethylenediamine, tetramethylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide or tetrapropylammonium hydroxide; wherein the concentration of the inorganic alkali liquor is 0.1-5 mol/L; the concentration of the organic amine is 0.01-5 mol/L.
8. A coating of a hierarchical pore titanium silicalite molecular sieve, prepared by the method of any one of claims 1 to 7.
9. The coating of claim 8, wherein the thickness of the coating is 200 nm to 100 μm, wherein the size of the titanium silicalite molecular sieve is 100 nm to 2 μm, and the mesopores and macropores in the coating account for more than 50% of the total pore volume; the titanium element in the hierarchical pore titanium silicalite molecular sieve is distributed in a gradient way, the titanium element content in the molecular sieve crystal is high, and the titanium element content on the outer surface is low, so that a crystal surface hydrophobic structure is formed; the atomic ratio of titanium and silicon is 6-infinity, and the mass fraction of the titanium of the four-coordination framework in the total titanium element is more than 95 percent.
10. Use of a coating of a hierarchical pore titanium silicalite molecular sieve according to claim 8 in catalytic reactions.
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| CN103252253A (en) * | 2013-05-07 | 2013-08-21 | 中国科学院金属研究所 | Porous silicon-carbide carrier surface gradient pore molecular sieve coating and preparation method thereof |
| CN104028300A (en) * | 2014-06-06 | 2014-09-10 | 郑州大学 | Modified TS-1 molecular sieve as well as preparation method and application thereof |
| CN108435245A (en) * | 2018-04-20 | 2018-08-24 | 中国石油大学(北京) | Little crystal grain grade hole SAPO-34@kaolin microspheres catalyst and its preparation and application |
| CN108479848A (en) * | 2018-04-16 | 2018-09-04 | 大连理工大学 | High stability monoblock type titanium-silicon molecular sieve catalyst and preparation method thereof |
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| CN103252253A (en) * | 2013-05-07 | 2013-08-21 | 中国科学院金属研究所 | Porous silicon-carbide carrier surface gradient pore molecular sieve coating and preparation method thereof |
| CN104028300A (en) * | 2014-06-06 | 2014-09-10 | 郑州大学 | Modified TS-1 molecular sieve as well as preparation method and application thereof |
| CN108479848A (en) * | 2018-04-16 | 2018-09-04 | 大连理工大学 | High stability monoblock type titanium-silicon molecular sieve catalyst and preparation method thereof |
| CN108435245A (en) * | 2018-04-20 | 2018-08-24 | 中国石油大学(北京) | Little crystal grain grade hole SAPO-34@kaolin microspheres catalyst and its preparation and application |
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