CN107640776B - Preparation method of MFI molecular sieve with micro-mesoporous structure - Google Patents
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Abstract
The invention discloses a preparation method of an MFI molecular sieve with a micro-mesoporous structure, which comprises the following steps: respectively weighing a silicon source, an organic template agent, an alkali source, an ammonium salt and a hard template agent, putting the silicon source, the organic template agent, the alkali source, the ammonium salt and the hard template agent into a mortar, and grinding; adding deionized water or infrared lamp to bake the ground powdery or semi-dry solid mixture, controlling water content, transferring to a reaction kettle, and heating in a drying oven at constant temperature to perform crystallization reaction; after crystallization is finished, cooling the reaction kettle to room temperature, taking out a solid crystalline product, washing, and drying in a 50 ℃ oven to obtain molecular sieve raw powder; and (3) carrying out temperature programming on the molecular sieve raw powder in a muffle furnace to 550 ℃ for calcination to obtain the MFI molecular sieve with the micro-mesoporous structure. The obtained MFI molecular sieve product has a uniform mesoporous micro-mesoporous structure, high crystallinity, pure phase, high yield and high carbon nanotube utilization rate, is environment-friendly, meets the requirements of energy conservation and emission reduction, and has great industrial application prospects.
Description
The technical field is as follows:
the invention relates to a molecular sieve, in particular to a preparation technology of a hierarchical pore molecular sieve.
Background art:
microporous ZSM-5 zeolite molecular sieves were synthesized by the company Mobile oil, USA, at the end of the sixties of the 20 th century. The zeolite molecular sieve has the advantages of special 3-dimensional crossed ten-membered ring pore channel, high hydrothermal stability, good acid resistance, excellent shape selectivity and the like, so that the ZSM-5 molecular sieve is widely applied to the fields of petrochemical industry and fine chemical industry. But the size of the guest molecule and the diffusion speed in the pore channel are greatly limited due to the insufficient pore diameter of the nano-micropores. Therefore, it is a current research focus to improve the permeability of the pore channel and the accessibility of the acid center by introducing mesopores and even macropores.
The multistage pore forming methods of molecular sieves are mainly classified into the following categories: soft template method, hard template method, post-treatment method, etc. The hard template method has wide scale synthesis prospect due to the characteristics of simple operation, easy obtainment of template agent and the like. Jacobsen et al [ alpha ], [ alpha ]J.Am.Chem.Soc., 2000, 122,7116-7117，Chem.Mater.2001,13, 4416-4418]The zeolite single crystal with the intragranular mesopores is successfully obtained by adding carbon nano particles or carbon nano tubes as a hard template in the crystallization process of the ZSM-5 molecular sieve. Xiaofengshou et al (CN 100439246C)]Using rice hulls, basic styrenic ion exchange resins orMesoporous carbon and the like are used as hard template agents to obtain mesopores and even macropores. Chenlihua et al [ CN106276957A, CN106283187A]The hierarchical porous Silicalite-1 and ZSM-5 molecular sieves with opal structures are prepared by using a composite of polymer microspheres, silica nanospheres and a sucrose carbonization product as a macroporous and mesoporous hard template.
However, in the process of synthesizing a hierarchical pore molecular sieve by the hard template method, phase separation is very likely to occur due to the difference in physicochemical properties such as density and surface functional groups between the hard template and the synthetic gel used. Particularly in dilute sols, the phenomenon of phase separation is particularly severe, resulting in inefficient use of hard templates. Chenlihua et al [ CN106276957A, CN106283187A]The "dry gel inversion method" was used to avoid phase separation. The method is characterized in that firstly, dry glue containing skeleton element species, directing agent species and alkali species is prepared and is placed above a special hydrothermal reaction kettle. Water is added below the reaction kettle, and then the reaction kettle is put into an oven for crystallization. Xiaofengshou et al (CN 102627287B)]A process for synthesizing molecular sieve by grinding solid-phase raw material under the condition of no solvent is disclosed. The method is characterized in that weighed solid raw materials, namely a silicon source, a metal ion source, an organic template agent and an alkalinity regulator, are ground and mixed, and the mixture is put into a hydrothermal reaction kettle for heating and crystallization after being ground. In addition, the Shispanish ITQ institute developed a zeolite molecular sieve synthesis technique called "dense gel" techniqueChem. Commum., 1996, 2365]The method is mainly characterized in that the amount of water in the gel is controlled by adding water or heating and drying the mixture to dryness after uniformly mixing a silicon source, a metal ion source, a guiding agent, a mineralizer and the like, so that H is ensured2The O/Si ratio is in the range of 0.5-10, the gel is usually a solid phase or a wet semi-solid phase, and then the gel is put into a common hydrothermal reaction kettle for heating and crystallization.
The invention content is as follows:
in view of the above, the present invention aims to prepare a micro-mesoporous composite MFI molecular sieve with uniform mesopores by using a carbon nanotube as a hard template method, and to avoid phase separation of the hard template and gel by using a "thick gel" technique, thereby improving the use efficiency of the hard template. Unlike the "xerogel conversion" process, the "concentrated gel" technique does not require the use of a specially made reaction vessel to separate the aqueous and gel phases. The method is also different from the synthesis of a solvent-free solid-phase zeolite molecular sieve, and the concentrated sol technology can accurately control the water content in gel, so that the fluctuation of the crystallinity of the zeolite molecular sieve caused by the water absorption or dehydration of a solid-phase reactant due to different external temperature and humidity in the grinding process is avoided. In some cases, the difference in water content may even result in the formation of a heterogeneous phase, which may result in synthesis failure or a reduction in zeolite molecular sieve quality.
In order to solve the problems of hard template phase separation, water quantity control and the like, the invention adopts a synthesis method of a solid-phase micro-mesoporous composite zeolite molecular sieve based on a 'thick gel' technology. The specific technical scheme is as follows:
a preparation method of MFI molecular sieve with micro-mesoporous structure comprises the following steps: respectively weighing a silicon source, an organic template agent, an alkali source, an ammonium salt and a hard template agent, putting the silicon source, the organic template agent, the alkali source, the ammonium salt and the hard template agent into a mortar, and grinding; adding deionized water or infrared lamp to bake the ground powdery or semi-dry solid mixture, controlling water content, transferring to a reaction kettle, and heating in a drying oven at constant temperature to perform crystallization reaction; after crystallization is finished, cooling the reaction kettle to room temperature, taking out a solid crystalline product, washing, and drying in a 50 ℃ oven to obtain molecular sieve raw powder; and (3) carrying out temperature programming on the molecular sieve raw powder in a muffle furnace to 550 ℃ for calcination to obtain the MFI molecular sieve with the micro-mesoporous structure.
In the above-mentioned production method, preferably, an aluminum source is further added.
In the above preparation method, preferably, the silicon source is sodium metasilicate nonahydrate, white carbon black or sodium silicate; the organic template agent is tetrapropylammonium bromide or tetraethylammonium bromide; the alkali source is sodium metasilicate nonahydrate, sodium hydroxide or sodium silicate; the ammonium salt is ammonium fluoride or ammonium chloride; the hard template agent is carbon nano tubes with different pipe diameters, nano calcium carbonate or straws; the aluminum source is aluminum sulfate octadecahydrate or sodium aluminate.
In the above preparation method, preferably, the ratio of the raw materials added during the crystallization reaction is:
the molar ratio of the silicon source, the organic template agent, the alkali source, the ammonium salt, the deionized water and the aluminum source is as follows: 1: (0.021-1.80): 0.50 (0.96-1.56) (1-15) and 0.520;
the mass ratio of the silicon source to the hard template agent is as follows: 1: (0.00020-0.250).
In the above preparation method, preferably, the tube diameter or particle diameter of the hard template agent is in the range of 2 to 50 nm.
In the above preparation method, preferably, the crystallization reaction temperature is 160 to 200 ℃, and the crystallization reaction time is 1 to 6 days.
Compared with the prior art, the invention has the following beneficial effects: the preparation method of the invention can accurately control the water content in the gel, and the synthesis operation is simplified to a certain extent. The obtained MFI molecular sieve product has a uniform mesoporous micro-mesoporous structure, high crystallinity, pure phase, high yield and high carbon nanotube utilization rate, is environment-friendly, meets the requirements of energy conservation and emission reduction, and has great industrial application prospects.
Description of the drawings:
FIG. 1: XRD spectrum of the product of example 1.
FIG. 2: SEM image of the product of example 1.
FIG. 3: the nitrogen desorption isotherm of the product of example 1.
FIG. 4: BJH pore size distribution of the product of example 1.
FIG. 5: XRD spectrum of the product of example 2.
FIG. 6: SEM image of the product of example 2.
FIG. 7: XRD spectrum of the product of example 3.
FIG. 8: SEM image of the product of example 3.
FIG. 9: the nitrogen desorption isotherm of the product of example 3.
FIG. 10: BJH pore size distribution of the product of example 3.
FIG. 11: XRD spectrum of the product of example 4.
FIG. 12: SEM image of the product of example 4.
FIG. 13: the nitrogen desorption isotherm of the product of example 4.
FIG. 14: BJH pore size distribution of the product of example 4.
FIG. 15: XRD spectrum of the product of example 5.
FIG. 16: SEM image of the product of example 5.
FIG. 17: XRD spectrum of the product of example 7.
FIG. 18: SEM image of the product of example 7.
FIG. 19: the nitrogen desorption isotherm for the product of example 7.
FIG. 20: BJH pore size distribution of the product of example 7.
FIG. 21: XRD spectrum of the product of example 8.
FIG. 22: SEM image of the product of example 8.
FIG. 23: the nitrogen desorption isotherm of the product of example 8.
FIG. 24: BJH pore size distribution of the product of example 8.
The specific implementation mode is as follows:
the present invention is described in further detail below with reference to specific examples.
Example 1: preparing the MFI molecular sieve with the micro-mesoporous structure of pure silicon.
Respectively weighing 1.315g of sodium metasilicate nonahydrate, 0.3g of white carbon black, 0.24g of tetrapropylammonium bromide, 0.6g of ammonium chloride and 0.1g of carbon nano tube with the tube diameter of 3-5nm, placing the materials in a mortar, grinding for 9-20min, weighing the mass of the materials, adding or baking a certain amount of water under an infrared lamp, controlling the mass of the concentrated gel to be 2.56g, transferring the concentrated gel into a reaction kettle, and heating and crystallizing the concentrated gel in a thermostat at 180 ℃ for 2 d. And after the crystallization reaction is finished, cooling the reaction kettle to room temperature, opening the kettle, taking out the solid crystallization product, washing, and drying in a 50 ℃ oven to obtain molecular sieve powder. Placing the molecular sieve powder in a muffle furnace, raising the temperature to 550 ℃ by a program, and calcining for 5 hours to obtain a final molecular sieve product, wherein the yield is 92.2%. Wherein the mol ratio of each component in the crystallization reaction is as follows: 1 SiO2: 0.481 Na2O: 1.166 NH4Cl: 0.0937 TPABr: 4.328 H2O, the mass ratio is: 1 SiO2: 0.173 CNTs。
FIG. 1 is an XRD characterization spectrum of a product, which has a typical MFI structure characteristic peak, and the product has good crystallinity and no impurity phase peak.
Fig. 2 is an SEM image of a product having a crystal morphology typical of MFI molecular sieves, as a pure phase.
FIG. 3 is a nitrogen desorption isotherm of a product having a microporous and mesoporous structure.
FIG. 4 is a BJH pore size distribution diagram of a product, and the distribution of mesopores of the product is concentrated between 3nm and 5 nm.
Example 2: preparing the MFI molecular sieve with the micro-mesoporous structure of pure silicon.
Respectively weighing 1.315g of sodium metasilicate nonahydrate, 0.24g of tetrapropylammonium bromide, 0.5g of ammonium fluoride and 0.01g of carbon nano tube with the tube diameter of 3-5nm, putting the materials into a mortar, grinding for 9-20min, weighing the mass of the materials, adding or baking a certain amount of water under an infrared lamp, controlling the mass of the concentrated gel to be 2.07g, transferring the concentrated gel into a reaction kettle, and heating and crystallizing the concentrated gel in a 180 ℃ constant temperature box for 2 d. And after the crystallization reaction is finished, cooling the reaction kettle to room temperature, opening the kettle, taking out the solid crystallization product, washing, and drying in a 50 ℃ oven to obtain molecular sieve powder. Placing the molecular sieve powder in a muffle furnace, raising the temperature to 550 ℃ by a program, and calcining for 5 hours to obtain a final molecular sieve product, wherein the yield is 90.4%. Wherein the mol ratio of each component in the crystallization reaction is as follows: 1 SiO2: 1 Na2O: 2.918 NH4F: 0.195 TPABr: 9 H2O, the mass ratio is: 1 SiO2: 0.036 CNTs。
Fig. 5 is an XRD characterization spectrum of the product, which has typical MFI structural characteristic peaks.
Fig. 6 is an SEM image of a product having a typical crystal morphology of an MFI molecular sieve.
Example 3: preparing the MFI molecular sieve with the micro-mesoporous structure of pure silicon.
Respectively weighing 1.315g of sodium metasilicate nonahydrate, 0.3g of white carbon black, 0.12g of tetrapropylammonium bromide, 0.6g of ammonium chloride, 0.4g of deionized water and 0.01g of carbon nano tube with the tube diameter of 3-5nm, putting the materials into a mortar, grinding for 9-20min, weighing the mass of the materials, adding or baking a certain amount of water under an infrared lamp, controlling the mass of the concentrated gel to be 2.75g, transferring the concentrated gel into a reaction kettle, and heating and crystallizing the concentrated gel in a thermostat at 180 ℃ for 2 d. And after the crystallization reaction is finished, cooling the reaction kettle to room temperature, opening the kettle, taking out the solid crystallization product, washing, and drying in a 50 ℃ oven to obtain molecular sieve powder. Placing the molecular sieve powder inAnd (3) heating the mixture in a muffle furnace to 550 ℃ by a program, and calcining the mixture for 5 hours to obtain a final molecular sieve product, wherein the yield is 92.1%. Wherein the mol ratio of each component in the crystallization reaction is as follows: 1 SiO2: 0.481 Na2O: 1.166 NH4Cl: 0.0469 TPABr: 6.638 H2O, the mass ratio is: 1 SiO2: 0.0173 CNTs。
FIG. 7 is an XRD characterization spectrum of a product, which has a typical MFI structure, and the product has good crystallinity and no hetero-phase peak.
Fig. 8 is an SEM image of a product having a crystal morphology typical of MFI molecular sieves, as a pure phase.
Fig. 9 is a nitrogen desorption isotherm of a product having a microporous and mesoporous structure.
FIG. 10 is a BJH pore size distribution diagram of a product, and the distribution of mesopores of the product is concentrated between 2 and 3 nm.
Example 4: preparing the MFI molecular sieve with the micro-mesoporous structure of pure silicon.
Respectively weighing 1.315g of sodium metasilicate nonahydrate, 0.3g of white carbon black, 0.12g of tetrapropylammonium bromide, 0.6g of ammonium chloride and 0.01g of carbon nano tube with the tube diameter of 8-15nm, placing the materials in a mortar, grinding for 9-20min, weighing the mass of the materials, adding or baking a certain amount of water under an infrared lamp, controlling the mass of the concentrated gel to be 2.75g, transferring the concentrated gel into a reaction kettle, and heating and crystallizing the concentrated gel in a thermostat at 180 ℃ for 2 d. And after the crystallization reaction is finished, cooling the reaction kettle to room temperature, opening the kettle, taking out the solid crystallization product, washing, and drying in a 50 ℃ oven to obtain molecular sieve powder. Placing the molecular sieve powder in a muffle furnace, raising the temperature to 550 ℃ by a program, and calcining for 5 hours to obtain a final molecular sieve product, wherein the yield is 92.5%. Wherein the mol ratio of each component in the crystallization reaction is as follows: 1 SiO2: 0.481 Na2O: 1.166 NH4Cl: 0.0469 TPABr: 4.328 H2O, the mass ratio is: 1 SiO2: 0.0173 CNTs。
FIG. 11 is an XRD characterization spectrum of a product with a typical MFI structure and a good crystallinity without a hetero-phase peak.
Fig. 12 is an SEM image of a product having a crystal morphology typical of MFI molecular sieves, as a pure phase.
Fig. 13 is a nitrogen desorption isotherm of a product having a microporous and mesoporous structure.
FIG. 14 is a BJH pore size distribution diagram of a product, and the distribution of mesopores of the product is concentrated between 4 and 10 nm.
Example 5: preparing the MFI molecular sieve with the micro-mesoporous structure of pure silicon.
Respectively weighing 0.3g of sodium metasilicate nonahydrate, 0.51g of white carbon black, 0.12g of tetrapropylammonium bromide and 0.01g of carbon nano tube with the tube diameter of 3-5nm, putting the materials into a mortar, grinding for 9-20min, weighing the mass of the materials, adding or baking a certain amount of water under an infrared lamp, controlling the mass of the concentrated gel to be 0.95g, transferring the concentrated gel into a reaction kettle, and heating and crystallizing the concentrated gel in a 180 ℃ constant temperature box for 2 d. And after the crystallization reaction is finished, cooling the reaction kettle to room temperature, opening the kettle, taking out the solid crystallization product, washing, and drying in a 50 ℃ oven to obtain molecular sieve powder. And placing the molecular sieve powder in a muffle furnace, and heating to 550 ℃ by a program to calcine for 5 hours to obtain a final molecular sieve product, wherein the yield is 93.3%. Wherein the mol ratio of each component in the crystallization reaction is as follows: 1 SiO2: 0.111 Na2O: 0.0469 TPABr: 0.995 H2O, the mass ratio is: 1 SiO2: 0.0174 CNTs。
FIG. 15 is an XRD characterization spectrum of a product with a typical MFI structure and a good crystallinity without a hetero-phase peak.
Fig. 16 is an SEM image of a product having a typical crystal morphology of an MFI molecular sieve.
Example 6: preparing the MFI molecular sieve with the micro-mesoporous structure of pure silicon.
Respectively weighing 1.315g of sodium metasilicate nonahydrate, 0.3g of white carbon black, 0.6g of ammonium chloride, 0.09g of tetraethyl ammonium bromide and 0.01g of carbon nano tube with the tube diameter of 3-5nm, placing the materials in a mortar, grinding for 9-20min, weighing the mass of the materials, adding or baking a certain amount of water under an infrared lamp, controlling the mass of the concentrated gel to be 2.32g, transferring the concentrated gel into a reaction kettle, and heating and crystallizing the concentrated gel for 2d in a 180 ℃ constant temperature box. And after the crystallization reaction is finished, cooling the reaction kettle to room temperature, opening the kettle, taking out the solid crystallization product, washing, and drying in a 50 ℃ oven to obtain molecular sieve powder. Placing the molecular sieve powder in a muffle furnace, raising the temperature to 550 ℃ by a program, and calcining for 5 hours to obtain a final molecular sieve product, wherein the yield is 90.3%. Wherein crystallization is carried outThe molar ratio of the reaction components is as follows: 1 SiO2: 0.111 Na2O: 0.0445 TEABr: 0.995 H2O, the mass ratio is: 1 SiO2: 0.0174 CNTs。
Example 7: preparing an aluminum-containing MFI molecular sieve with a micro-mesoporous structure.
1.315g of sodium metasilicate nonahydrate, 0.3g of white carbon black, 0.12g of tetrapropylammonium bromide, 0.6g of ammonium chloride and 0.04g of Al are weighed respectively2(SO4)3·18H2O and 0.01g of carbon nano tube with the tube diameter of 3-5nm are put in a mortar, ground for 9-20min, weighed and added with or baked with a certain amount of water under an infrared lamp, the mass of the concentrated gel is controlled to be 2.41g and transferred into a reaction kettle, and the concentrated gel is heated and crystallized in a thermostat at 180 ℃ for 2 d. And after the crystallization reaction is finished, cooling the reaction kettle to room temperature, opening the kettle, taking out the solid crystallization product, washing, and drying in a 50 ℃ oven to obtain molecular sieve powder. Placing the molecular sieve powder in a muffle furnace, raising the temperature to 550 ℃ by a program, and calcining for 5 hours to obtain a final molecular sieve product, wherein the yield is 91.8%. Wherein the mol ratio of each component in the crystallization reaction is as follows: 1 SiO2: 0.0063 Al2O3: 0.481 Na2O: 1.166 NH4Cl: 0.0469 TPABr: 4.441 H2O, the mass ratio is: 1 SiO2: 0.0173 CNTs。
FIG. 17 is an XRD characterization spectrum of a product with a typical MFI structure and a good crystallinity without a hetero-phase peak.
Fig. 18 is an SEM image of a product having a typical crystal morphology of an MFI molecular sieve.
Fig. 19 is a nitrogen desorption isotherm of a product having a microporous and mesoporous structure.
FIG. 20 is a BJH pore size distribution diagram of a product, and the distribution of mesopores of the product is concentrated between 2 and 4 nm.
Example 8: preparing an aluminum-containing MFI molecular sieve with a micro-mesoporous structure.
1.315g of sodium metasilicate nonahydrate, 0.3g of white carbon black, 0.12g of tetrapropylammonium bromide, 0.6g of ammonium chloride and 0.04g of Al are weighed respectively2(SO4)3·18H2O, 0.3g deionized water and 0.01g carbon nano tube with the tube diameter of 3-5nm are placed in a mortarGrinding for 9-20min, weighing, adding water or baking under infrared lamp, controlling the mass of concentrated gel at 2.71g, transferring to a reaction kettle, and heating and crystallizing in a 180 deg.C thermostat for 2 d. And after the crystallization reaction is finished, cooling the reaction kettle to room temperature, opening the kettle, taking out the solid crystallization product, washing, and drying in a 50 ℃ oven to obtain molecular sieve powder. Placing the molecular sieve powder in a muffle furnace, raising the temperature to 550 ℃ by a program, and calcining for 5 hours to obtain a final molecular sieve product, wherein the yield is 91.4%. Wherein the mol ratio of each component in the crystallization reaction is as follows: 1 SiO2: 0.0063 Al2O3 : 0.481 Na2O: 1.166 NH4Cl: 0.0469 TPABr: 6.173 H2O, the mass ratio is: 1 SiO2: 0.0173 CNTs。
Fig. 21 is an XRD characterization spectrum of the product, which has typical MFI structural characteristic peaks.
Fig. 22 is an SEM image of a product having a typical crystal morphology of an MFI molecular sieve.
Fig. 23 is a nitrogen desorption isotherm of a product having a microporous and mesoporous structure.
FIG. 24 is a BJH pore size distribution diagram of a product with a mesoporous distribution centered between 3-4 nm.
Example 9: preparing an aluminum-containing MFI molecular sieve with a micro-mesoporous structure.
1.315g of sodium metasilicate nonahydrate, 0.3g of white carbon black, 0.12g of tetrapropylammonium bromide, 0.6g of ammonium chloride and 0.04g of Al are weighed respectively2(SO4)3·18H2O and 0.01g of carbon nano tube with the tube diameter of 10-20nm are put in a mortar, ground for 9-20min, weighed and added with or baked with a certain amount of water under an infrared lamp, the mass of the concentrated gel is controlled to be 2.41g and transferred into a reaction kettle, and the concentrated gel is heated and crystallized in a thermostat at 180 ℃ for 2 d. And after the crystallization reaction is finished, cooling the reaction kettle to room temperature, opening the kettle, taking out the solid crystallization product, washing, and drying in a 50 ℃ oven to obtain molecular sieve powder. Placing the molecular sieve powder in a muffle furnace, raising the temperature to 550 ℃ by a program, and calcining for 5 hours to obtain a final molecular sieve product, wherein the yield is 92.3%. Wherein the mol ratio of each component in the crystallization reaction is as follows: 1 SiO2: 0.0063 Al2O3: 0.481 Na2O: 1.166 NH4Cl: 0.0469 TPABr: 4.441 H2O, the mass ratio is: 1 SiO2: 0.0173 CNTs。
Example 10: preparing an aluminum-containing MFI molecular sieve with a micro-mesoporous structure.
0.3g of sodium metasilicate nonahydrate, 0.51g of white carbon black, 0.12g of tetrapropylammonium bromide and 0.04g of Al were weighed out respectively2(SO4)3·18H2O and 0.01g of carbon nano tube with the tube diameter of 3-5nm are put in a mortar, ground for 9-20min, weighed and added with or baked with a certain amount of water under an infrared lamp, the mass of the concentrated gel is controlled to be 1.01g and transferred into a reaction kettle, and the concentrated gel is heated and crystallized in a thermostat at 180 ℃ for 2 d. And after the crystallization reaction is finished, cooling the reaction kettle to room temperature, opening the kettle, taking out the solid crystallization product, washing, and drying in a 50 ℃ oven to obtain molecular sieve powder. Placing the molecular sieve powder in a muffle furnace, raising the temperature to 550 ℃ by a program, and calcining for 5 hours to obtain a final molecular sieve product, wherein the yield is 92.6%. Wherein the mol ratio of each component in the crystallization reaction is as follows: 1 SiO2: 0.0063 Al2O3:0.111 Na2O: 0.0469 TPABr: 1.109 H2O, the mass ratio is: 1 SiO2: 0.0173 CNTs。
Example 11: preparing an aluminum-containing MFI molecular sieve with a micro-mesoporous structure.
0.3g of sodium metasilicate nonahydrate, 0.51g of white carbon black, 0.12g of tetrapropylammonium bromide and 0.04g of Al were weighed out respectively2(SO4)3·18H2Placing O, 0.3g deionized water and 0.01g carbon nano tube with the tube diameter of 3-5nm in a mortar, grinding for 9-20min, weighing the mass, adding or baking a certain amount of water under an infrared lamp, controlling the mass of the concentrated gel to be 1.31g, transferring the concentrated gel into a reaction kettle, and heating and crystallizing for 2d in a thermostat at 180 ℃. And after the crystallization reaction is finished, cooling the reaction kettle to room temperature, opening the kettle, taking out the solid crystallization product, washing, and drying in a 50 ℃ oven to obtain molecular sieve powder. Placing the molecular sieve powder in a muffle furnace, raising the temperature to 550 ℃ by a program, and calcining for 5 hours to obtain a final molecular sieve product, wherein the yield is 92.0%. Wherein the mol ratio of each component in the crystallization reaction is as follows: 1 SiO2: 0.0063 Al2O3:0.111 Na2O: 0.0469 TPABr: 2.855 H2O, the mass ratio is: 1 SiO2: 0.0173 CNTs。
Example 12: preparing an aluminum-containing MFI molecular sieve with a micro-mesoporous structure.
0.3g of sodium metasilicate nonahydrate, 0.51g of white carbon black, 0.12g of tetrapropylammonium bromide and 0.08g of Al were weighed out respectively2(SO4)3·18H2O and 0.01g of carbon nano tube with the tube diameter of 3-5nm are put in a mortar, ground for 9-20min, weighed and added with or baked with a certain amount of water under an infrared lamp, the mass of the concentrated gel is controlled to be 1.05g and transferred into a reaction kettle, and the concentrated gel is heated and crystallized in a thermostat at 180 ℃ for 2 d. And after the crystallization reaction is finished, cooling the reaction kettle to room temperature, opening the kettle, taking out the solid crystallization product, washing, and drying in a 50 ℃ oven to obtain molecular sieve powder. Placing the molecular sieve powder in a muffle furnace, raising the temperature to 550 ℃ by a program, and calcining for 5 hours to obtain a final molecular sieve product, wherein the yield is 92.4%. Wherein the mol ratio of each component in the crystallization reaction is as follows: 1 SiO2: 0.0126 Al2O3:0.111 Na2O: 0.0469 TPABr: 1.109 H2O, the mass ratio is: 1 SiO2: 0.0173 CNTs。
Claims (4)
1. A preparation method of MFI molecular sieve with micro-mesoporous structure is characterized by comprising the following steps: respectively weighing a silicon source, an organic template agent, an alkali source, an ammonium salt and a hard template agent, putting the silicon source, the organic template agent, the alkali source, the ammonium salt and the hard template agent into a mortar, and grinding; adding deionized water or infrared lamp to bake the ground powdery or semi-dry solid mixture, controlling water content, transferring to a reaction kettle, and heating in a drying oven at constant temperature to perform crystallization reaction; after crystallization is finished, cooling the reaction kettle to room temperature, taking out a solid crystalline product, washing, and drying in a 50 ℃ oven to obtain molecular sieve raw powder; the molecular sieve raw powder is calcined in a muffle furnace by temperature programming to 550 ℃ to obtain the MFI molecular sieve with the micro-mesoporous structure;
the silicon source is sodium metasilicate nonahydrate, white carbon black or sodium silicate; the organic template agent is tetrapropylammonium bromide or tetraethylammonium bromide; the alkali source is sodium metasilicate nonahydrate, sodium hydroxide or sodium silicate; the ammonium salt is ammonium fluoride or ammonium chloride; the hard template agent is carbon nano tubes with different pipe diameters, nano calcium carbonate or straws;
an aluminum source is also added in the preparation method, and the aluminum source is aluminum sulfate octadecahydrate or sodium aluminate.
2. The method of claim 1, wherein: the proportion of the raw materials added during the crystallization reaction is as follows:
the molar ratio of the silicon source, the organic template agent, the alkali source, the ammonium salt, the deionized water and the aluminum source is as follows: 1: (0.0312-1.171): 0.481, (0.836-1.166), (3-10) 0.481;
the mass ratio of the silicon source to the hard template agent is as follows: 1: (0.00087-0.173).
3. The method of claim 1, wherein: the pipe diameter or the grain diameter range of the hard template agent is 2-50 nm.
4. The method of claim 1, wherein: the crystallization reaction temperature is 160-200 ℃, and the crystallization reaction time is 1-6 days.
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| CN111484034A (en) * | 2019-01-28 | 2020-08-04 | 上海恩昆化工科技有限公司 | Preparation method of hierarchical pore ZSM-5 molecular sieve |
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