CN112624142A - Preparation method of nano hierarchical pore Beta molecular sieve - Google Patents
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Abstract
The invention provides a preparation method of a nanometer hierarchical pore Beta molecular sieve, belonging to the technical field of Beta molecular sieve preparation. Compared with the existing method for preparing the Beta molecular sieve by the steam-assisted xerogel conversion method, the method avoids the process of synthesizing the xerogel by evaporating the gel, and directly uses the solid-phase reaction mixture obtained by ball milling the raw materials such as tetraethylammonium bromide, solid silica gel and the like in the steam-assisted conversion, thereby simplifying the synthesis steps and reducing the synthesis cost; meanwhile, the migration and dispersion of solid phase raw materials are promoted due to the existence of steam, so that the nano hierarchical pore Beta molecular sieve which is small in nano particle size, dispersed and rich in intra-crystalline mesopores is prepared.
Description
Technical Field
The invention relates to the technical field of Beta molecular sieve preparation, in particular to a preparation method of a nanometer hierarchical pore Beta molecular sieve.
Background
The Beta molecular sieve has a unique pore structure, a high specific surface area, and good thermal stability and hydrothermal stability, and is widely applied to the fields of industrial catalysis, adsorption separation, biomass conversion and the like. The traditional method for synthesizing the Beta molecular sieve is a hydrothermal synthesis method (hydro-thermal synthesis), which needs a large amount of water as a solvent, generates higher pressure in the reaction process, generates a large amount of strong alkali waste liquid and pollutes the environment. Matsukata applied xerogel conversion technology (dry gel conversion) to the synthesis of Beta molecular sieve for the first time in 1996, and the method is characterized in that water in the synthesized hydrogel is evaporated to dryness to obtain xerogel, and then the xerogel is ground to obtain a solid phase mixture, the solid phase mixture is separated from a water phase and placed in a reaction kettle, and molecular sieve crystals are prepared under the steam-assisted action. Compared with the traditional hydrothermal synthesis method, the Beta molecular sieve synthesized by the xerogel conversion method has the advantages of short crystallization time, low template agent consumption, high yield and the like. However, tetraethyl ammonium hydroxide must be used as a template agent in the prior method, which is expensive, and a large amount of water is still required to be used as a solvent in the preparation process of the initial synthetic gel, so that the process of synthesizing the gel and evaporating the gel to obtain the xerogel is complicated. The 2012 shochu team developed a new method (solvent-free synthesis) for synthesizing Beta molecular sieve directly by grinding solid raw materials under the solvent-free condition, and the method is characterized in that the solid raw materials are ground and mixed and then are put into a reaction kettle, and are directly heated at high temperature to prepare molecular sieve crystals under the solvent-free condition. The solvent-free method greatly simplifies the synthesis steps of the Beta molecular sieve and improves the single kettle utilization rate and the product yield. However, in the method, the product is in an aggregated state due to the coagulation of the solid raw material, so that the microporous pore passages of the Beta molecular sieve cannot be effectively utilized in the catalytic application.
Disclosure of Invention
The invention aims to provide a preparation method of a nanometer hierarchical pore Beta molecular sieve, which is used for preparing the Beta molecular sieve and has the advantages of simple steps, low cost, small and dispersed crystal grain size of the Beta molecular sieve and rich in-crystal mesoporous structure.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a nanometer hierarchical pore Beta molecular sieve, which comprises the following steps:
(1) performing ball milling mixing on a silicon source, an aluminum source, inorganic base, a template agent, Beta seed crystals and water to obtain a solid-phase reaction mixture; the silicon source, the aluminum source and the inorganic base are respectively used in SiO2、Al2O3And Na2Calculated on the content of O, SiO2、Al2O3、Na2The molar ratio of O, the template and water is 1: (0.0083-0.05): (0.113-0.168): (0.28-0.40): (1.5-3);
(2) separating the solid-phase reaction mixture from water, placing the mixture in a reaction kettle, and performing steam-assisted crystallization reaction to obtain a molecular sieve precursor; the temperature of the steam-assisted crystallization reaction is 140 ℃, and the time is 24-72 hours;
(3) and roasting the molecular sieve precursor to obtain the nanometer hierarchical pore Beta molecular sieve.
Preferably, the templating agent is tetraethylammonium bromide.
Preferably, the silicon source is solid silica gel and/or white carbon black; the aluminum source is sodium aluminate; the inorganic base is sodium hydroxide.
Preferably, in the step (2), the mass ratio of the solid-phase reaction mixture to water is 1: (2-4).
Preferably, the mass of the Beta seed crystal is 10 percent of that of the silicon source
Preferably, the temperature of the calcination is 550 ℃.
Preferably, the roasting heat preservation time is 6 hours.
Preferably, the firing is performed in an air atmosphere.
Preferably, after the steam-assisted crystallization reaction, the method further comprises washing and drying the solid product of the reaction.
Preferably, the frequency of the ball milling is 30Hz, and the time of the ball milling is 5 h.
The invention provides a preparation method of a nanometer hierarchical pore Beta molecular sieve, which comprises the following steps: (1) performing ball milling mixing on a silicon source, an aluminum source, inorganic base, a template agent, Beta seed crystals and water to obtain a solid-phase reaction mixture; the silicon source, the aluminum source and the inorganic base are respectively used in SiO2、Al2O3And Na2Calculated on the content of O, SiO2、Al2O3、Na2The molar ratio of O, the template and water is 1: (0.0083-0.05): (0.113-0.168): (0.28-0.40): (1.5-3); (2) separating the solid-phase reaction mixture from water, placing the mixture in a reaction kettle, and performing steam-assisted crystallization reaction to obtain a molecular sieve precursor; the temperature of the steam-assisted crystallization reaction is 140 ℃, and the time is 24-72 hours; (3) and roasting the molecular sieve precursor to obtain the nanometer hierarchical pore Beta molecular sieve.
Compared with the existing method for preparing the Beta molecular sieve by the steam-assisted xerogel conversion method, the method avoids the process of synthesizing the xerogel by evaporating the gel, and directly uses the solid-phase reaction mixture obtained by ball milling of the raw materials in the steam-assisted conversion, thereby simplifying the synthesis steps; meanwhile, the migration and dispersion of solid phase raw materials are promoted due to the existence of steam, so that the nano hierarchical pore Beta molecular sieve with small and dispersed nano particles and large specific surface is prepared.
Furthermore, the invention does not use tetraethyl ammonium hydroxide as a template agent (2 kg, 3200 yuan produced by Alfa) but uses cheap tetraethyl ammonium bromide (2 kg, 200 yuan produced by the shin-chemical research institute) as the template agent, thereby greatly reducing the cost of raw materials.
In addition, the method also inherits the advantages of the Beta molecular sieve prepared by the traditional steam-assisted xerogel conversion method, and can prepare the nano hierarchical pore Beta molecular sieve with a wide silicon-aluminum ratio range, wherein the silicon-aluminum ratio range of the nano hierarchical pore Beta molecular sieve prepared by the method is 10-60.
The steam-assisted xerogel conversion method can prepare a hierarchical pore molecular sieve, but the mesopores in the hierarchical pore molecular sieve are nanocrystalline stacked intergranular mesopores, and the mesoporous structure of the Beta molecular sieve prepared by the invention mainly contains rich intracrystalline mesopores (about 10nm) besides stacked intergranular mesopores.
Drawings
FIG. 1 shows an XRD pattern (a), a nitrogen adsorption/desorption isotherm (b), a transmission electron microscope picture (c) and a scanning transmission electron microscope picture (d) of Beta-1 prepared in example 1;
FIG. 2 is an XRD pattern of Beta-2 prepared in example 2 and Beta-D5 prepared in comparative example 5;
FIG. 3 is a scanning electron micrograph of Beta-2 prepared in example 2 and Beta-D5 prepared in comparative example 5;
FIG. 4 is a transmission electron micrograph of Beta-2 prepared in example 2 and Beta-D5 prepared in comparative example 5;
FIG. 5 is an XRD spectrum of the Beta molecular sieves prepared in examples 3-4;
FIG. 6 is a scanning electron microscope image of a sample prepared in examples 3 to 4;
FIG. 7 is a transmission electron microscope image of Beta molecular sieves prepared in examples 3-4;
FIG. 8 is an XRD spectrum of the Beta molecular sieves prepared in examples 5-6;
FIG. 9 is a scanning electron micrograph of Beta molecular sieves prepared in examples 5-6;
FIG. 10 is an XRD pattern of the Beta molecular sieves prepared in examples 7-8;
FIG. 11 is a scanning electron micrograph of Beta molecular sieves prepared in examples 7-8;
FIG. 12 is a transmission electron micrograph of Beta molecular sieves prepared in examples 7 to 8;
figure 13 is an XRD pattern of the molecular sieves prepared in comparative example 1 and comparative example 2;
FIG. 14 is a scanning electron micrograph of the molecular sieves prepared in comparative example 1 and comparative example 2;
figure 15 is an XRD pattern of the molecular sieves prepared in comparative example 3 and comparative example 4;
FIG. 16 is a scanning electron micrograph of the molecular sieves prepared in comparative example 3 and comparative example 4;
fig. 17 is a transmission electron micrograph of the molecular sieves prepared in comparative example 3 and comparative example 4.
Detailed Description
The invention provides a preparation method of a nanometer hierarchical pore Beta molecular sieve, which comprises the following steps:
(1) performing ball milling mixing on a silicon source, an aluminum source, inorganic base, a template agent, Beta seed crystals and water to obtain a solid-phase reaction mixture; the silicon source, the aluminum source and the inorganic base are respectively used in SiO2、Al2O3And Na2Calculated on the content of O, SiO2、Al2O3、Na2The molar ratio of O, the template and water is 1: (0.0083-0.05): (0.113-0.168): (0.28-0.40): (1.5-3);
(2) separating the solid-phase reaction mixture from water, placing the mixture in a reaction kettle, and performing steam-assisted crystallization reaction to obtain a molecular sieve precursor; the temperature of the steam-assisted crystallization reaction is 140 ℃, and the time is 24-72 hours;
(3) and roasting the molecular sieve precursor to obtain the nanometer hierarchical pore Beta molecular sieve.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
The method comprises the following steps of ball-milling and mixing a silicon source, an aluminum source, an inorganic base, a template agent, Beta seed crystals and water to obtain a solid-phase reaction mixture; the silicon source, the aluminum source and the inorganic base are respectively used in SiO2、Al2O3And Na2Calculated on the content of O, SiO2、Al2O3、Na2The molar ratio of O, the template and water is 1: (0.0083-0.05): (0.113-0.168): (0.28-0.40): (1.5 to 3).
In the invention, the silicon source is preferably solid silica gel and/or white carbon black, and more preferably solid silica gel; the aluminum source is preferably sodium aluminate; the inorganic base is preferably sodium hydroxide; the template agent is preferably tetraethylammonium bromide; the water is preferably deionized water. The raw materials of the invention have low cost.
In the present invention, the SiO2、Al2O3、Na2The molar ratio of O, templating agent and water is preferably 1: 1: (0.01-0.04): 0.135: 0.28: (1.5 to 3). The invention adds a small amount of water, canTo promote sufficient contact between the silica and aluminum sources and depolymerization polycondensation.
In the present invention, the ball-milling mixing is preferably performed in a ball mill. The invention uses ball milling to mix the solid phase raw materials, can reduce the human factor of grinding, and leads the mixing to be more uniform and the repeatability to be high.
In the invention, the grinding balls used for ball milling comprise grinding balls with the diameter of 1mm, grinding balls with the diameter of 5mm and grinding balls with the diameter of 10mm, and the number ratio of the grinding balls with the diameter of 1mm to the grinding balls with the diameter of 5mm to the grinding balls with the diameter of 10mm is 10: 10: 1. in the present invention, the frequency of the ball milling is preferably 30Hz, and the time of the ball milling is preferably 5 h. The invention has no special requirement on the rotation speed of the ball milling, and the rotation speed of the ball milling which is well known in the field can be adopted.
After the solid-phase reaction mixture is obtained, the solid-phase reaction mixture and water are separated and placed in a reaction kettle for steam-assisted crystallization reaction, and a molecular sieve precursor is obtained.
In the present invention, the mass ratio of the solid-phase reaction mixture to water is preferably 1: (2-4), more preferably 1: 2 or 1: 4. in the invention, the solid-phase reaction mixture and the water are placed in a separated way, that is, the solid-phase reaction mixture and the water are not contacted when placed. The solid-phase reaction mixture is preferably filled into a polytetrafluoroethylene inner liner, and then the polytetrafluoroethylene inner liner filled with the solid-phase reaction mixture is embedded into a reaction kettle with water at the bottom for steam-assisted crystallization reaction.
In the invention, the temperature of the steam-assisted crystallization reaction is 140 ℃, and the time is 24-72 hours, preferably 30-65 hours, and more preferably 40-60 hours. In the steam-assisted crystallization process, water is evaporated into water vapor at high temperature and high pressure, the water vapor promotes the migration of a solid-phase reaction mixture and the transmission of raw materials, the full contact and reaction of the raw materials are ensured, and a silicon source, an aluminum source and inorganic base undergo polymerization-depolymerization-secondary polymerization and other processes in the steam-assisted crystallization process to nucleate and crystallize, so that a molecular sieve precursor is obtained. In addition, the existence of the water vapor ensures the material transmission, and the water vapor can also form a liquid film on the surface of the material, so that a crystallization area is divided into a plurality of micro areas to synchronously nucleate and crystallize, thereby reducing the size of the molecular sieve precursor.
The invention ensures the smooth crystallization by controlling the temperature and time of the steam-assisted crystallization.
After the steam-assisted crystallization reaction is completed, the method preferably further comprises washing and drying the reacted solid product to obtain the molecular sieve precursor. In the present invention, the washing is preferably performed with deionized water until the washing liquid is neutral. In the present invention, the drying temperature is preferably 60 ℃, and the drying time is preferably 12 hours.
After a molecular sieve precursor is obtained, roasting the molecular sieve precursor to obtain the nanometer hierarchical pore Beta molecular sieve.
In the present invention, the temperature of the calcination is preferably 550 ℃, and the time of the calcination is preferably 6 hours. The calcination according to the invention is preferably carried out in an air atmosphere. The invention removes the template agent by roasting.
The following examples are provided to illustrate the preparation method of the nanoscale hierarchical pore Beta molecular sieve provided by the present invention, but they should not be construed as limiting the scope of the present invention.
In the following examples and comparative examples, tetraethylammonium bromide was used from Tianjin Guangfu Fine chemical research institute, sodium aluminate was used from national reagent, solid silica gel was used from Aladdin reagent or Qingdao ocean chemical Co., Ltd, white carbon black was used from Xuzhou Tiancheng chlor-alkali chemical Co., Ltd, sodium hydroxide was used from Tianjin Yongcheng Fine chemical Co., Ltd, and Beta seed crystal was used from Alfa reagent.
Example 1
Weighing 0.5g of solid silica gel, 0.495g of tetraethylammonium bromide, 0.068g of sodium hydroxide, 0.052g of sodium aluminate, 0.05g of seed crystal and 0.45g of deionized water as solid-phase raw materials, adding the solid-phase raw materials into a spheroidal graphite tank, and ball-milling for 5 hours to obtain a solid-phase reaction mixture; weighing 0.5g of solid-phase reaction mixture, filling the solid-phase reaction mixture into a 5mL polytetrafluoroethylene lining, embedding the solid-phase reaction mixture into a 50mL reaction kettle with 1g of deionized water at the bottom, performing steam assisted crystallization for 72h at 140 ℃, performing centrifugal washing on a product to neutrality by using the deionized water after crystallization is completed, drying the product for 12h at 60 ℃, and finally roasting the product for 6h at 550 ℃ under the air condition to obtain the Beta molecular sieve which is marked as sample Beta-1.
The solid silica gel is purchased from Qingdao ocean chemical Co Ltd, and the molar ratio of each raw material in the solid-phase reaction mixture is SiO2：Al2O3：Na2O：TEABr：H2O＝1：0.025：0.135：0.28：3。
Example 2
Weighing 0.5g of solid silica gel, 0.495g of tetraethylammonium bromide, 0.068g of sodium hydroxide, 0.052g of sodium aluminate, 0.05g of seed crystal and 0.225g of deionized water as solid-phase raw materials, adding the solid-phase raw materials into a nodular graphite tank, and ball-milling for 5 hours to obtain a solid-phase reaction mixture; weighing 0.5g of solid-phase reaction mixture, filling the solid-phase reaction mixture into a 5mL polytetrafluoroethylene lining, embedding the solid-phase reaction mixture into a 50mL reaction kettle with 2g of deionized water at the bottom, performing steam assisted crystallization for 72h at 140 ℃, performing centrifugal washing on a product to neutrality by using the deionized water after crystallization is completed, drying the product for 12h at 60 ℃, and finally roasting the product for 6h at 550 ℃ under the air condition to obtain the Beta molecular sieve which is marked as sample Beta-2.
The solid silica gel is purchased from Qingdao ocean chemical Co Ltd, and the molar ratio of each raw material in the solid-phase reaction mixture is SiO2：Al2O3：Na2O：TEABr：H2O＝1：0.025：0.135：0.28：1.5。
Example 3
Weighing 0.5g of solid silica gel, 0.495g of tetraethylammonium bromide, 0.068g of sodium hydroxide, 0.104g of sodium aluminate, 0.05g of seed crystal and 0.45g of deionized water as solid-phase raw materials, adding the solid-phase raw materials into a spheroidal graphite tank, and performing ball milling for 5 hours to obtain a solid-phase reaction mixture; weighing 0.5g of solid-phase reaction mixture, filling the solid-phase reaction mixture into a 5mL polytetrafluoroethylene lining, embedding the solid-phase reaction mixture into a 50mL reaction kettle with 1g of deionized water at the bottom, performing steam assisted crystallization for 72h at 140 ℃, performing centrifugal washing on a product to neutrality by using the deionized water after crystallization is completed, drying the product for 12h at 60 ℃, and finally roasting the product for 6h at 550 ℃ under the air condition to obtain the Beta molecular sieve which is marked as sample Beta-3.
The solid silica gel is purchased from Qingdao ocean chemical Co Ltd, and the molar ratio of each raw material in the solid-phase reaction mixture is SiO2：Al2O3：Na2O：TEABr：H2O＝1：0.05：0.168：0.28：3。
Example 4
Weighing 0.5g of solid silica gel, 0.495g of tetraethylammonium bromide, 0.068g of sodium hydroxide, 0.017g of sodium aluminate, 0.05g of seed crystal and 0.45g of deionized water as solid-phase raw materials, adding the solid-phase raw materials into a spheroidal graphite tank, and performing ball milling for 5 hours to obtain a solid-phase reaction mixture; weighing 0.5g of solid-phase reaction mixture, filling the solid-phase reaction mixture into a 5mL polytetrafluoroethylene lining, embedding the solid-phase reaction mixture into a 50mL reaction kettle with 1g of deionized water at the bottom, performing steam assisted crystallization for 72h at 140 ℃, performing centrifugal washing on a product to neutrality by using the deionized water after crystallization is completed, drying the product for 12h at 60 ℃, and finally roasting the product for 6h at 550 ℃ under the air condition to obtain the Beta molecular sieve which is marked as sample Beta-4.
The solid silica gel is purchased from Qingdao ocean chemical Co Ltd, and the molar ratio of each raw material in the solid-phase reaction mixture is SiO2：Al2O3：Na2O：TEABr：H2O＝1：0.0083：0.113：0.28：3。
Example 5
Weighing 0.5g of solid silica gel, 0.495g of tetraethylammonium bromide, 0.068g of sodium hydroxide, 0.052g of sodium aluminate, 0.05g of seed crystal and 0.45g of deionized water as solid-phase raw materials, adding the solid-phase raw materials into a spheroidal graphite tank, and ball-milling for 5 hours to obtain a solid-phase reaction mixture; weighing 0.5g of solid-phase reaction mixture, filling the solid-phase reaction mixture into a 5mL polytetrafluoroethylene lining, embedding the solid-phase reaction mixture into a 50mL reaction kettle with 1g of deionized water at the bottom, performing steam assisted crystallization at 140 ℃ for 24h, after crystallization is completed, centrifugally washing a product with deionized water to be neutral, drying at 60 ℃ for 12h, and finally roasting at 550 ℃ for 6h under the air condition to obtain the Beta molecular sieve, wherein the Beta molecular sieve is marked as sample Beta-5.
The solid silica gel is purchased from Qingdao ocean chemical Co Ltd, and the molar ratio of each raw material in the solid-phase reaction mixture is SiO2：Al2O3：Na2O：TEABr：H2O＝1：0.025：0.135：0.28：3。
Example 6
Weighing 0.5g of solid silica gel, 0.708g of tetraethylammonium bromide, 0.068g of sodium hydroxide, 0.052g of sodium aluminate, 0.05g of seed crystal and 0.45g of deionized water as solid-phase raw materials, adding the solid-phase raw materials into a spheroidal graphite tank, and performing ball milling for 5 hours to obtain a solid-phase reaction mixture; weighing 0.5g of solid-phase reaction mixture, filling the solid-phase reaction mixture into a 5mL polytetrafluoroethylene lining, embedding the solid-phase reaction mixture into a 50mL reaction kettle with 1g of deionized water at the bottom, performing steam assisted crystallization for 72h at 140 ℃, performing centrifugal washing on a product to neutrality by using the deionized water after crystallization is completed, drying the product for 12h at 60 ℃, and finally roasting the product for 6h at 550 ℃ under the air condition to obtain the Beta molecular sieve which is marked as sample Beta-6.
The solid silica gel is purchased from Qingdao ocean chemical Co Ltd, and the molar ratio of each raw material in the solid-phase reaction mixture is SiO2：Al2O3：Na2O：TEABr：H2O＝1：0.025：0.135：0.40：3。
Example 7
Weighing 0.5g of solid silica gel, 0.495g of tetraethylammonium bromide, 0.068g of sodium hydroxide, 0.052g of sodium aluminate, 0.05g of seed crystal and 0.45g of deionized water as solid phase raw materials, adding the solid phase raw materials into a spheroidal graphite tank, performing ball milling for 5 hours to obtain a solid phase reaction mixture, weighing 0.5g of the solid phase reaction mixture, filling the solid phase reaction mixture into a 5mL polytetrafluoroethylene lining, then embedding the solid phase reaction mixture into a 50mL reaction kettle with 1g of deionized water at the bottom, performing steam assisted crystallization for 72 hours at 140 ℃, performing centrifugal washing on a product to neutrality by using the deionized water after crystallization is completed, then drying for 12 hours at 60 ℃, and finally roasting for 6 hours at 550 ℃ and under the air condition to obtain a Beta molecular sieve which is marked as a sample Beta-7.
The solid silica gel is purchased from Aladdin reagent company, and the molar ratio of each raw material in the solid-phase reaction mixture is SiO2：Al2O3：Na2O：TEABr：H2O＝1：0.025：0.135：0.28：3。
Example 8
Weighing 0.5g of white carbon black, 0.495g of tetraethylammonium bromide, 0.068g of sodium hydroxide, 0.052g of sodium aluminate, 0.05g of seed crystal and 0.45g of deionized water as solid phase raw materials, adding the solid phase raw materials into a spheroidal graphite tank, performing ball milling for 5 hours to obtain a solid phase reaction mixture, weighing 0.5g of the solid phase reaction mixture, filling the solid phase reaction mixture into a 5mL polytetrafluoroethylene lining, then embedding the solid phase reaction mixture into a 50mL reaction kettle with 1g of deionized water at the bottom, performing steam assisted crystallization for 72 hours at 140 ℃, centrifugally washing a product to be neutral by using the deionized water after crystallization is completed, then drying for 12 hours at 60 ℃, and finally roasting for 6 hours at 550 ℃ and under the air condition to obtain a Beta molecular sieve which is marked as a sample Beta-8.
The white carbon black is purchased from Xuzhou Tian chlor-alkali chemical Co., Ltd, and the molar ratio of each raw material in the solid-phase reaction mixture is SiO2：Al2O3：Na2O：TEABr：H2O＝1：0.025：0.135：0.28：3。
Table 1 shows the initial charge ratios of examples 1 to 8.
TABLE 1 initial compounding ratio (molar ratio) of examples 1 to 8
Comparative example 1
Beta molecular sieves were prepared using a solvent-free method reported in the literature:
weighing 0.5g of solid silica gel, 0.495g of tetraethylammonium bromide, 0.068g of sodium hydroxide, 0.052g of sodium aluminate, 0.05g of seed crystal and 0.45g of deionized water as solid phase raw materials, adding the solid phase raw materials into a mortar, grinding for 15min to obtain a solid phase reaction mixture, weighing 0.5g of the solid phase reaction mixture, directly putting the solid phase reaction mixture into a 50mL reaction kettle, heating at 140 ℃ for 72h, centrifugally washing the product with the deionized water to be neutral after crystallization is completed, drying at 60 ℃ for 12h, and finally roasting at 550 ℃ for 6h under the air condition to obtain the Beta molecular sieve which is marked as a sample Beta-D1.
The solid silica gel is purchased from Qingdao ocean chemical Co Ltd, and the molar ratio of each raw material in the solid phase reaction mixture of the comparative example is SiO2：Al2O3：Na2O：TEABr：H2O＝1：0.025：0.135：0.28：3。
Comparative example 2
Weighing 0.5g of solid silica gel, 0.495g of tetraethylammonium bromide, 0.068g of sodium hydroxide, 0.052g of sodium aluminate, 0.05g of seed crystal and 0.45g of deionized water as solid phase raw materials, adding the solid phase raw materials into a spheroidal graphite tank, performing ball milling for 5 hours to obtain a solid phase reaction mixture, weighing 0.5g of the solid phase reaction mixture, directly filling the solid phase reaction mixture into a 50mL reaction kettle, heating at 140 ℃ for 72 hours, performing crystallization, performing centrifugal washing on the product with the deionized water to neutrality, drying at 60 ℃ for 12 hours, and finally roasting at 550 ℃ and air for 6 hours to obtain a Beta molecular sieve which is marked as a sample Beta-D2.
The solid silica gel is purchased from Qingdao ocean chemical Co Ltd, and the molar ratio of each raw material in the solid phase reaction mixture of the comparative example is SiO2：Al2O3：Na2O：TEABr：H2O＝1：0.025：0.135：0.28：3。
Comparative example 3
The difference from example 1 is that the molar ratio of each raw material in the solid-phase reaction mixture of the present comparative example is SiO2：Al2O3：Na2O：TEABr：H2O＝1：0.005：0.083：0.28：3。
Comparative example 4
The difference from example 1 is that the molar ratio of each raw material in the solid-phase reaction mixture of the present comparative example is SiO2：Al2O3：Na2O：TEABr：H2O＝1：0.0025：0.080：0.28：3。
Comparative example 5
The difference from the example 1 is that the solid phase mixed raw material contains no water, specifically:
weighing 0.5g of solid silica gel, 0.495g of tetraethylammonium bromide, 0.068g of sodium hydroxide, 0.052g of sodium aluminate and 0.05g of seed crystal as solid phase raw materials, adding the solid phase raw materials into a spheroidal graphite tank, performing ball milling for 5 hours to obtain a solid phase reaction mixture, weighing 0.5g of the solid phase reaction mixture, filling the solid phase reaction mixture into a 5mL polytetrafluoroethylene lining, embedding the solid phase reaction mixture into a 50mL reaction kettle with 2g of deionized water at the bottom, performing steam assisted crystallization for 72 hours at 140 ℃, centrifugally washing a product to be neutral by using deionized water after the crystallization is finished, drying the product for 12 hours at 60 ℃, and finally roasting the product for 6 hours at 550 ℃ and under the air condition to obtain a Beta molecular sieve which is marked as a sample Beta-D5.
The solid silica gel is purchased from Qingdao ocean chemical Co Ltd, and the molar ratio of each raw material in the solid-phase reaction mixture is SiO2：Al2O3：Na2O：TEABr＝1：0.025：0.135：0.28。
Table 2 shows the initial charge ratio and crystallization conditions of comparative examples 1 to 5.
TABLE 2 initial compounding ratio and crystallization conditions (molar ratio) of comparative examples 1 to 5
Structural and performance characterization
The following XRD test adopts a Rigaku DMax 2550 instrument of Rigaku company, the scanning range is 4-40 degrees, and the scanning speed is 9 degrees/min; the transmission electron microscope analysis adopts a GrandARM300 type instrument of JEOL company; adopting JSM-6510 type instrument of JEOL company for scanning electron microscope analysis; the scanning transmission electron microscope analysis adopts a JEM-2100F type instrument of JEOL company; nitrogen adsorption/desorption characterization was performed using an automatic Micromeritics SAP 2020 Analyzer from Micromerics, at an analysis temperature of 77.35K, and degassing was performed at 350 ℃ under vacuum.
1. FIG. 1 shows an XRD pattern (a), a nitrogen adsorption/desorption isotherm (b), a transmission electron microscope picture (c) and a scanning transmission electron microscope picture (d) of Beta-1 prepared in example 1. From the XRD pattern of fig. 1, the Beta molecular sieve prepared in example 1 is a pure phase and has good crystallinity; the nitrogen adsorption/desorption isotherm can indicate that Beta-1 has both a microporous structure and a mesoporous structure, and hysteresis loops at low and high relative pressures respectively correspond to intragranular mesopores and intergranular mesopores; from the transmission electron microscope picture, Beta-1 is a crystal of 200nm formed by the accumulation of several nm nanocrystals. The abundant intracrystalline mesoporous structures in Beta-1 can be clearly seen by scanning a transmission electron microscope picture.
2. FIG. 2 is an XRD pattern of Beta-2 prepared in example 2 and Beta-D5 prepared in comparative example 5. As can be seen from FIG. 2, both Beta-2 and Beta-D5 are phase-pure Beta molecular sieves with good crystallinity.
3. FIG. 3 is a scanning electron micrograph of Beta-2 prepared in example 2 and Beta-D5 prepared in comparative example 5, wherein (a) is Beta-2 and (b) is Beta-D5. As can be seen from FIG. 3, as the amount of water added in the experimental formulation gradually decreased, when H was reached2When the O/Si is gradually reduced from 3 to 1.5 (example 2) and 0 (comparative example 5), the dispersity of the prepared Beta molecular sieve is gradually reduced, and particularly, when no water is contained in the synthesis raw material, the product is in a condensed state.
4. FIG. 4 is a transmission electron micrograph of Beta-2 prepared in example 2 and Beta-D5 prepared in comparative example 5, wherein (a) is Beta-2 and (b) is Beta-D5. As can be seen from FIG. 4, when H is2When the O/Si is reduced to 1.5, the Beta-2 product still maintains better dispersion degree, the crystal is formed by stacking nano crystals with the size of 20nm, and when the H is reduced to H2When the O/Si is reduced to 0, the Beta-D5 sample is in an aggregation state, the grain size is increased to 100nm, the dispersion degree is poor, and the grains are aggregated. In conclusion, the appropriate amount of water (H) in the synthesis raw material2O/Si is 1.5-3) is a necessary condition for preparing the nanometer hierarchical pore Beta molecular sieve.
5. FIG. 5 is an XRD spectrum of the Beta molecular sieves prepared in examples 3-4. As can be seen from FIG. 5, the Beta molecular sieves prepared in examples 3-6 are pure phase Beta molecular sieves, and have good crystallinity. The Beta molecular sieve with a wide silicon-aluminum ratio range (Si/Al is 10-60) can be prepared by the method.
6. FIG. 6 is a scanning electron micrograph of samples prepared in examples 3-4, wherein (a) is Beta-3 and (b) is Beta-4. As can be seen from fig. 6, the prepared samples of Si/Al ═ 10 and 60 each had regular morphology and were relatively dispersed, and the nanoparticles were formed by stacking of nanocrystals of several nanometers, with a size of about 200 nm.
7. FIG. 7 is a transmission electron microscope image of Beta molecular sieves prepared in examples 3-4, wherein (a) is Beta-3 and (b) is Beta-4. As is clear from FIG. 7, both Beta-3 and Beta-4 were formed by stacking nanocrystals of 10nm and contained abundant intracrystalline mesopores.
8. FIG. 8 is an XRD pattern of Beta molecular sieves prepared in examples 5-6, wherein (a) is Beta-5 and (b) is Beta-6. As can be seen from FIG. 8, the Beta molecular sieves prepared in examples 5 to 6 were all pure phase Beta molecular sieves, and had good crystallinity. It is shown that the Beta molecular sieve with high crystallinity can be prepared by shortening the crystallization time to 24h (example 5) or increasing the content of the template agent to 0.40 TEA/Si (example 6) on the basis of example 1, and other conditions are not changed.
9. FIG. 9 is a scanning electron micrograph of Beta molecular sieves prepared in examples 5-6, wherein (a) is Beta-5 and (b) is Beta-6. As can be seen from fig. 9, when the crystallization time is shortened to 24h (example 5), or the content of the templating agent is increased to TEA/Si of 0.40 (example 6), the prepared Beta molecular sieve has regular morphology and more dispersed particles, and each particle is formed by stacking smaller nanocrystals.
10. FIG. 10 is an XRD spectrum of the Beta molecular sieves prepared in examples 7-8. As can be seen from FIG. 10, the Beta molecular sieves prepared in examples 7 to 8 were all pure phase Beta molecular sieves, and had good crystallinity. The method is shown in the fact that solid silica gel and white carbon black (Xuzhou Tiancheng) of other manufacturers (alpha) are used as solid silicon sources, and the Beta molecular sieve with high crystallinity can be prepared.
11. FIG. 11 is a scanning electron micrograph of Beta molecular sieves prepared in examples 7-8, wherein (a) is Beta-7 and (b) is Beta-8. As can be seen from FIG. 11, the Beta molecular sieve prepared by using the above two silicon sources has regular morphology and relatively dispersed particles.
12. FIG. 12 is a transmission electron micrograph of Beta molecular sieves prepared in examples 7-8, wherein (a) is Beta-7 and (b) is Beta-8. As can be seen from FIG. 12, both of the Beta molecular sieves prepared using the above two silicon sources were formed by stacking nanocrystals at-10 nm.
13. FIG. 13 is an XRD pattern of Beta molecular sieves prepared in comparative example 1 and comparative example 2. As can be seen from FIG. 10, the Beta molecular sieves prepared in comparative examples 1-2 are pure phase Beta molecular sieves, and have good crystallinity. The method shows that the pure phase Beta molecular sieve can be prepared by grinding or ball milling the solid phase mixed raw materials and then adopting a high-temperature heating treatment method, and has good crystallinity.
14. FIG. 14 is a scanning electron micrograph of Beta molecular sieves prepared in comparative example 1 and comparative example 2, wherein (a) is Beta-D1 and (b) is Beta-D2. As can be seen from fig. 11, the Beta molecular sieve obtained by the above high-temperature heating treatment has an aggregated crystal morphology, a large crystal size in the order of micrometers, and no mesoporous structure is generated, which indicates that steam assistance in the method is a necessary condition for preparing the nano hierarchical pore Beta molecular sieve.
15. FIG. 15 is an XRD pattern of Beta molecular sieves prepared in comparative example 3 and comparative example 4. As can be seen from FIG. 15, the Beta molecular sieves prepared in comparative examples 3 to 4 are pure phase Beta molecular sieves, and have good crystallinity. The pure phase Beta molecular sieve can be prepared by increasing the silicon-aluminum ratio (Si/Al is 100-200) in the initial charge ratio.
16. FIG. 16 is a scanning electron micrograph of Beta molecular sieves prepared in comparative example 3 and comparative example 4, wherein (a) is Beta-D3 and (b) is Beta-D4. As can be seen from FIG. 16, the Beta molecular sieves prepared by increasing the initial Si/Al ratio (Si/Al is 100-200) have regular morphology and relatively dispersed particles.
17. FIG. 17 is a transmission electron micrograph of Beta molecular sieves prepared in comparative example 3 and comparative example 4, wherein (a) is Beta-D3 and (b) is Beta-D4. As can be seen from FIG. 17, the Beta molecular sieve prepared by increasing the initial Si/Al ratio (Si/Al is 100-200) is a nanoparticle with a size of 50nm, which indicates that when the initial Si/Al ratio is greater than 100, only the nano Beta molecular sieve can be obtained, and the crystal has no hierarchical pore structure.
18. N runs were performed on Beta-1 prepared in example 1, Beta-7 prepared in example 7, Beta-8 prepared in example 8, Beta-D1 prepared in comparative example 1, Beta-D2 prepared in comparative example 22The results of the adsorption/desorption tests are shown in table 3.
TABLE 3 pore parameters of the molecular sieves prepared in examples 1, 7, 8 and comparative examples 1-2
In Table 3, SBETRepresents the total surface area, SmicroRepresents the micropore surface area, SexternalsurfaceRepresents the external surface area, VtotalRepresents the total pore volume, VmicroRepresents the micropore volume, VmesoRepresents the mesopore volume.
As can be seen from Table 2, the Beta molecular sieve synthesized by the method of the invention has large specific surface area and mesopore volume, which indicates that the method is favorable for synthesizing the nano hierarchical pore Beta molecular sieve with large specific surface area. The Beta molecular sieve prepared by the solid silica gel produced by Qingdao ocean research institute has larger specific surface area and mesopore volume compared with the Beta molecular sieve prepared by the solid silica gel produced by alpha and the white carbon black produced by Xuzhongtian. And because the Beta molecular sieve obtained by high-temperature heating treatment is condensed into micron-sized crystals, the specific surface area and the mesopore volume of the sample are smaller.
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. A preparation method of a nanometer hierarchical pore Beta molecular sieve is characterized by comprising the following steps:
(1) performing ball milling mixing on a silicon source, an aluminum source, inorganic base, a template agent, Beta seed crystals and water to obtain a solid-phase reaction mixture; the silicon source, the aluminum source and the inorganic base are respectively used in SiO2、Al2O3And Na2Calculated on the content of O, SiO2、Al2O3、Na2The molar ratio of O, the template and water is 1: (0.0083-0.05): (0.113-0.168): (0.28-0.40): (1.5-3);
(2) separating the solid-phase reaction mixture from water, placing the mixture in a reaction kettle, and performing steam-assisted crystallization reaction to obtain a molecular sieve precursor; the temperature of the steam-assisted crystallization reaction is 140 ℃, and the time is 24-72 hours;
(3) and roasting the molecular sieve precursor to obtain the nanometer hierarchical pore Beta molecular sieve.
2. The method of claim 1, wherein the templating agent is tetraethylammonium bromide.
3. The preparation method according to claim 1, wherein the silicon source is solid silica gel and/or white carbon black; the aluminum source is sodium aluminate; the inorganic base is sodium hydroxide.
4. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the solid-phase reaction mixture to water is 1: (2-4).
5. The method according to claim 1, wherein the Beta seed crystal has a mass of 10% of the mass of the silicon source.
6. The method of claim 1, wherein the firing temperature is 550 ℃.
7. The method of claim 6, wherein the roasting is carried out for a holding time of 6 hours.
8. The production method according to claim 6 or 7, wherein the firing is performed in an air atmosphere.
9. The method of claim 1, wherein the steam assisted crystallization reaction further comprises washing and drying the solid product of the reaction.
10. The preparation method according to claim 1, wherein the frequency of the ball milling is 30Hz, and the time of the ball milling is 5 h.
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