CN1342608A - Process for preparing multi-class sequential macroreticular-micropore material - Google Patents

Abstract

The invention belongs to the field of molecular sieve inorganic materials, and in particular relates to a preparation method of a macroporous microporous multi-level ordered pore material which is favorable for material transmission and has a high degree of order. The present invention uses hydrothermally synthesized microporous molecular sieve nanocrystals (X, Y, A, ZSM-5, Beta, TS-1, silicalite-1, etc.) Forming at low temperature and demoulding at high temperature, a highly ordered macroporous-microporous multi-level ordered pore material is prepared. The prepared dense porous membranes and hierarchical porous materials are widely used in adsorption, separation, sensors and other aspects.

Description

A kind of preparation method of macroporous microporous multilevel ordered pore material

technical field

The invention belongs to the field of inorganic porous materials, and in particular relates to a preparation method of a macroporous microporous multilevel ordered pore material.

technical background

Microporous materials are widely used in catalysis, separation, adsorption, sensors, etc. However, due to the small void volume of microporous molecular sieves and abundant active hydroxyl groups on the surface, the particles are easily bonded, which makes the mass transfer rate and diffusion rate in the reaction process There are serious defects in the field, which often cause difficulties in material transportation, and the pre-column or membrane pre-pressure is very high. Especially as the use time increases, the particles of microporous molecular sieves bond together, causing more inconvenience in material transportation, not only consumes a lot of energy, but also requires stricter material requirements for equipment, and at the same time increases the instability of production. With the development of porous materials, porous materials have developed from micropores (below 2nm) to mesoporous materials (2-50nm) and finally to macroporous materials above 50nm. How to organically combine macropores and micropores to solve this difficult production problem is a challenge for materials chemists. The emergence of nanotechnology and materials provides a way to solve this problem.

Contents of the invention

The object of the present invention is to propose a method for preparing a multi-level ordered pore material capable of organically combining macropores and micropores.

The preparation method of the multi-level ordered pore material that the present invention proposes can make macropores and micropores organically combine is based on microporous zeolite molecular sieves (X, Y, A, ZSM-5, Beta, TS-1, silicalite-1 ) Nanocrystals are the building units of multi-level structures. Macroporous film plates are used to guide the orderly arrangement of nano-units containing microporous structures. After high-temperature calcination, microporous-macroporous molecular sieves with different multilevel ordered structures are obtained. . The specific steps are as follows:

(1) Preparation of microporous molecular sieve nanocrystals with a particle size of less than 100nm under hydrothermal conditions below 100°C, such as X, Y, A, ZSM-5, Beta, TS-1, silicalite-1 zeolites, etc., nanocrystal size below 150 nm;

(2) using absolute ethanol to make the microporous molecular sieve nanocrystal monodisperse, the weight percentage of the nanocrystal in ethanol (i.e. the concentration of the nanocrystal ethanol solution) is 1 to 10%;

(3) Use a macroporous film plate agent to guide the orderly arrangement of monodisperse nanocrystalline units, and form them at low temperature;

(4) Calcining the macroporous-microporous material formed in step (3) at a temperature of 500-600° C., setting the shape, and demolding to obtain a macroporous-microporous hierarchically porous material.

In the present invention, the polystyrene balls with good dispersibility are used as the macroporous template agent, and the diameter of the balls is between 50nm and 400nm, and can be formed by close-packed infiltration method, that is, the polystyrene balls are densely packed first, and then the Monodisperse microporous molecular sieve nanocrystals infiltrate into the gaps of close-packed polystyrene spheres, and add surfactants to self-assemble into a macroporous-microporous multi-level ordered pore structure. Here the consumption of macroporous template agent polystyrene ball is 25～45% (percentage by weight) of total amount (total amount refers to the sum of polystyrene ball and nanocrystal), surfactant adopts the all can of anion or cationic, for example Hexadecyltrimethylammonium bromide, etc., the dosage is 0.1-1% of polystyrene balls. The surfactant makes the templating agent and the nanocrystal have a better affinity and acts as an "adhesive". In this method, if 300nm polystyrene balls are selected, they can be arranged according to cubic close packing by suction filtration, and if 230 nm polystyrene balls are selected, they can be arranged according to hexagonal close packing. Using close-packed polystyrene spheres as a template to obtain a dense film can completely eliminate the intercrystalline gap. This macroporous-microporous multi-level ordered film is characterized by large pores that are conducive to the transformation of macromolecules, and small pores that facilitate the transformation of macromolecules. Molecules react in the microwells. Therefore, it is widely used in sensors, nano-reactors, catalysis, separation, adsorption, etc., and completely solves the problem of material diffusion.

In the present invention, polystyrene spheres are used as the macroporous template agent, and the diameter of the spheres is between 50nm and 400nm, which can also be formed by mechanical tableting. That is, mechanically mix polystyrene balls and microporous molecular sieve nanocrystals evenly, wherein the amount of polystyrene balls is 5-45% (weight percent) of the total amount, and the meaning of the total amount is the same as before. Then the film is made by tableting method, and the mechanical pressure of tableting is 4-12 kg/cm ² . The method is used to prepare a membrane with uniform micropore and macropore diameter and multiple order, and the thickness of the membrane can be 1 millimeter to 1 centimeter. Among them, the amount of polystyrene balls is 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, and a 3 mm thick large ball with an orderly distribution and uniform macropores is obtained. Porous microporous composite membrane materials. Under the condition that the treatment process and membrane thickness are the same, and only the dosage of the macroporous template is different, the mechanical strength obtained is equivalent to that of the molecular sieve membrane with zero macroporous template agent. More than 45% of the film, the strength dropped sharply. Gas permeability tests were performed on this series of membranes. The specific method is: through a glass tube with different apertures at both ends, one end is 1 cm in diameter and the other end is 0.5 cm in diameter. A membrane with a thickness of 3mm and a diameter of 1cm was sealed and fixed in a 1cm tube, and the pre-column pressure was measured. The measured pre-column pressure drop has a linear relationship with the increase of the template component. The membrane obtained by the mechanical tablet method can effectively reduce the pre-column pressure in the process of catalysis and separation, which is the promotion of the application of the close packing method.

Among the present invention, macroporous template agent also can adopt polydimethylsilane soft mold (abbreviated as PDMS), and this soft mold is engraved with the decorative pattern of various shapes such as strip, linear, grid, star, and its decorative pattern size is Micron and submicron levels. And use soft printing technology (that is, Molding technology) to guide the molding. That is, the monodisperse ethanol solution of microporous molecular sieve nanocrystals obtained in step (2) is dropped onto the reaction platform or silicon wafer, and the PAMS engraved with the desired pattern is pressed from top to bottom to the ethanol containing microporous molecular sieve nanocrystals. On the solution, the pressure is 1-2 atmospheric pressure, and it is maintained for at least 12 hours until the ethanol is completely volatilized, so that the nanocrystals can fully self-assemble into a continuous multi-level and ordered microporous network structure.

In the present invention, the preparation of zeolite nanocrystals can adopt the methods recorded in the existing literature. Appropriate improvements can also be made in combination with raw material conditions. It is prepared by using 25% silica sol (pH=9), 25% tetramethylammonium hydroxide, sodium aluminate and the like. Because nanocrystals are smaller and more difficult to separate, the present invention adopts the method of adding flocculant, that is, adding 4 to 10% glucose or sucrose (total mass ratio of feed), which can improve the yield, reaching 90%, and simultaneously make the centrifugal rate from The 20,000r/min of high-speed centrifugation is reduced to 2,000r/min of low-speed centrifugation.

The present invention can use close-packed polystyrene spheres to obtain a hierarchically porous material with macropores, micropores and high degree of order, and the high order property is conducive to its application in adsorption, separation, nanoreactors, etc.; Sensors and reactors with special shapes can be prepared by applying molding technology; unsupported macroporous microporous multi-level materials can be prepared at the polished metal interface. Microporous and macroporous fibers can be prepared on glass substrates, ranging from several microns to several centimeters.

Detailed ways

The following application examples further illustrate the present invention:

Example 1 First, zeolite A nanocrystals were prepared according to the method described in the literature (Thomas Bein et al, Science, 1999, 283, 958). The reaction ingredients are 0.3Na ₂ O: 11.25 SiO ₂ : 1.8 Al ₂ O ₃ : 13.4(TMA) ₂ O: 700H ₂ O, the system uses 25% silica sol (pH=9) instead of 30 % of the silica sol, the reported 97% tetramethylammonium hydroxide was replaced by 25% tetramethylammonium hydroxide in water. Specific process: adjust 25% silica sol (pH 9) to pH=10 with sodium hydroxide solution, accurately weigh 27g of the silica sol, add 15g of water, and stir to prepare precursor solution I. Simultaneously weigh 7.5g of aluminum isopropoxide, 100g of 25% tetramethylammonium hydroxide, 6g of 1M sodium hydroxide solution, and 25g of water, and stir to prepare precursor solution II. Finally, mix the two precursor solutions under vigorous stirring, stir and react at room temperature for one week, add flocculant-glucose 7.22g, reduce the high-speed centrifugation (20,000r/min) in the literature to low-speed centrifugation (2,000r/min), pour out In the supernatant, a pale yellow solid substance was obtained, which was washed repeatedly with water and ethanol to obtain a pale yellow final product, which was verified as zeolite A nanocrystal by XRD, and TEM showed that the zeolite A crystal grain size was tens of nanometers.

Secondly, ethanol is used to disperse the zeolite nanocrystals well, so that it becomes a monodisperse zeolite nanocrystal ethanol solution with a concentration of 8%.

Again, on the filter cloth of filtering, be deposited on the thick polystyrene ball layer of one deck millimeter, the diameter of ball is 300nm, is cubic phase regular arrangement (9.9wt%, 300nm diameter, Bangs Laboratory), the pore between q ball is 160nm . The zeolite nanocrystal dispersed with ethanol diffuses into the void, and the quality of the nanocrystal is three times that of the polystyrene ball, that is, 75% of the total weight of the unbaked film. Assemble and dry at room temperature for 3 to 24 hours, until the ethanol is completely volatilized, and the nanocrystals are fully assembled into a prototype of a macroporous, microporous, and hierarchically porous material.

Finally, by calcination at 550°C for about 10 hours, a three-dimensional highly ordered macroporous and microporous composite material is obtained. The macropore diameter is around 300nm.

Example 2 Zeolite X nanocrystals were prepared from silica sol, sodium aluminate, sodium hydroxide and water. The reaction process is as follows: 104g silica sol (25%SiO ₂ ) (pH is 9), after cooling to 5°C, add 55g sodium hydroxide solution (50%), accurately weigh 27g of this silica sol, add 78g water, and stir to prepare into precursor solution I. Mix 61g of water, 30g of 50% sodium hydroxide solution and 20.36g of sodium aluminate (Al ₂ O ₃ 43%) at below 5°C and stir to prepare precursor solution II. After adding 75g of crushed ice to each flooding solution, the two flooding solutions were mixed rapidly under vigorous stirring, and left for five minutes to form a gel. 22.5g of sucrose was added to the gel, and aged for 16 hours with stirring at room temperature. Dynamic hydrothermal reaction at 100°C for 2-4 hours, after repeated washing with water, a white final product was obtained, which was verified to be zeolite X nanocrystals by XRD, and SEM showed that the zeolite X crystal grain size was 100 nanometers. The ratio of silicon to aluminum is 6.

Secondly, ethanol is used to disperse the zeolite nanocrystals well, so that it becomes a monodispersed zeolite nanocrystal ethanol solution with a concentration of 1%.

Again, on the filter cloth of filtering, be deposited on the thick polystyrene ball layer of one deck millimeter, the diameter of ball is about 300nm, is cubic phase regular arrangement (9.9wt%, 300nm diameter, Bangs Laboratory), the pore between q ball is 160nm. The zeolite nanocrystals dispersed with ethanol diffuse into the voids, and the quality of the nanocrystals is 1.5 times that of polystyrene spheres, that is, 60% of the total weight of the unbaked film. After assembling and drying at room temperature for 3 hours, until the ethanol is completely volatilized, the nanocrystals are fully assembled into a prototype of a macroporous, microporous, and hierarchically porous material.

Finally, by calcination at 500°C for 12 hours, a three-dimensional highly ordered macroporous and microporous composite material is obtained. The macropore diameter is around 300nm.

Example 3 Zeolite Y nanocrystals were prepared from silica sol, sodium aluminate, sodium hydroxide, 25% tetramethylammonium hydroxide and water. Reaction molar composition: 2.46(TMA) ₂ O : 0.04 Na ₂ O : 1Al ₂ O _{3 :} 3.4SiO _{2 :} 37OH ₂ O. The reaction process is as follows: first prepare the sodium aluminate sol containing TMA, mix 895g TMA, 5500g water, 6.4g 50% sodium hydroxide solution and 244g sodium aluminate (Al ₂ O ₃ 43%) below 5°C, stir to make a clear Precursor solution I. The body-dispelling solution was added to 816g of silica sol (25%), stirred vigorously to obtain a homogeneous solution, and 228.9 grams of glucose was added. Static hydrothermal reaction at 100°C for 2-4 hours, and repeated washing with water to obtain a white final product, which was verified as zeolite Y nanocrystals by XRD, and SEM showed that the zeolite Y crystal grain size was below 80 nanometers.

Secondly, ethanol is used to disperse the zeolite nanocrystals well, so that it becomes a monodisperse zeolite nanocrystal ethanol solution with a concentration of 2%.

Again, on the filter cloth of filtering, be deposited on the thick polystyrene sphere layer of one deck millimeter, obtain 300nm polystyrene sphere and be cubic phase regular arrangement (9.9wt%, 300nm diameter, Bangs Laboratory), the pore between q ball is 160nm . Zeolite nanocrystals dispersed with ethanol diffuse into the voids, and the mass of nanocrystals is 1.7 times that of polystyrene spheres, that is, 63% of the total weight of the unbaked film. After being assembled and dried at room temperature for 5 hours, until the ethanol is completely volatilized, the nanocrystals are fully assembled into a prototype of a macroporous, microporous, and hierarchically porous material.

Finally, by calcination at 500°C for 12 hours, a three-dimensional highly ordered macroporous and microporous composite material is obtained. The macropore diameter is around 300nm.

Example 4 Zeolite ZSM-5 nanocrystals were prepared from ethyl orthosilicate, sodium aluminate, sodium hydroxide, 98% tetrapropylammonium hydroxide and water. Reaction molar composition: 6TPAOH: 0.1Na ₂ O: 0.25Al ₂ O ₃ : 25SiO ₂ : 300H _{2 O:} 100EtOH The reaction process is as follows: first prepare the sodium aluminate sol containing TMA, mix 84g TPA, 432g water below 5°C , 16g of 50% sodium hydroxide solution and 6.1g of sodium aluminate (Al ₂ O ₃ 43%) were stirred to prepare a clear precursor solution I. Dissolve 520g of tetraethyl orthosilicate in 100g of water and 460g of ethanol, then mix it with 50g of TPA and vigorously stir at room temperature, and pre-hydrolyze for 12-14 hours to obtain the flooding solution II. Add the precursor solution II to the flooding solution I under vigorous stirring to obtain a homogeneous solution. After 2-4 hours of dynamic hydrothermal reaction at 80°C, after repeated washing with water, a white final product is obtained, which is verified by XRD as zeolite in ZSM-5. Nanocrystalline. TEM showed that the grain size of zeolite ZSM-5 was below 80-100 nm.

Secondly, ethanol is used to disperse the zeolite nanocrystals well, so that it becomes a monodisperse zeolite nanocrystal ethanol solution with a concentration of 6%.

Again, on the filter cloth of filtering, be deposited on the thick polystyrene sphere layer of one deck millimeter, obtain 300nm polystyrene sphere and be cubic phase regular arrangement (9.9wt%, 300nm diameter, Bangs Laboratory), the pore between q ball is 160nm . The zeolite nanocrystal dispersed with ethanol diffuses into the void, and the quality of the nanocrystal is 1.4 times that of the polystyrene ball, that is, 58% of the total weight of the unbaked film. After being assembled and dried at room temperature for 7 hours, until the ethanol is completely volatilized, the nanocrystals are fully assembled into a prototype of a macroporous, microporous, and hierarchically porous material.

Finally, by calcination at 580°C for 10 hours, a three-dimensional highly ordered macroporous and microporous composite material is obtained. The macropore diameter is around 300nm.

Example 5 Zeolite ZSM-5 nanocrystals were prepared from ethyl orthosilicate, 20-25 wt% tetrapropylammonium hydroxide (Zhejiang) and water. Reaction molar composition: 1TPAOH: 2.8SiO ₂ : 11.2 EtOH: 40H ₂ O. The reaction process is as follows: 600g ethyl orthosilicate is dissolved in 90g water and 515g ethanol, then mixed with 844g TPA (20-25wt%) and vigorously stirred, pre-hydrolyzed at 30°C for 72 hours to obtain a gel. 80°C dynamic hydrothermal reaction for 3 days (constant speed 250rpm). Add 82g of flocculant-glucose, and centrifuge at low speed (2,000r/min) to obtain a white final product, which is verified by XRD to be zeolite ZSM-5 all-silicon nanocrystals, and TEM shows that the grain size of ZSM-5 zeolite is below 50-80 nanometers .

Secondly, ethanol is used to disperse the zeolite nanocrystals well, so that it becomes a monodisperse zeolite nanocrystal ethanol solution with a concentration of 5%.

Again, on the filter cloth of filtering, be deposited on the thick polystyrene sphere layer of one deck millimeter, obtain 300nm polystyrene sphere and be cubic phase regular arrangement (9.9wt%, 300nm diameter, Bangs Laboratory), the pore between q ball is 160nm . The zeolite nanocrystals dispersed with ethanol diffuse into the gaps. The quality of the nanocrystals is 2.7 times that of polystyrene balls, which is 73% of the total weight of the unfired film. After assembling and drying at room temperature for 10 hours, until the ethanol is completely volatilized, the nanocrystals Fully assembled into a prototype of macroporous, microporous and hierarchically porous materials.

Finally, by calcination at 500°C for 12 hours, a three-dimensional highly ordered macroporous and microporous composite material is obtained. The macropore diameter is around 300nm.

Example 6 Synthesize all-silicon ZSM-5 according to Example 5. Secondly, ethanol is used to disperse the zeolite nanocrystals well, so that it becomes a monodisperse zeolite nanocrystal ethanol solution with a mass concentration of 9%. Then apply the soft printing technique, drop the prepared ethanol solution of 9% monodisperse zeolite nanocrystals onto a silicon wafer cleaned with ethanol, select a star-shaped polydimethylsilane stamp (Mold ), the channel width is 0.5 microns. From top to bottom, press onto the pile of ethanol solution containing zeolite nanocrystals at a pressure of 1 to 2 atmospheres, and keep it for at least 12 hours until the ethanol is completely evaporated and the nanocrystals are fully assembled into a continuous multi-level organic structure. Ordered microporous network structure.

Then, take off the stamp (Mold) of the star-shaped polydimethylsilane.

Finally, by firing at 550°C for 12 hours, the nanocrystals are fully assembled into a continuous multi-level ordered microporous network structure. The grid width is about 500nm.

Example 7 Synthesize all-silicon ZSM-5 according to Example 5. Secondly, ethanol is used to disperse the zeolite nanocrystals well, so that it becomes a monodisperse zeolite nanocrystal ethanol solution with a mass concentration of 9%. Then apply soft printing technology, drop the prepared ethanol solution of 9% monodisperse zeolite nanocrystals on a silicon wafer cleaned with ethanol, and select a linear polydimethylsilane stamp (Mold) , with a channel width of 1 μm. From top to bottom, press onto the pile of ethanol solution containing zeolite nanocrystals at a pressure of 1 to 2 atmospheres, and keep it for at least 12 hours until the ethanol is completely evaporated and the nanocrystals are fully assembled into continuous root fibers structure

Then, take off the stamp (Mold) of the star-shaped polydimethylsilane.

Finally, the nanocrystals are fully assembled into a continuous fiber structure by firing at 580° C. for 11 hours. The shaft diameter is about 1 micron and the length is 1 cm.

Example 8 Zeolite X nanocrystals were prepared from silica sol, sodium aluminate, sodium hydroxide and water. The reaction process is as follows: 104g silica sol (25%SiO ₂ ) (pH is 9), after cooling to 5°C, add 55g sodium hydroxide solution (50%), accurately weigh 27g of this silica sol, add 78g water, and stir to prepare into precursor solution I. Mix 61g of water, 30g of 50% sodium hydroxide solution and 20.36g of sodium aluminate (Al ₂ O ₃ 43%) at below 5°C and stir to prepare precursor solution II. After adding 75g of crushed ice to each flooding solution, the two flooding solutions were mixed rapidly under vigorous stirring, and left for five minutes to form a gel. 12g of sucrose was added to the gel, and aged for 16 hours with stirring at room temperature. Static hydrothermal reaction at 100°C for 1 day, filtered, washed with water and ethanol repeatedly until neutral or weakly alkaline, the white final product was obtained, and air-dried. It is verified as zeolite X nanocrystal by XRD, and SEM shows that the zeolite X crystal grain size is 150 nanometers. The ratio of silicon to aluminum is 6.

Secondly, mix polystyrene balls and zeolite nanocrystalline dry powder in proportion (polystyrene balls account for 25% of the total mass) and fully mix them evenly, and press them into a film with a pressure of 7 kg/cm ² for a duration of 5 minutes. 3mm.

Finally, by calcination at 550°C for 12 hours, a macroporous and microporous membrane composite material with uniform macropore diameter is obtained. The macropore diameter is around 300nm.

Example 9 Zeolite ZSM-5 nanocrystals were prepared from ethyl orthosilicate, sodium aluminate, sodium hydroxide, 98% tetrapropylammonium hydroxide and water. Reaction molar composition: 6TPAOH: 0.1Na ₂ O: 0.25Al ₂ O ₃ : 25SiO ₂ : 300H _{2 O:} 100EtOH The reaction process is as follows: first prepare the sodium aluminate sol containing TMA, mix 84g TPA, 432g water below 5°C , 16g of 50% sodium hydroxide solution and 6.1g of sodium aluminate (Al ₂ O ₃ 43%) were stirred to prepare a clear precursor solution I. Dissolve 520g of tetraethyl orthosilicate in 100g of water and 460g of ethanol, then mix it with 50g of TPA and vigorously stir at room temperature, and pre-hydrolyze for 12-14 hours to obtain the flooding solution II. Add the precursor solution II to the flooding solution I under vigorous stirring to obtain a homogeneous solution. After 24 hours of static hydrothermal reaction at 80°C, after repeated washing with water, a white final product was obtained, which was verified by XRD as zeolite in ZSM-5 nanometers. crystal. TEM showed that the grain size of zeolite ZSM-5 was below 120 nm.

Secondly, mix polystyrene balls and zeolite nanocrystalline dry powder in proportion (polystyrene balls account for 10% of the total mass) and fully mix them evenly, and press them to form a film at a pressure of 12 kg/cm ² for a duration of 2 minutes. 3mm.

Finally, by calcination at 550°C for 12 hours, a macroporous and microporous membrane composite material with uniform macropore diameter is obtained. The macropore diameter is around 300nm.

Claims (5)

1, a kind of preparation method of multi-class sequential macroreticular-micropore material, it is characterized in that nanocrystalline with micro porous molecular sieve is the construction unit of multilevel hierarchy, the nano unit ordered arrangement that contains microvoid structure with the guiding of macropore template, through high-temperature roasting, obtain the macropore-micro porous molecular sieve integral body of different multilevel ordered structures, concrete steps are as follows:

(1) be lower than under 100 ℃ of hydrothermal conditions the micro porous molecular sieve of preparation particle diameter less than 100nm: X, Y, A,

ZSM-5, Beta, TS-1, silicalite-1 zeolite are nanocrystalline, and nanocrystalline size is less than 150 nanometers;

(2) make with dehydrated alcohol that micro porous molecular sieve is nanocrystalline singly to scatter, the concentration of nanocrystalline ethanolic soln is 1～10%;

(3) with the brilliant unit of macropore template guiding mono-dispersed nano ordered arrangement, low temperature moulding;

(4) the macropore-poromerics of moulding in the step (3) at 500～600 ℃ of roasting temperatures, typing, the demoulding,

Obtain macropore-micropore multilevel hole material.

2, multilevel ordered hole according to claim 1 preparation methods, it is characterized in that the macropore template adopts polystyrene spheres, the diameter of ball is 50nm～400nm, and with close-packed infiltration method guiding moulding: earlier polystyrene spheres is carried out close-packed, then in the closely packed poly-stupid ethene sphere gap of the nanocrystalline infiltration of monodispersed micro porous molecular sieve, and adding tensio-active agent, be self-assembled into the multilevel ordered pore structure of macropore-micropore, here the consumption of polystyrene spheres is 25～45% of a total amount, and dosage of surfactant is 0.1～1% of poly-stupid ethene ball consumption.

3, multilevel ordered hole according to claim 1 preparation methods, it is characterized in that the macropore template adopts polystyrene spheres, the diameter of ball is 50nm～400nm, and with mechanical pressed disc method guiding moulding: with mechanical system polystyrene spheres with micro porous molecular sieve is nanocrystalline mixes, wherein the consumption of polystyrene spheres is 5～45% of a total amount, use compressing tablet legal system film then, the mechanical pressure of compressing tablet is the 4-12 kilogram.

4, multilevel ordered hole according to claim 1 preparation methods, it is characterized in that the macropore template adopts polydimethyl silane soft mode, this soft mode is carved with bar shaped, linear, grid, the decorative pattern of multiple shape such as star, decorative pattern is of a size of micron, sub-micrometer scale, and adopt soft printing technology guiding moulding: the single nanocrystalline ethanolic soln of micro porous molecular sieve that disperses that is obtained by step (2) is dripped on reaction platform or the silicon chip, polydimethyl silane soft mode that is carved with required decorative pattern from top to bottom is pressed onto on the nanocrystalline ethanolic soln, pressure is 1-2 normal atmosphere, at least kept 12 hours, until ethanol is volatilized fully, make the nanocrystalline multilevel ordered microporous network structure of successive that fully is self-assembled into.

5, multilevel ordered hole according to claim 1 preparation methods is characterized in that preparing micro porous molecular sieve when nanocrystalline, uses sucrose or glucose as flocculation agent, and add-on is 5～25% of a nanocrystalline weight.