CN112919491B - Preparation method and application of zeolite molecular sieve dominant silicon source material - Google Patents
Preparation method and application of zeolite molecular sieve dominant silicon source material Download PDFInfo
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- CN112919491B CN112919491B CN201911233629.XA CN201911233629A CN112919491B CN 112919491 B CN112919491 B CN 112919491B CN 201911233629 A CN201911233629 A CN 201911233629A CN 112919491 B CN112919491 B CN 112919491B
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
The invention relates to a preparation method and application of a dominant silicon source material of a zeolite molecular sieve, and particularly discloses a method for uniformly embedding necessary alkali metal elements into a silicon source, which comprises the following steps: 1) placing a compact silicon source and an alkali metal source in a grinding container, and adding more than 2 sets of ball grinding beads with different diameters, wherein the size of the ball grinding beads is selected from 0.2mm-20mm, and the particle size of the ball grinding bead with the largest diameter is 2-100 times of that of the ball grinding bead with the smallest diameter; 2) performing ball milling in a ball mill to obtain a primary mixture of silicon source particles and an alkali metal source; 3) preparing a mixed solution of an intercalation mineralizer and an intercalation agent, adding the mixed solution into the primary mixture obtained in the step 2), and carrying out intercalation expansion treatment to obtain a silicon-alkali metal binary uniform intercalation mixture. The silicon source of the invention can obviously improve the crystallization rate of the molecular sieve and even obtain the zeolite molecular sieve ultra-small nanocrystal product.
Description
Technical Field
The invention belongs to the technical field of zeolite molecular sieve synthesis, and particularly relates to an upgrading method of a common silicon source of a zeolite molecular sieve. By embedding the alkali metal elements, the preparation process efficiency can be greatly improved, and even the ultra-small nanocrystal product with high added value can be obtained.
Background
Zeolite molecular sieves have a very wide range of industrial applications, in all aspects relating to production and living. In many application fields, zeolite molecular sieve ultra-small nanocrystals with the particle size of less than 100nm often have performances obviously superior to those of common crystals, and even reflect performances which some common crystals do not have, so that the preparation of the ultra-small nanocrystals is a long-term research hotspot in the field of zeolite molecular sieve research. However, due to the great technical difficulty, only about 20 kinds of zeolite molecular sieve structures reported at present successfully obtain nanocrystals below 100nm [1], and zeolite materials with the size below 20nm are more flexo-exponential, so that the results are mostly published in international top-level journals [2-3 ]. Previous work has found that with the presence of a novel source of silicon (e.g. potassium silicate) with a uniform distribution of alkali metal within the particles, uniform contact of the alkali metal with the silicon promotes crystallization of a feldspar type inorganic mineral with a structure similar to that of zeolite molecular sieves. By using the mineral structure as a precursor, the ultra-small zeolite molecular sieve with the size of less than 20nm can be quickly formed, and the total time required is only 1/6 of the traditional preparation method. [4] In further research, researchers have compared with novel silicon sources, and introduced alkali metal ions into traditional silicon source (such as white carbon black) particles with a loose structure by using an impregnation method, so that the synthesis rate is greatly improved, and the same nanocrystals are obtained. [4]
In practical industrial applications, various silicon sources can be used for preparing the zeolite molecular sieve, and the selection of the types of the silicon sources has very significant influence on the performance of the final zeolite molecular sieve crystal and the process flow used for preparation. Since the physical states of various silicon sources are different, and there are gas, solid, and powder states, it is not easy to replace the silicon source used in a mature industrial process. A suitable prerequisite for the prior art described in reference 4 is that the upgraded silicon source must have a relatively loose microstructure, able to accommodate alkali metal ions. In the report of the work [4], a silicon source with a more compact microstructure is also researched, and as a result, alkali metal cannot enter, so that the improvement of the crystallization rate and the preparation of ultra-small nanocrystals cannot be realized. This obviously limits the practical application of such advantageous preparation concepts, since many common silicon sources do not have a loose microstructure and are difficult to incorporate with alkali metals.
In summary, if alkali metal elements are uniformly distributed in the silicon source particles used in the zeolite molecular sieve synthesis process, the crystallization routes of the system are completely different, so that the total synthesis time is greatly shortened, and even ultra-small nanocrystals with particle sizes below 20nm are obtained. If a silicon source with a loose structure is adopted for preparation, alkali metal can be introduced into the microstructure of the silicon source by a simple dipping methodAnd the original common silicon source is upgraded to obtain the advantage result of rapid crystallization of the ultra-small crystal. However, most of the silicon sources commonly used in the prior zeolite molecular sieves are dense structures (such as colloidal silica)
Etc.), it is difficult to introduce alkali metal ions using a general impregnation method, which makes it difficult to upgrade a silicon source and to popularize a superior preparation technique. While some common material mixing techniques (such as ball milling) are very popular, even at high rotation speed, it is difficult to achieve uniform mixing of the silicon material and the alkali metal component in common ball milling equipment. Therefore, after the common ball milling processing is used, the material still has obvious silicon-rich and alkali metal-rich areas, the embedding effect is not ideal, and the expected product optimization effect cannot be obtained.
[1]Valtchev,V.；Tosheva,L.,Porous Nanosized Particles:Preparation,Properties,and Applications.,Chem.Rev.,2013,113(8),6734–6760.
[2]Ng,E.-P.；Chateigner,D.；Bein,T.；Valtchev,V.；Mintova,S.,Capturing Ultrasmall EMT Zeolite from Template-Free Systems.,Science,2012,335(6064),70–73.
[3]Awala,H.；Gilson,J.-P.；Retoux,R.；Boullay,P.；Goupil,J.-M.；Valtchev,V.；Mintova,S.,Template-free nanosized faujasite-type zeolites.,Nature Mater.,2015,14,447–451.
[4]Li,R.,Linares,N.,Sutjianto,J.G.,Chawla,A.,Garcia-Martinez,J.,Rimer,J.D.,Ultrasmall Zeolite L Crystals Prepared from Highly-Interdispersed Alkali-Silicate Precursors.,Angew.Chem.Int.Ed.,2018,57(35),11283-11288.
[5]Li,R.；Chawla,A.；Linares,N.；Sutjianto,J.G.；Chapman,K.W.；Garcia-Martinez,J.；Rimer,J.D.,Diverse Physical States of Amorphous Precursors in Zeolite Synthesis.,Ind.Eng.Chem.Res.,2018,57,8460-8471.
Disclosure of Invention
The common ball milling technology can crush the raw materials, but the uniform embedding of the raw materials and the raw materials is difficult to realize, so a set of complete and effective process flow needs to be designed and optimized on the basis of ball milling in order to achieve the aim of the invention. Through exploration, the multistage macro-crushing of raw materials can be realized by using a plurality of sets of grinding beads with different sizes. And the compactness of the crushed silicon material is reduced, and an intercalation agent can be further used for constructing a micro-pore structure in a water phase so as to allow alkali metal elements to enter. Therefore, alkali metal elements can be uniformly introduced into any kind of compact silicon source to construct a binary uniform mixture.
The invention introduces alkali metal into the compact silicon source, solves the defect that the previously reported silicon source upgrading mode is only suitable for loose silicon sources, and can efficiently and quickly obtain the ultra-small nanocrystals in wider practical application environments. Meanwhile, the defect that the uniformly distributed silicon-alkali metal binary uniformly-embedded mixture cannot be obtained by simply grinding or ball-milling the mixture of the alkali metal source and the compact silicon source is overcome. The zeolite molecular sieve is prepared by using the compact silicon source upgraded by the process innovatively designed by the invention, so that the improvement of the crystallization rate of the product and the preparation of the ultra-small zeolite molecular sieve crystal with high added value and high performance can be realized, the production cost can be obviously reduced, and the competitiveness can be improved.
One aspect of the present invention provides a method for preparing a silicon-alkali metal binary homogeneous intercalation mixture, comprising the steps of:
1) placing a compact silicon source and an alkali metal source in a grinding container, and adding more than 2 sets of ball grinding beads with different diameters, wherein the size of the ball grinding beads is selected from 2mm-20mm, and the particle size of the ball grinding bead with the largest diameter is more than 10 times of that of the ball grinding bead with the smallest diameter;
2) performing ball milling in a ball mill to obtain a primary mixture of silicon source particles and an alkali metal source;
3) preparing a mixed solution of an intercalation mineralizer and an intercalation agent, adding the mixed solution into the primary mixture obtained in the step 2), and carrying out intercalation expansion treatment to obtain a silicon-alkali metal binary uniform intercalation mixture.
In another aspect, the present invention provides a method for rapidly preparing zeolite molecular sieve ultra-small nanocrystals, comprising the steps of:
1) placing a compact silicon source and an alkali metal source in a grinding container, and adding more than 2 sets of ball grinding beads with different diameters, wherein the size of the ball grinding beads is selected from 0.2mm-20mm, and the particle size of the ball grinding bead with the largest diameter is 2-100 times, preferably 10-100 times, of the particle size of the ball grinding bead with the smallest diameter;
2) performing ball milling in a ball mill to obtain a primary mixture of silicon source particles and an alkali metal source;
3) preparing a mixed solution of an intercalation mineralizer and an intercalation agent, adding the mixed solution into the primary mixture obtained in the step 2), and performing intercalation expansion treatment to obtain a silicon-alkali metal binary uniform intercalation mixture;
4) and (4) uniformly embedding the silicon-alkali metal binary mixture prepared in the step (3) into the mixture to serve as an improved silicon source for synthesizing the zeolite molecular sieve, and crystallizing the silicon source and other components required for synthesizing the zeolite molecular sieve to obtain the zeolite molecular sieve ultra-small nanocrystal product.
In the technical scheme of the invention, the intercalation mineralizer in the step 3): intercalation agent: the mass ratio of the primary mixture obtained in the step 2) is 0.05-1: 0.1-5: 1.
In the technical scheme of the invention, the temperature of the interlayer expansion treatment in the step 3) is 80-400 ℃.
In the technical scheme of the invention, the time for the treatment of interlayer expansion in the step 3) is more than 1 hour.
In the technical scheme of the invention, the solvent adopted in the intercalation expansion link in the step 3) is at least one of water, ethanol, acetone, DMF and IMP.
In the technical scheme of the invention, the compact silicon source is selected from dried silicon source
Or at least one of other series of colloidal silica, tetramethoxysilane, tetraethoxysilane, silica gel, silica powder, silicate.
In the technical scheme of the present invention, the alkali metal source is an alkali metal salt or an alkali metal hydroxide, and preferably is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, cesium carbonate, lithium carbonate, sodium carbonate, potassium carbonate, and rubidium carbonate.
In the technical scheme of the invention, the intercalation mineralizer is hydroxide, preferably at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
In the technical scheme of the invention, the intercalator is cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, cetyl triethyl ammonium chloride, cetyl triethyl ammonium bromide, cetyl tripropyl ammonium chloride, cetyl tripropyl ammonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium chloride, tetrabutyl ammonium chloride, tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrapropyl ammonium bromide, tetrabutyl ammonium bromide, polydiallyl dimethyl ammonium chloride, 3-trimethylsilylpropyl hexadecyl dimethyl ammonium chloride, polyacrylic acid, pseudocumene, Triton X-100, Pluronic P123, Pluronic F127, C22-6-6 (C22-6) 22 H 45 -N(CH 3 ) 2 -C 6 H 12 -N(CH 3 ) 2 -C 6 H 13 Br 2 )、C 22 H 45 -N(CH 3 ) 2 -(CH 2 ) 4 -N(CH 3 ) 2 -C 4 H 9 Br 2 、C 18 H 37 Me 2 N(CH 2 ) 6 NPr 3 Br 2 At least one or a combination of more of the same.
In the technical scheme of the invention, the molar ratio of the alkali metal source to the compact silicon source in the step 1) is 0.1-50.
In the technical scheme of the invention, the grinding link in the step 2) can adopt dry grinding or wet grinding, wherein the dry grinding refers to processing the material in an air atmosphere, the wet grinding refers to processing the material in a solvent environment, and the solvent amount is 50-90% of the volume of the ball milling tank.
In the technical scheme of the invention, the volume ratio of the ball milling beads to the material to be ball milled in the step 1) is 5: 1-20: 1.
In the technical scheme of the invention, the number of the ball milling beads is 2, 3 or 4.
According to the technical scheme, the diameter size ratio of the ball milling beads is 1: 2-100, 1: 2-30: 50-100 or 1: 2-20: 30-60: 70-100.
In the technical scheme of the invention, the crystallization method in the step 4) is thermal synthesis, hydrothermal synthesis and anhydrous synthesis.
In the technical scheme of the invention, the other components required for synthesis in the step 4) are one or more of aluminum source, mineralizer, structure directing agent and solvent.
In the technical scheme of the invention, the aluminum source is at least one of aluminum sulfate, aluminum nitrate, aluminum isopropoxide, aluminum hydroxide, sodium aluminate, potassium aluminate, alumina, aluminum foil, sodium aluminosilicate and potassium aluminosilicate.
In the technical scheme of the invention, the mineralizer for preparing the zeolite molecular sieve is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonium fluoride and hydrofluoric acid.
In the technical scheme of the invention, the structure directing agent is nothing (not added), tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrapropyl ammonium bromide, tetrabutyl ammonium bromide, diaminoethane, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, diaminodecane, diaminoundecane, diaminododecane, hexadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, diethylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-diethylethylenediamine, N '-diethylethylenediamine, N-di (N/i) propyl ethylenediamine, N' -di (i) propyl ethylenediamine, N '-di (N/i) propyl ethylenediamine, N' -di (i) propyl ethylenediamine, N-di (i) ethyl ethylenediamine, N-tri (i) propyl ethylenediamine, N-pentamine, N-di (i) ethyl ethylenediamine, N-ethyl, N-ethyl, N-N-, At least one of diethanolamine, triethanolamine, 1-amantadine, and N, N, N-trimethyl-1-adamantyl ammonium hydroxide.
In a further aspect of the invention, a silicon-alkali metal binary homogeneous intercalation mixture is provided, which is obtainable by the process of the invention.
In still another aspect, the invention provides zeolite molecular sieve ultra-small nanocrystals rapidly prepared by the method of the invention.
In the technical scheme of the invention, the particle size range of the zeolite molecular sieve ultra-small nanocrystal is 5 nm-100 nm.
The invention provides in one aspect the use of the silicon-alkali metal binary homogeneous intercalation mixture prepared by the method of the invention for increasing the rate of crystallization and even for preparing zeolite molecular sieve ultra-small nanocrystals.
Advantageous effects
The alkali metal-silicon binary uniform embedding mixture obtained by the method has simple preparation method and high efficiency. And simultaneously, the alkali metal in the prepared embedding mixture is uniformly distributed in the silicon. Furthermore, the alkali metal-silicon binary uniform embedding mixture can quickly obtain zeolite molecular sieve ultra-small nano crystals, and the crystallization time can be shortened from dozens of hours to several days to less than 5 hours.
Drawings
FIG. 1 is a composition profile analysis of a milled intercalated binary homogeneous potassium-silicon intercalation mixture obtained in example 1 of the present invention. As can be seen from fig. 1, the potassium metal is uniformly distributed within the silicon source.
FIG. 2 is a scanning electron micrograph of the FAU type zeolite molecular sieve ultra-small nanocrystals prepared using the potassium-silicon binary homogeneous intercalation mixture of example 2 of the present invention.
FIG. 3 is a composition profile analysis chart of a material after being ground by a single set of grinding beads obtained in comparative example 1 of the present invention. As can be seen from fig. 1, the sodium metal is not uniformly distributed within the silicon source.
FIG. 4 is an XRD pattern of a raw material after a ball milling treatment of a conventional single set of milling beads of comparative example 1 of the present invention and a product obtained using the same under the same zeolite molecular sieve preparation conditions.
FIG. 5 is a composition profile analysis chart of example 1 and comparative example 2 of the present invention, in which the left side shows a single set of beads and the right side shows a multi-set of beads.
Detailed Description
Example 1
(1) The usual dense silicon source dry colloidal silica and alkali metal source potassium bromide required for zeolite molecular sieve synthesis are placed in a milling vessel. Mixing a plurality of sets of ball grinding beads with different diameters, wherein the diameter size proportion of the plurality of sets of grinding beads is two sets 1: 10 (big beads 20mm, small beads 2mm) are added into the materials according to a certain ball-to-material ratio.
(2) Carrying out dry grinding on the mixture in the step (1) in a high-energy ball mill to realize macroscopic multistage crushing of silicon source particles and preliminarily mixing with an alkali metal source;
(3) preparing a mixed solution of an intercalation mineralizer and an intercalation agent, adding the macroscopic mixture ground in the step (2), wherein the mixture ratio of the three substances is intercalation mineralizer potassium hydroxide: intercalation agent hexadecyltriethyl ammonium bromide: the mixture obtained in step 2) was 0.5:1:1 (mass ratio). Stirring and mixing uniformly at room temperature, and then carrying out intercalation expansion treatment at the temperature of 100-200 ℃ for more than 1 hour. The intercalation agent can construct a micro-pore channel structure in the silicon particles after primary crushing and mineralization, so that alkali metal can enter the pore channels, and uniform mixing of different elements on a micro scale is realized.
(4) The silicon-alkali metal binary uniformly-embedded mixture prepared in the step (3) is used as an improved silicon source for synthesizing the zeolite molecular sieve, and other components required for synthesis, such as aluminum sulfate, a molecular sieve mineralizer sodium hydroxide, a structure directing agent (no), and solvent water according to the ratio of NaOH to Al 2 O 3 :SiO 2 :H 2 Mixed aging was performed at a molar ratio of O10: 1.88:7.5:173, and crystallization was performed only for 3 hours at a hydrothermal temperature of 65 degrees to obtain a crystalline material. This crystalline material is washed using centrifugation to remove excess mineralizer and unreacted materials (if any). And drying the sample to obtain the zeolite molecular sieve ultra-small nanocrystal product.
Example 2
The same procedure as in example 1, except that three sets of beads 1: 7: 100 (20 mm for large beads, 1.4mm for medium beads, 0.2mm for small beads).
The results after the two types of grinding are not very different, so that it is known that it is difficult to obtain more uniform and fine grinding results by continuously increasing the number of grinding bead sets, and only the energy consumption and the equipment loss are increased. The difference of the sizes of the grinding beads in the two experiments is large, but the difference of the results is not obvious, which indicates that the sizes of the grinding beads can be selected in a large range.
Example 3
The same procedure as in example 1 is followed, except that sodium hydroxide is chosen for the intercalated mineralizer.
Example 4
The process is the same as in example 1 except that the intercalating agent is cetyltripropylammonium chloride.
Example 5
The same procedure as in example 1, except that the sodium hydroxide: cetyl trimethylammonium bromide: step 2) the resulting mixture was 1:5: 1.
Comparative example 1 Single set of beads common ball milling treatment
The dense silicon material dry colloidal silica is selected as a raw material for synthesizing silicon by using the zeolite molecular sieve. The test method is the same as that of example 1, except that 10mm or 2mm milling beads are selected in step 1, sodium bromide is used to replace potassium bromide, ordinary ball milling treatment is carried out, and XRD verifies that even embedding of the alkali metal source cannot be realized if ordinary ball milling treatment is carried out by using only a single set of milling beads. The results of the tests are shown in figures 3 and 4, indicating that the alkali metal is not homogeneously intercalated, with only a slight formation of the primary silicoaluminous oxide structure (middle line in figure 4). If the material is used as a silicon source for synthesis, the ratio of 10 NaOH: 1.88Al 2 O 3 ：7.5SiO 2 ：173H 2 The molar ratio of O is that after hydrothermal for 3 hours at 65 ℃, no zeolite crystal is obtained (top line of figure 4), and only amorphous bulges of the silicon material move from 2 theta 20 degrees to about 30 degrees, which marks the formation of a silicon-aluminum oxide structure, but no crystal can be generated yet.
Comparative example 2 ordinary ball-milling intercalation treatment of single set of milling beads
Comparing the analysis chart of the composition plane of the products of step 3) of example 1 and comparative example 1 respectively (see fig. 5), the material structure after single set of milling beads treatment is still compact, and the intercalation agent cannot enter, so that the final alkali metal element exists only outside the silicon particles and cannot be uniformly embedded. However, the matching and grinding of a plurality of sets of grinding beads makes it possible for the intercalation agent to enter the material and generate a micro-pore structure in the amorphous material, and the degree of the uniform distribution of the alkali metal elements is obviously improved.
Examples of effects
The ground intercalated potassium-silicon binary homogeneous intercalation mixture obtained in example 1 was subjected to composition surface analysis, and as a result, referring to fig. 1, it was found that the alkali metal was uniformly intercalated in the binary intercalation mixture obtained by the method of the present invention. The scanning results of the ultra-small FAU-type zeolite nanocrystals obtained in example 1 are shown in fig. 2, which results in a significant increase in the production rate and product quality of the zeolite product. The process can also be applied to the preparation of other zeolite materials (such as LTA, SOD and the like), and the flow of the raw material treatment process (steps 1-3) reported in the patent does not need to be adjusted when the process is applied, and only different alkali metal sources, intercalation agents and intercalation mineralizers are used according to the preparation formula requirements of different zeolites. Step 4 needs to be adjusted according to preparation formulas of different zeolite molecular sieves.
Claims (20)
1. A method for preparing a silicon-alkali metal binary homogeneous intercalation mixture, comprising the steps of:
1) placing a compact silicon source and an alkali metal source in a grinding container, and adding more than 2 sets of ball grinding beads with different diameters, wherein the size of the ball grinding beads is selected from 2mm-20mm, and the particle size of the ball grinding bead with the largest diameter is 10 times of that of the ball grinding bead with the smallest diameter;
2) performing ball milling in a ball mill to obtain a primary mixture of silicon source particles and an alkali metal source;
3) preparing a mixed solution of an intercalation mineralizer and an intercalation agent, adding the mixed solution into the primary mixture obtained in the step 2), and carrying out intercalation expansion treatment to obtain a silicon-alkali metal binary uniform intercalation mixture.
2. The method of claim 1, wherein the dense silicon source is selected from the group consisting of silicon oxide and silicon nitride after drying
Or at least one of other series of colloidal silica, tetramethoxysilane, tetraethoxysilane, silica gel, silica powder, silicate.
3. The process of claim 2 wherein the intercalating agent is cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltriethylammonium chloride, cetyltriethylammonium bromide, cetyltripropylammonium chloride, cetyltripropylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, polydiallyldimethylammonium chloride, 3-trimethylsilylpropylhexadecyldimethylammonium chloride, polyacrylic acid, pseudocumene, Triton X-100, Pluronic P123, Pluronic F127, C22-6-6 (C22-6) 22 H 45 -N(CH 3 ) 2 -C 6 H 12 -N(CH 3 ) 2 -C 6 H 13 Br 2 )、C 22 H 45 -N(CH 3 ) 2 -(CH 2 ) 4 -N(CH 3 ) 2 -C 4 H 9 Br 2 、C 18 H 37 Me 2 N(CH 2 ) 6 NPr 3 Br 2 A combination of at least one or more of;
the intercalation mineralizer is hydroxide.
4. The production method according to claim 2, wherein the alkali metal source is an alkali metal salt or an alkali metal hydroxide.
5. The method of claim 2, wherein the ball milling beads are 2, 3 or 4 sets.
6. The preparation method of claim 5, wherein the ratio of the diameters of the ball milling beads ranges from 1:2 to 100, from 1:2 to 30:50 to 100, or from 1:2 to 20:30 to 60:70 to 100.
7. The production method according to claim 2, wherein the alkali metal source is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, cesium carbonate, lithium carbonate, sodium carbonate, potassium carbonate, and rubidium carbonate.
8. The production method according to claim 2, wherein the intercalation mineralizer in step 3): intercalation agent: the mass ratio of the primary mixture obtained in the step 2) is 0.05-1: 0.1-5: 1.
9. the method of claim 2, wherein the intercalation mineralizer is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide.
10. A method for preparing zeolite molecular sieve ultra-small nanocrystals using an upgraded silicon source, comprising the steps of:
1) placing a compact silicon source and an alkali metal source in a grinding container, and adding more than 2 sets of ball grinding beads with different diameters, wherein the size of the ball grinding beads is selected from 0.2mm-20mm, and the particle size of the ball grinding bead with the largest diameter is 2-100 times of that of the ball grinding bead with the smallest diameter;
2) performing ball milling in a ball mill to obtain a preliminary mixture of silicon source particles and an alkali metal source;
3) preparing a mixed solution of an intercalation mineralizer and an intercalation agent, adding the mixed solution into the primary mixture obtained in the step 2), and performing intercalation expansion treatment to obtain a silicon-alkali metal binary uniform intercalation mixture;
4) the silicon-alkali metal binary uniformly-embedded mixture prepared in the step (3) is used as an improved silicon source for synthesizing the zeolite molecular sieve, and is crystallized with other components required by synthesis to obtain a zeolite molecular sieve ultra-small nanocrystal product;
the other components required for synthesis in the step 4) are one or more of aluminum source, mineralizer, structure directing agent and solvent; the particle size range of the zeolite molecular sieve ultra-small nanocrystal is 5 nm-100 nm.
11. The process of claim 10 wherein the dense silicon source is selected from the group consisting of those after drying
Or at least one of other series of colloidal silica, tetramethoxysilane, tetraethoxysilane, silica gel, silica powder, silicate.
12. The method of claim 11, wherein the ball milling beads are 2, 3 or 4 sets.
13. The method of claim 12, wherein the ratio of the diameter size of the ball milling beads ranges from 1:2 to 100, from 1:2 to 30:50 to 100, or from 1:2 to 20:30 to 60:70 to 100.
14. The process of claim 11, wherein the alkali metal source is an alkali metal salt or an alkali metal hydroxide.
15. The method of claim 14, wherein the alkali metal source is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, cesium carbonate, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate.
16. The production method according to claim 11, wherein the intercalated mineralizer in step 3): intercalation agent: the mass ratio of the primary mixture obtained in the step 2) is 0.05-1: 0.1-5: 1.
17. The preparation method according to claim 11, wherein the aluminum source is at least one of aluminum sulfate, aluminum nitrate, aluminum isopropoxide, aluminum hydroxide, sodium aluminate, potassium aluminate, alumina, aluminum foil, sodium aluminosilicate and potassium aluminosilicate;
the preparation mineralizer of the zeolite molecular sieve is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonium fluoride and hydrofluoric acid;
the structure directing agent is tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrapropyl ammonium bromide, tetrabutyl ammonium bromide, diaminoethane, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, diaminodecane, diaminoundecane, diaminododecane, hexadecyltrimethyl ammonium chloride, hexadecyltrimethyl ammonium bromide, diethylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-diethylethylenediamine, N '-diethylethylenediamine, N-di-N-propyl ethylenediamine, N' -diisopropylethylenediamine, diethanolamine, triethanolamine, 1-adamantanamine, N, at least one of N-trimethyl-1-adamantyl ammonium hydroxide.
18. A silicon-alkali metal binary homogeneous intercalation mixture obtained by the process of any one of claims 2 to 9.
19. The zeolite molecular sieve ultra-small nanocrystals obtained by the preparation method of any one of claims 11 to 17, having a particle size ranging from 5nm to 100 nm.
20. Use of the silicon-alkali metal binary homogeneous intercalation mixture of claim 19 in the preparation of zeolitic molecular sieve ultra-small nanocrystals.
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