WO2005123587A2

WO2005123587A2 - Recovery of nano zeolite crystallites

Info

Publication number: WO2005123587A2
Application number: PCT/EP2005/052816
Authority: WO
Inventors: Shuguang Zhang; Zongchao Zhang; Peter Bergoo
Original assignee: Akzo Nobel N.V.
Priority date: 2004-06-18
Filing date: 2005-06-17
Publication date: 2005-12-29
Also published as: WO2005123587A3; TW200613222A

Abstract

The invention is a process for the recovery of nano zeolite crystallites having a particle size of less than about 5 microns from an aqueous suspension. The process comprises the sequential steps of adding a harvesting agent to the suspension comprising a water soluble organic compound, subjecting the suspension to a means for applying centrifugal force to obtain supernatant and solid phases, removing the supernatant phase and recovering the solid phase containing the crystallites. The invention includes compositions containing the nano zeolite crystallites and uses of those compositions.

Description

RECOVERY OF NANO ZEOLITE CRYSTALLITES

The field to which this invention relates is the synthesis and recovery of nanosized zeolites.

The paper, Preparation and Characterization of Monodispersed YSZ Nanocrystals, Guangsheng Pang, Siguang Chen, Yingchun Zhu, Oleg Palchik, Yuri Koltypin, Afie Zaban, and Aharon Gedanken (Department of Chemistry, Bar-Man University, Ramat-Gan 52900, Israel), mentions the use of ethanol during a synthesis of nano Yttria-stablized zirconia particles. The ethanol is used with centrifuge to wash and disperse the nano particles after water washing. The ethanol is mainly used later as a reagent to modify the surface of the particle to change the textile structure after calcinations and to prevent the agglomerization during the synthesis. The ethanol is not used to facilitate the separation of nano particles from the liquid phase.

The article, Preparation and Characterization of Gold Nanoshells Coated with Self-Assembled Monolayers, Tan Pham, Joseph B. Jackson, Naomi J. Halas, and T. Randall Lee (Department of Chemistry, University of Houston, Houston, Texas 77204-5003, and Department of Electrical and Computer Engineering, Rice University, Houston, Texas 77005), describes the use of ethanol to disperse modified silica particles. Combined with centrifuge, the ethanol is also used to remove unreacted reagents from the surface of gold coated silica nano particles.

Like the first paper above, the paper Influence of ethanol washing of the hydrous precursor on the textural and structural properties of zirconia, P. D. L. Mercera et. al., The Netherlands, describes a method of using ethanol to wash a precipitate. Filtration is used for separation. The work Colloidal synthesis of nanocrystals and nanocrystal superlattices, C. B. Murray et. al., only mentions ethanol to be used once to isolate a precipitate. Neither centrifuge nor filtration is used.

None of the above four papers mentions zeolite.

The paper Preferentially Oriented Submicron Silicalite Membranes, Mark C. Lovallo and Michael Tsapatsis (Dept. of Chemical Engineering, University of Massachusetts, Amherst, MA 01003, AIChE Journal, November 1996, Vol. 42, No. 11, 3020-3029), presents a more detailed hydrothermal synthesis procedure to obtain 100 nm Silicalite zeolite crystals. The nano crystals were purified by washing with water and repeated ceπtrifuging. No chemical besides water was used during this purification process. The crystals were dispersed into water and deposited to form zeolitic membrane for use in separations.

The paper Structure of the Silica Phase Extracted from Silica/(TPA)OH Solutions Containing Nanoparticles, David D. Kragten, Joseph M. Fedeyko, Kaveri R. Sawant, Jeffrey D. Rimer, Dionisios G. Vlachos, and Raul F. Lobo (Center for Catalytic Science and Technology, Department of Chemical Engineering, University of Delaware, Newark, Delaware 19716) and Michael Tsapatsis (Department of Chemical Engineering, University of Massachusetts, Amherst, Massachusetts 01003), teaches the synthesis, extraction and characterization of nano silica particles (3-5 nm). The particles were synthesized following a procedure used to prepare Silicalite-1. The extraction involved acid neutralization, THF and NaCI acid phase separation and solvent evaporation by freeze-drying. However, the authors claim that the extracted nano particles did not have well defined MFI zeolite structure.

The paper Characterization of Nanosized Material Extracted from Clear Suspensions for MFI Zeolite Synthesis, Raman Ravishankar, Christine E. A.

Kirschhock, Peter-Paul Knops-Gerrits, Eddy J. P. Feijen, Piet J. Grobet, Peter Vanoppen, Frans C. De Schryver, Gerhard Miehe, Hartmut Fuess, Brian J. Schoeman, Pierre A. Jacobs, and Johan A. Martens, reports that the silica species contained in an aged clear suspension, which upon heating gives rise to the crystallization of Silicalite-1 , have MFI structure after an extraction process. The process is the same as the one described in the paper by Kragten et al. except that tert-butyl alcohol instead of THF was used.

No centrifuge was used in the processes described in the last two papers, and for both papers, it was said that all the sodium salt and template used for synthesis and extraction should remain with the solid particles. Neither process was in fact an actual purification method.

In one embodiment, the present invention is a process for the recovery of nano zeolite crystallites having a particle size of less than about 5 microns from an aqueous suspension. The process comprises the sequential steps of adding a harvesting agent to the suspension comprising a water soluble organic compound, subjecting the suspension to a means for applying centrifugal force to obtain supernatant and solid phases, removing the supernatant phase and recovering the solid phase containing the crystallites.

In another embodiment, the present invention is a composition comprising zeolitic material wherein one or more properties of the composition are altered with regard to the utility of the composition by the zeolitic material comprising nano zeolite crystallites having a particle size of less than about 1 micron.

Further embodiments of the invention relate to specific compositions that benefit from comprising nano zeolite crystallites having a particle size of less than about 1 micron, including catalysts, flame retardaπts, semi-conductors, coloring agents, paints and cosmetics, sensors, fungicides, chemical mechanical planarization agents, methods for removal of toxic chemicals from water and for in-vivo drug delivery. The above embodiments are described in greater detail below.

Fig. 1 is a TEM analysis associated with Example 5. Fig. 2 is a TEM analysis associated with Example 6.

The synthesis of nanoclusters with zeolite primary and secondary structure building units has been reported in the literature. The general synthesis procedure involves the heating of an aluminosilicate or silica gel composition in the presence of a template at a temperature of from about ambient temperature to about 140°C for a few hours. The template is usually a tetraalkylammonium hydroxide. The selection of alkyl in the template, for example a lower alkyl group such as, methyl, ethyl or propyl, dictates the structure of the zeolite. Once the nano-zeolite is obtained, it can be used as a seed to prepare a template-free nano-zeolite composition from the alumina-silica gel. Nano Y zeolite usually does not need a template and is more stable in a strongly basic environment. Isolation of the nanosized zeolites, however, has been a major challenge and previous isolation attempts have yielded amorphous silicate.

The silanation of zeolites is known to increase the hydrophobicity of the zeolites, thereby facilitating the separation of hydrophobized zeolites from water. However, such treatment unavoidably alters the properties of the zeolites.

The present invention relates to the synthesis, isolation and end use application of nano zeolite crystallites with Beta, ZSM-5, or Y structures. The isolation method of this invention does not cause any substantial change in the properties of the zeolite.

There are many compositions comprising zeolitic material wherein one or more properties of the composition are altered with regard to the utility of the composition by the zeolitic material comprising nano zeolite crystallites having a particle size of less than about 5 microns, or, more likely, less than 1 micron.

In many aspects of properties, the nanosized zeolites from this invention differ from conventional zeolites. Single nanosized crystals of various types of zeolites obtained from the invented process can exist in a stable colloidal form or in a dry powder form which can be redispersed uniformly into different solvents. Their small size also makes the dispersion of nano size zeolites into a polymeric material easy, leading to its application as an additive for special functions, such as flame retardancy and anti-abrasion. Conventional zeolites often consist of micrometer sized crystals due to their synthesis conditions. Sometimes they may contain nano sized crystals, but during processing these crystals usually agglomerate or inter-grow to form larger particles with diversified sizes in the range of several to a few hundred micrometers. When mixed with a liquid, these big particles can hardly form a stable colloidal solution and tend to settle down. The bigger particle size also results in mass and heat transfer obstacles. Compared to conventional zeolites, nanosized zeolites have much larger external surface areas which are easily accessible for molecules during adsorption or reaction. This is desired for catalysis and sensor applications.

The nanosized zeolites are also different from other nano particles, such as colloidal silica, metal or metal oxide nano particles. The colloidal silica is amorphous. Metal or metal oxide nano particles are usually non porous. The framework structures and surface properties of nano sized zeolites can be easily varied by changing synthesis conditions or by post synthesis modifications. These variations will lead to different properties, such as hydrophobicity, catalytic activity, hardness, reflection index, conductivity, adsorption property, etc. Because they are highly porous, nanosized zeolites can be used as inert carriers of active agents for suspension or delivery purposes. The means for applying centrifugal force to the aqueous suspension containing the nanosized zeolite crystallites include cyclonic type devices and centrifuges. Cyclonic type devices are typically structures having conical shaped interiors of vertical orientation with inlets at the upper portion of the interior wall and outlets at the top and at the bottom apex. A suspension will be pumped into the structure at high velocity and flow around the interior wall in a circular motion, thereby subjecting the suspension to centrifugal force to obtain a supernatant phase that exits the structure at the top outlet and a relatively solid phase that will exit the structure at the bottom apex.

A centrifuge is a structure having an interior cylindrical wall of vertical orientation that is made to spin. A suspension will be pumped into the structure and will flow around the spinning interior wall, thereby subjecting the suspension to centrifugal force to obtain a supernatant phase and a relatively solid phase.

Typically, the solid phase containing the crystallites is re-dispersed in water to form an aqueous suspension with the sequential steps repeated to obtain a purified solid phase containing the crystallites.

The primary requirement for the harvesting agent is that it be a water soluble organic compound. Although alcohols, particularly ethanol, are preferred, other water soluble compounds may be just as effective, so long as they do not react in an undesirable manner with the nano zeolite particles. The harvesting agent will most likely be used in aqueous solution, ethanol in water being preferred.

There are compositions comprising zeolitic material where one or more properties of the composition are altered with regard to the utility of the composition by the zeolitic material comprising nano zeolite crystallites having a particle size of less than about 5 microns, but more typically less than about 1 2005/123587

micron. Examples of end use applications of the nanosized zeolites of this invention (in these particular applications, the crystallite particle sizes are typically less than 1 micron) are as follows:

1. Flame retardant - they may function similarly to or better than nanoclay materials. The possibility of being able to modify the nanozeolite material with a large range of other molecules makes it quite attractive. For example, organophosphorous and organosilane materials could be anchored to the nanozeolites. The structural parameters of the nanozeolites, as discussed above, can be tailored. The hydrophobicity/hydrophilicity characteristics can be adjusted, while such flexibility is not readily available with many other nanosized materials, including nanoclays.

2. Nanoparticles of different hardness have been used for chemical mechanical planarization of semiconductors. Zeolite nanoparticles could be used for the same application. The surface hardness can be modified by the presence of soft molecules when desired. Chemicals, such as peroxides, and catalysts, such as metals or metal ions, can be encapsulated in the zeolite cages/channels. They can be slowly released during the planarization process to accelerate the process. The adjustment of the hardness of the zeolite nanoparticles can also be achieved by changing the zeolite structure and composition, such as silica to alumina ratio and accommodation of other elements in the framework besides silicon, aluminum and oxygen.

3. Flexible catalyst formulation. Nanozeolites can be prepared to contain various active catalyst components, e.g., metal clusters and anchored organometallic catalysts. Such materials could be used to make supported catalysts by simple dosing onto a supporting material on demand. Since the catalysts are already in activated form, no additional treatment would be necessary. They could also be directly applied as catalysts depending on the reaction system. They can be used in a membrane-type reactor with very high surface area.

They can be treated with certain conductive materials by ion-exchange or impregnation and used as semi-conductor carriers. While zeolites of large crystal size are an insulator, the nanosized zeolite may allow conductivity through the channel when doped or ion exchanged with conductive molecular materials.

5. They can be loaded with various coloring agents, including transition metal ions. The zeolite structure may provide a stable carrier for the coloring agents that is easier to disperse than coloring agents carried on conventional zeolites. They can be used as additives to plastics or as fillers to papers to make special color effects for use in cosmetics and paint.

6. They can be blended with or form a segregated layer with a polymer membrane to bring additional absorption/separation functions.

7. They can be used to host small metal clusters that change color upon adsorption of toxic molecules or biomolecules thereby allowing them to be used as biosensors and toxic material detectors.

8. They could be used for the removal of toxic metals in rivers and water. The water-dispersible nanozeolites can be much more effective than the conventional zeolites because the conventional ones will quickly settle to the bottom of the river or water sample being treated. 9. Nanozeolite particles or titania modified nanozeolites may inhibit fungi growth. Because they are water-dispersible, applications in waste water treatment and perhaps wood treatment are envisioned.

10. Because they are re-dispersible and do not aggregate, they may have application for in-vivo drug delivery depending on their drug absorptive abilities.

11. A new composition consisting of at least one organic solvent and a nano-zeolite has been made, such as nanozeolite in toluene. A nanozeolite in a solvent may show some kind of color, it depends on the zeolite and the solvent. This new composition has shown unique properties of transparency and light absorption/scattering. The intensity and wavelength of scattered light is dependent on the particle size of nanozeolite crystallites and the concentration of the nanozeolites. The color and intensity also change when viewed from differing angles. Such new materials can be used as a medium to deliver the nanozeolites into polymers or resins to produce a desired color property in coatings. The color can be further altered by the introduction of a variety of metal ions through ion exchange. This application may not be used directly as a coating because the solvent has to be removed for coating, although it could be used as a displaying media, like an LCD.

12. Through the disclosed invention, dry and purified nanozeolite particles of differing crystallite sizes, from 1 nm to 500 nm, can be produced with a controlled narrow particle size distribution.

13. Nanozeolites may have utility in phase transfer catalysis. They can be dispersed in solvents and products of different polarity and density. The distribution of nanozeolites in two or more adjacent phases, such as immiscible solvents, can also be adjusted so that they can effectively catalyze reactions across the phases because nanozeolite-reactant complex intermediates can form in one phase and transfer into another to release the products.

A colloidal sample (termed "Superseeds" hereinafter) containing nano Y zeolite crystals was obtained from Akzo Nobel Catalysts LLC. The particle size was in the range of 30-100 nm based on SEM images, and the pH of the Superseeds was higher than 13. The zeolite crystalline size is far smaller, in the range of 2- 20 nm.. Specific, non-limiting purification techniques using the method of the present invention and modification of the sample are described in Examples 1- 4, which appear below.

Some Silicalite-1 nano-zeolite particles were also synthesized with controlled particle size distributions in colloidal suspensions following procedures described in the literature. Silicalite-1 has a topology very similar to ZSM-5 so it was considered as the aluminum free end member of the MFI type zeolites. New synthetic procedures were also invented in this lab for non-sodium form nanocrystalline zeolites since sodium ion may be harmful for certain applications. These nano-particles can be harvested, dried and purified from their aqueous mother liquor using the present invention, as described in Examples 5-10, which follow. The washed nano zeolite particles can be easily redispersed into water to form stable colloidal solutions containing different zeolite compositions.

The dried nano-zeolite particles have a high surface area and a high absorption capacity for organic molecules. The dried nano-zeolites can also be redispersed into various solvents at differing zeolite to solvent ratios to form solutions that exhibit differing physical and chemical properties. The structures of the nano zeolite particles have been confirmed using IR and XRD analysis. The particle size distribution was using the capillary hydrodynamic flow method, SEM, and TEM.

Some nanozeolite particles contain amino-organic templates. The removal of such templates in conventional zeolites has been performed using high temperature calcination in an oxygen-containing gas stream. This calcination method can cause sintering and agglomeration of the nano-zeolite material. It is envisioned that a low temperature oxidation of the templates can be performed by using an oxidant, such as peroxides, superoxides, ozone, halogens, chlorine dioxides, radicals, plasmas, etc., which can be combined with an extraction medium.

The following examples illustrate the practice of the process of the invention for the recovery of nano zeolite crystallites having a particle size of less than about 5 microns from an aqueous suspension, both with regard to already prepared crystallites (Superseeds) dispersed in water and with regard to the mother liquor in which the crystallites were prepared.

Example 1

Superseeds (100 g), 80 g of distilled water, and 20 g of ethanol were added to a 250 ml polypropylene bottle. The bottle was then sealed and shaken to insure good mixing. Centrifugation at 2000 RPM was conducted for thirty minutes. Two layers were formed, a white precipitate at the bottom and a clear supernatant solution. The solution was then decanted, and 80 g of distilled water and 20 g of ethanol were added. The bottle was put into an ultrasound water bath for one hour to re-disperse the seeds and then was subjected to centrifugation for one hour at 2000 RPM. These operations were repeated three more times. After the solution was then decanted, 50 g of ethanol was added and further mixing was done using ultrasound. After another centrifugation step, the ethanol solution, which was the supernatant phase, was removed, and the seeds were dried at 50°C under vacuum for twelve hours. The final product (about 10 g) was a white fluffy powder having a surface area of about 500 m²/g. A water solution containing the seed product had a pH of about 7. IR analysis indicated that the seeds maintained a Y zeolite structure.

Example 2

The seed obtained in Example 1 can be modified by ion exchange using different salts. For example, Cu²⁺, Eu³⁺, and Fe³⁺-exchanged seeds have been obtained, respectively. The general procedure is as follow: the seeds produced in Example 1 , before vacuum drying, were mixed with 3 to 6 g of the desired metal salt, namely, Cu(NO₃)2, Eu(NO₃)₃ and Fe(NO₃)3, and 500 g of distilled water for five hours. Washing with ethanol followed by centrifugation was performed twice. The samples were then dried under vacuum. Each sample had a final weight of about 9 g with a surface area from about 475 m²/g to about 715 m²/g.

Example 3

The seeds obtained in Examples 1 and 2 have been used for oleic acid isomerization in a high throughput system. They showed comparable or higher activity than conventional Y zeolites.

Example 4

The seed product from Example 1 were used for ASA encapsulation. It had a capacity of 2.1 g ASA/g of seed. For a conventional HY zeolite, the capacity is 1.4 g ASA/g seed.

Example 5

In a TEFLON autoclave, 25.75 g of distilled water and 5.25 g of 40 % tetrapropylammonium hydroxide solution (TPAOH) were mixed well by magnetic stirring. Then, 10.0 g of tetraethoxysiiane was added into the mixture drop by drop with fast stirring. The whole mixture was stirred for another two hours. After sealing the autoclave, the autoclave was heated to 130°C while maintaining the magnetic stirring and kept at that temperature for seven hours. The autoclave was quenched with cold water and opened. A white colloidal composition had formed. It was washed with water/ethanol following the previous procedure and was redispersed into 50 ml of distilled water with ultrasonification. TEM analysis (Figure 1) showed an average particle size of about 300 nm. IR analysis indicated that the particles had a zeolite structure.

Example 6

In a glass beaker, 0.283 g of sodium hydroxide was dissolved in 20 ml of 20% TPAOH solution. Then, 5.0 g of fumed silica was added into the mixture with fast mechanical stirring. Then, the mixture was transferred into a glass bottle and a magnetic stirring bar was added. The whole mixture was heated in an oven to 80°C with stirring for one and one half hours and was transferred into a TEFLON autoclave. After sealing the autoclave, the autoclave was heated to 125°C while maintaining the magnetic stirring and was kept at that temperature for seven hours. The autoclave was quenched with cold water and was opened. A white colloidal composition had formed. It was washed with water/ethanol following the previous procedure and was redispersed into 50 ml of distilled water using ultrasonification. TEM analysis (Figure 2) showed an average particle size of about 100 nm. IR analysis indicated that the particles had a zeolite structure.

Example 7

This is a scale-up of the preparation made by the process described in Example 2. The obtained nano zeolite particles were dried overnight under vacuum at 55°C.

In a glass beaker, 3.54 g of sodium hydroxide was dissolved in 250 ml of 20% TPAOH solution. Then, 62.5 g of fumed silica was added into the mixture with fast mechanical stirring. The mixture was thereafter transferred into a glass bottle and a magnetic stirring bar was added. The whole mixture was heated in an oven to 80°C with stirring for one and one half hours and was transferred into a TEFLON autoclave. After sealed, the autoclave was heated to 125°C while maintaining the magnetic stirring and was kept at that temperature for eight hours. The autoclave was quenched with cold water and was opened. A white colloidal composition had formed. It was washed with water/ethanol following the previously decribed procedure. Instead of being redispered, the nano zeolite particles were dried at 55°C under vacuum overnight to obtain a white powder. XRD analysis indicated that it had a ZSM-5 zeolite structure with a relative crystallinity of 82.2% in reference to a commercial crystalline ZSM-5 sample.

Example 8 The nano zeolite powder obtained from Example 3 was dispersed into a variety of solvents using ultrasonification. Another mixture was prepared for comparison using the same technique by adding a commercial ZSM-5 zeolite to toluene. For all mixtures, the powder was 10 wt% of the total weight. Those mixtures containing the nano zeolite composition, except for the one in acetone, were colloidal, although the one containing ether as the solvent formed a clear upper layer after a few hours. The mixture of nano zeolite in toluene was transparent and had a light blue color. The color varied in intensity with different light sources and angles of incidence of the light. The conventional ZSM-5 formed a cloudy mixture in the toluene and separated into two layers after a few hours.

Example 9

In this Example, potassium hydroxide, instead of sodium hydroxide, was used as the base for the synthesis of nano zeolite particles. In a glass beaker, 0.2 g of KOH was dissolved in 10 ml of 20% TPAOH solution. Then, 2.5 g of fumed silica was added into the mixture with fast mechanical stirring. The mixture was then transferred into a glass bottle and a magnetic stirring bar was added. The whole mixture was heated in an oven to 80°C with stirring for one and one half hours and was transferred into a TEFLON autoclave. After being sealed, the autoclave was heated to 125°C while maintaining the magnetic stirring and was kept at that temperature for eight hours. The autoclave was quenched with cold water and was opened. A white colloidal composition had formed. Particle size analysis using the capillary hydrodynamic flow (CHDF) method showed an average particle size of 70 nm. IR analysis indicated that the particles had a zeolite double ring structure. Example 10

In this Example, ammonium hydroxide, instead of sodium hydroxide, was used as the base for the synthesis of nano zeolite particles.

In a glass flask, 2.5 g of NH₄OH (17%), 10 ml of 20% TPAOH solution, and 2.5 g of fumed silica were mixed with fast magnetic stirring for ten minutes. Then, the mixture was transferred into a TEFLON autoclave. After being sealed, the autoclave was heated to 125°C while maintaining the magnetic stirring and was kept at that temperature for eight hours. The autoclave was quenched with cold water and was opened. A white colloidal composition had formed. Particle size analysis using CHDF showed an average particle size of 70 nm. IR analysis indicated that the particles had a zeolite double ring structure.

Comparative Example The Superseeds product (25 g) was mixed with 40 g of distilled water and was then split into four polystyrene bottles for centrifugation at 12,000 RPM for twenty to thirty minutes. Two layers were formed, a white precipitate as the bottom layer and a clear supernatant. The supernatant solution was then decanted, and 40 g of distilled was added. The bottles were put into an ultrasound water bath for five hours to re-disperse the seeds, and they were then subjected to centrifugation for twenty to thirty minutes at 12,000 RPM. These operations were repeated two more times. The final sample had a weight of about 0.65g after vacuum drying at 75°C for five hours. The yield (final weight/original weight) was much lower than that in Example 1 , although this Example employed a higher speed centrifugation.

Claims

We claim:

1. A process for the recovery of nano zeolite crystallites having a particle size of less than about 5 microns from an aqueous suspension, said process comprising the sequential steps of adding a harvesting agent to said suspension comprising a water soluble organic compound, subjecting said suspension to a means for applying centrifugal force to obtain supernatant and solid phases, removing said supernatant phase and recovering said solid phase containing said crystallites.

2. The process of claim 1 wherein said crystallites have a particle size of less than about 1 micron.

3. The process of claim 1 wherein said harvesting agent comprises ethanol.

4. The process of claim 1 wherein said harvesting agent comprises an organic compound in aqueous solution.

5. The process of claim 1 wherein said harvesting agent comprises ethanol in aqueous solution.

6. The process of claim 1 wherein said means for applying centrifugal force comprises a centrifuge.

7. The process of claim 1 wherein said means for applying centrifugal force comprises a cyclonic device.

8. The process of claim 1 wherein said solid phase containing said crystallites is re-dispersed in water to form an aqueous suspension with said sequential steps repeated to obtain a purified solid phase containing said crystallites.

9. The process of claim 1 wherein said nano zeolite crystallites have structures selected from the group consisting of Beta, ZSM-5, and Y type zeolites.

10. A composition comprising zeolitic material wherein one or more properties of said composition are altered with regard to the utility of said composition by said zeolitic material comprising nano zeolite crystallites having a particle size of less than about 1 micron.

11. The composition of claim 10 wherein chemicals relating to the utility of said composition are encapsulated within the structure of said crystallites.

12. The composition of claim 10 wherein said composition comprises a catalyst with said crystallites containing active catalytic components.

13. A flame retardant comprising nano zeolite crystallites having particle sizes less than about 1 micron.

14. A semi-conductor comprising nano zeolite crystallites having particle sizes less than about 1 micron with said crystallites doped or ion exchanged with conductive molecular materials.

15. The composition of claim 10 wherein the zeolite structure of said crystallites is loaded with desired coloring agents.

16. A paint or cosmetic comprising the composition of claim 15.

17. The composition of claim 10 further comprising an organic solvent and a polymer or resin.

18. The composition of claim 17 wherein said solvent comprises toluene.

19. The composition of claim 17 wherein the color of said composition is altered by the ion exchange of the nano zeolite crystallite with metal ions, or by manipulating the particle size, structure or silica to alumina ratio of the nano zeolite crystallite.

20. A sensor comprising the composition of claim 10 wherein the nano zeolite crystallites are loaded with metal clusters or other materials which are anchored on the zeolite surface that change color upon adsorption of toxic molecules or biomolecules.

21. A fungicide comprising the composition of claim 10.

22. The fungicide of claim 21 wherein the nano zeolite crystallites are synthesized from a titanium, silver or copper precursor.

23. A method for the chemical mechanical planarization of a semiconductor wherein nano zeolite crystallites having particle sizes less than about 1 micron are applied to the surface of said semiconductor.

24. The method of claim 23 wherein chemicals selected from the group consisting of peroxides, metals or metal ions are encapsulated in the structure of the nano zeolite crystallites to enhance the planarization process.

25. A method to obtain color effects in a plastic comprising dispersing the composition of claim 15 in said plastic.

26. A method to obtain color effects in paper comprising adding the composition of claim 15 as a filler to said paper.

27. A method for the removal of toxic chemicals from water comprising contacting the water with nano zeolite crystallites having particle sizes less than about 1 micron that adsorb said toxic chemicals.

28. A method for in-vivo drug delivery comprising adsorbing the drug on nano zeolite crystallites having particle sizes less than about 1 micron.

29. The process of claim 1 wherein said nano zeolite crystallites contain amino-organic templates employed in their synthesis, said amino- organic templates being removed by adding an oxidant to said suspension.

30. The process of claim 29 wherein said oxidant is selected from the group consisting of superoxides, ozone, halogens, chlorine dioxides, radicals and plasmas.

31. The process of claim 1 wherein said nano zeolite crystallites contain amino-organic templates employed in their synthesis, said amino- organic templates being removed by solvent extraction.

32. The composition of claim 10 wherein nanozeolites are dispersed in two or more adjacent immiscible phases and catalyze reactions across the phases by nanozeolite-reactant complex intermediates forming in one phase and transfering into an adjacent phase to release the products.