International Science conference 4th - 5th June 2009, Stara Zagora, BULGARIA "Economics and Society development on the

Base of Knowledge" SYNTHETIC ZEOLITES AND THEIR INDUSTRIAL AND ENVIRONMENTAL APPLICATIONS REVIEW Bogdan Bogdanov, Dimitar Georgiev, Krasimira Angelova, Yancho Hristov Prof. Dr. Assen Zlatarov University, 8010 Burgas, Bulgaria, e-mail: bogdanov_b@abv.bg; ABSTRACT
Nowadays, the increasing interest in zeolite synthesis from low-cost materials has promoted the development of various studies on their conversion into zeolitic materials, giving rise to an extensive literature. The enhancing demands for a healthy environment, particularly with regards to high quality drinking water and removal of pollutants from industrial, agricultural and municipal wastewater, are a major reason to search for new materials. Nearly every application of zeolites has driven by environmental concerns, or plays a significant role in reducing toxic waste and energy consumption. Because of their unique porous properties, zeolites are used in a variety of applications with a global market of several million tones per year. Major uses are in petrochemical cracking, ion-exchange (water softening and purification), and in the separation and removal of gases and solvents. Other applications are in construction, agriculture, animal husbandry, medicine etc. In this study a brief overview of the zeolites fields of industrial and environmental applications covering the fundamentals and recent developments is proposed.
Key words: synthetic zeolites, structure, properties, industrial and environmental applications

INTRODUCTION The term zeolite was firstly mentioned by Swedish mineralogist A. F. Cronstedt in 1756 as a name of an aluminosilicate mineral (stilbite) that seemed to steam when is heated. The word zeolite is derived from the Greek words zeo (boil) and lithos (stone). Since then, about 50 naturally occurring and topologically different zeolites have been identified as a separate group of minerals. Natural zeolites cannot meet the huge demands in industry; therefore it becomes an urgent necessity to use synthesized zeolites besides the natural ones. From the early 1940's onwards systematic synthesis studies on zeolites were started [1]. Nowadays, a large number of synthetic zeolite structures and compositions are available, most of them having no natural analogues. In comparison with natural zeolites, synthesized zeolites have many advantages such as high purity, uniform pore size, and better ion-exchange abilities. The new structures and compositions and hence, the new physicochemical properties enlarge the range of applications of zeolites. Zeolites have been well studied in terms of the relations among structure, properties and synthesis. Nowadays 180 synthetic zeolites are known. Some of the earlier synthetic zeolites include zeolites A, X, Y, L, ZSM-5 and omega [3]. ZEOLITE INDUSTRY Since the first definitive synthesis of an analogue of a natural zeolite reported in 1948 by Barrer many efforts were focused on their applications in the field of adsorption, ion exchange and catalysis. The number of scientific publications, including several thousands PhD theses, books and monographs, showed an exponential growth in zeolite investigations and the broad present researchers interest in zeolite science and technology. At the beginning researchers tried to synthesize zeolites using hydrothermal synthesis techniques at temperatures of around 25~150 C (usually 100 C). In the 1940s, low-silica zeolites were synthesized. By the end of 1954, zeolites A and X began to be produced industrially. Volume IV Natural & Mathematical science. 1

International Science conference 4th - 5th June 2009, Stara Zagora, BULGARIA "Economics and Society development on the Base of Knowledge" Following this, a number of companies in the United States, such as Linde, Mobil, and Exxon, imitated the formation of natural zeolites and produced a series of synthesized zeolites with an intermediate Si/Al ratio (Si/Al= 2~5), including NaY, mordenite, zeolite L, erionite, chabazite, clinoptilolite, and so on, which were widely applied in the fields of gas purification and separation, catalytic processes of petroleum refining and petrochemistry, and ion exchange. The golden age for the development of zeolites is from 1954 to the early 1980s when zeolites with low, medium, and high Si/Al ratios were extensively explored [4]. A variety of zeolites with a Si/Al ratio of 2~5, i.e., intermediate silica zeolites which include mordenite, zeolite L, erionite, chabazite, clinoptilolite, zeolite omega, etc, have been synthesized. The progress of zeolite synthesis is considered in the early 1960s, when scientists at Mobil Corporation started to use organic amines and quaternary alkylammonium cations as templates in the hydrothermal synthesis of high-silica zeolites. In 1970, Flanigen first synthesized pure-silica forms of ZSM-5 (silicalite-I) and ZSM-11 (silicalite-II). In the past 25 years, the emergence of zeolites with low (Si/Al=1.0~1.5), medium (Si/Al=2.0~5.0), and high Si/Al ratios (Si/Al=10~100), as well as pure-silica zeolites, facilitated the study of both the structure and property of molecular sieves and porous compounds, and promoted their applications. Table 1 summarizess the major discoveries and advances in synthetic zeolites. Table 1. Evolution of Synthetic Zeolites [5, 6] Low Si/Al Ratio zeolites Late 40s to Early 50s High Si/Al ratio zeolites Mid to Late 60s SiO2 Molecular sieves Early 70s Late 70s AlPO4 Molecular sieves Early 80s SAPO and MeAPO Molecular sieves Late 70s Metallo-silicates, aluminosilicates Mid 80s AlPO4 based Molecular sieves Late 80s Large pore zeolites Early 90s Mesoporous molecular sieves ZEOLITES APPLICATIONS There are three traditional fields of application for zeolites: separation, purification, drying and environment treatment process; petroleum refining, petrochemical, coal and fine chemical industries; ionexchange, detergent industry, radioactive waste storage, and treatment of liquid waste. Zeolites has been widely used in many applications due to their unique properties (thermal stability, acidity, hydrophobicity/hydrophilicity of surfaces, ion-exchange capacity, low density and large void volume, uniform molecular sized channels, adsorption for gas and vapor and catalytic properties). Zeolites are very important: being used widely in catalysis, adsorption and ion exchange; becoming increasingly important in several environmental applications - in water purification, particularly for the removal of ammonia, heavy metals, radioactive species and organic substances. Catalysis. In the 1950s it was the first application of NaA zeolite in the separation of normal and isoalkanes by the Linde Company. In the 1960s X- and Y- zeolites were introduced as catalysts for cracking reactions of hydrocarbon conversion. Since then NaA, NaX, and NaY have been widely used in the petroleum industry in reactions such as cracking, alkylation, isomerization, shapeselective reforming, hydrogenation and dehydrogenation, methanol-to-gasoline conversion (MTG), etc. These porous materials have also been extensively used in the detergent industry and in a variety of adsorption and separation processes such as the drying, the removal of CO2 from natural gas, and the separation of xylene isomers, of alkenes, and of O2/N2 from air [1-3]. Despite this, there are still many prospects for development of molecular sieves in the above three main traditional fields. Volume IV 2 Natural & Mathematical science.

International Science conference 4th - 5th June 2009, Stara Zagora, BULGARIA "Economics and Society development on the Base of Knowledge" Examples of synthesized zeolite are zeolite A (Na, Ca, K), zeolite X (Na, K, Ba), zeolite Y (Na, Ca, NH4), zeolite L (K, NH4), zeolite omega (Na, H), zeolon (MOR-H, Na), ZSM-5, zeolite F (K) and zeolite W (K). These materials have been widely used as commercial adsorbents for drying and purification of gases and for bulk separation of, for example, normal-/iso-paraffins, isomers of xylenes and olefins, and O2 from air, as catalysts for petroleum refining and petrochemistry, and as ion exchangers. Because of their excellent ion-exchange capacities, zeolites A and X can be used as auxiliary agents in the detergent industry, in radioactive waste treatment and storage, and in the treatment of industrial liquid wastes. Although there are approximately 180 frameworks, currently only a few frameworks, including LTA, FAU, MOR, LTL, MFI, BEA, MTW, CHA, FER, AEL, and TON, have been widely used in industry [7]. Fluid catalytic cracking catalysts account for more than 95% of zeolite catalyst consumption and consist of various forms of zeolite Y. Detergents represent the largest volume. LTA-type zeolites substitute phosphate compounds in the water softening process in laundry. The largest market value for zeolites is in refinery catalysis. The second most used catalyst is MFI-type zeolite. The main applications are summarized in Table 2. Table 2. Main commercial catalytic applications [8] Process catalyst products Catalytic cracking Re-Y, US-Y ZSM-5 Gasoline, fuels Hydrocracking Y, Mordenite + Mo, W, Ni Kerosene, diesel, Benzene Alkylation of aromatics ZSM-5, Mordenite p-xylene, ethyl-benzene Hydroisomerization Mordenite + Pt, Pd i-pentane, i-hexane Xylene isomerization ZSM-5 p-xylene Catalytic dewaxing Mordenite, ZSM-5 + Ni, Improvement of cold flow noble metals properties Transalkylation Mordenite Xylenes, cumene Adsorption. Adsorption is a special characteristic of zeolites which is usually quite a complex process, generally involving much more than simple ion exchange into the pore openings of the ion exchanger. The amount of metal ion to be adsorbed is strongly affected by nature and concentration of the counter ion (metal ion), pH, metal solubility, presence of competing and complexing ions [9]. Since it is considered to be a particularly effective technique, adsorption is the preferred method for heavy metal removal such as Cu2+, Pb2+, Cd2+ and PO43- [10], H2 [11], CO2, CH4 and N2[12], NOx[13], N2 and O2 [14], volatile nitrozamines [15]. The large daily output and the limited landfill capacity have resulted in social and environmental problems. Severe water pollution and insufficient water source are major problems all over the world. One effective alternative to environmental problems is to convert the ash into zeolite absorbents for environmental applications such as water purification and soil conditioning [16, 17]. The researches are concerned mainly to the application of fly based zeolites to the removal of heavy metals [18, 19], NH4+[20], Cs+[21], As3+ and Cr6+[22]. Ion exchange. Zeolite frameworks provide substrates that support the mobility of the nonframework cations that make them good ion exchangers. Ammonia and its compounds in the wastewaters and effluents have harmful effects on water resources. For that reason of researches are made for removal of NH4+ [23, 24]. Zeolites are an excellent avenue for removal of cationic and anionic pollutants such as Cr6+and As5+ [ 25, 26], Cu2+, Pb2+ and Cd2+ [27], Fe3+and Zn2+ [28], Sr2+[29], etc. Researches have been made about zeolites exchange capacity. For example, cation exchange capacity from 160 to 260 meq 100g-1 were obtained for NaP1, Herschelite, KM, Linde F and K-Chabazite for the cation investigated. The results showed: NaP1: + + + 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ Ba >Pb >NH4 =Cd >Zn , KM: NH4 > Pb = Ba >Cd = Zn , Linde F: NH4 = Ba2+= Volume IV Natural & Mathematical science. 3

International Science conference 4th - 5th June 2009, Stara Zagora, BULGARIA "Economics and Society development on the Base of Knowledge" Pb2+>Cd2+> Zn2+, K-Chabazite: Ba2+= Pb2+> NH4+=Cd2+>Zn2+, Herschelite: NH4+= Pb2+> Ba2+= Cd2+> Zn2+ [30]. In the last years there has been an increase in the usage of zeolites in different compositions to delete and bury different radio-contaminations. The presence of radionuclides in wastes is a major environmental concern. Recent paper published researched the interaction of synthetic zeolites with Cs+ [21, 31] and Ur6+ [32] and sowed that zeolites are very effective adsorbents for radiocontaminant removal. Zeolites will continue to be used in the separation and purification technology through the chemical process industry. Future trends involve environmental and biopharmaceutical application. ACKNOWLEDGEMENTS: The financial support of the Bulgarian Ministry of Education and Sciences (National Science Fund), contract DO-02-110/2008, is gratefully acknowledged. REFERENCES 1. Breck, D. W., 1974. Zeolite Molecular Sieves: Structure, Chemistry and Use. London: John Wiley and Sons, p.4 2. Bekkum, V. H., Flanigen, E.M., Jacobs, P.A., Jansen, J.C., 1991. Introduction to Zeolite Science and Practice, 2nd. Revised Edn., Elsevier, Amsterdam 3. Meier, W. M., Olson, D. H., 1987. Atlas of Zeolites Structure Types. 2nd. Revised Edn., Butterworth 4. Barrer, R.M., 1982. Hydrothermal Chemistry of Zeolites, Academic Press, London 5. Hamdan, H., 2003. Design and molecular engineering of nanostructured zeolites and mesomorphous materials: Advancing through the pores, Penerbit Universiti Teknologi Malaysia, p.1-44 6. Ros, C.A., 2008. Synthesis of zeolites from geological materials and industrial wastes for potential application in environmental problems, PhD thesis, University of Wolverhampton, School of Applied Sciences 7. Marcilly, C., 2001. Evolution of Refining and Petrochemicals: What ins the Place of Zeolites, Oil and Gas Science and Technology, 56, p. 499-514 8. Houssin, Christophe, J.Y., 2003. Nanoparticles in zeolite synthesis, PhD thesis, Eindhoven, Technische Universiteit Eindhoven 9. Ikhsan, J., Johnson, I.B.B., Wells, J.D., 1999. A comparative study of the adsorption of transition metals on kaolinite, Journal of Colloid and Interface Science, 217, p. 403-410 10. Kugbe, J., Matsue N., Henmi T., 2009. Synthesis of Linde type A zeolitegoethite nanocomposite as an adsorbent for cationic and anionic pollutants, Journal of Hazardous Materials, 164, p.929-935 11. Palomino, G.T., Carayol, M.R.L., Aren, C.O., 2008. Thermodynamics of hydrogen adsorption on the zeolite Ca-Y, Catalysis Today, 138, p.249-252 12. Xu, X., Zhao, X., Sun, L., Liu, X., 2008. Adsorption separation of carbon dioxide, methane, and nitrogen on H and Na-exchanged -zeolite Journal of Natural Gas Chemistry, 17, p.391-396 13. Yang, J., Zhuang, T.T., Wei, F., Zhou, Y., Cao, Y., Wu, Z.Y., Zhu, J.H., Liu, C., 2009. Adsorption of nitrogen oxides by the moisture-saturated zeolites in gas stream, Journal of Hazardous Materials, 162, p.866-873 14. Shang, A.Y., Wu, J., Zhu, J., Wang, Y., Meng, Y., 2009. Study on adsorption of N2 and O2 by magnesium (II)-exchanged zeolite A , Journal of Alloys and Compounds, 478, p.L5-L7 15. Gu, F.N., Zhuang, T.T., Cao, Y., Zhou, C.F., Zhu, J.H., 2008. Effect of copper cation on the adsorption of nitrosamines in zeolite, Solid State Sciences, 10, p.1658-1665 Volume IV Natural & Mathematical science. 4

International Science conference 4th - 5th June 2009, Stara Zagora, BULGARIA "Economics and Society development on the Base of Knowledge" 16. Ishimoto, H., Origuchi, T., Yasuda, M., 2000. Use of papermaking sludge as new material, Journal of Materials in Civil Engineering, 12, p.310313 17. Ishimoto, H., Yasuda, M., Sasaki, O., 2003. Application of new materials from paper recycling for purifying domestic wastewater, NTT Review, 15, p.4347 18. Scott, J., Deyan,. G., Naeramitmarnsuk, K., Thabuot, M., Amal, R., 2001. Zeolite synthesis from coal fly ash for the removal of lead ions from aqueous solution, Journal of Chemical Technology and Biotechnology, 77, p.6369 19. Querol, X., Alastuey, A., Moreno, N., Alvarez-Ayuso, E., Garca-Snchez, A., Cama, J., Ayora, C., Simn, M., 2006. Immobilization of heavy metals in polluted soils by the addition of zeolitic material synthesized from fly ash, Chemosphere, 62, p.171-180 20. Querol, X., Plana, F., Alastuey, A., Lopez-Soler, A., Andres, J.M., Juan, R., Ferrer, P., Ruiz, C.R., 1997. A fast method for recycling fly ash: Microwave assisted zeolite synthesis, Environmental Sciences and Technology, 31, p.2527-2532 21. Mimura, H., Yokota, K., Akiba, K., Onodera, Y., 2001. Alkali hydrothermal synthesis of zeolites from coal fly ash and their uptake properties of cesium ion, Journal of Nuclear Science and Technology, 38, p.766-772 22. Kumar, P., Jadhav, P.D., Rayalu, S.S., Devotta, S., 2007. Surface-modified zeoliteA for sequestration of arsenic and chromium anions, Current Science, 92, p.512-517 23. T. Wajima, T. Shimizu, Y. Ikegami, 2007. Synthesis of zeolites from paper sludge ash and their ability to simultaneously remove NH4+ and PO43, Journal of Environmental Science and Health Part A, 42, p.345350 24. Wang, Y., Lin, F., Pang, W., 2008. Ion exchange of ammonium in natural and synthesized zeolites, Journal of Hazardous Materials, 160, p.371-375 25. Kumar, P., Jadhav, P.D., Rayalu, S.S., Devotta, S., 2007. Surface-modified zeoliteA for sequestration of arsenic and chromium anions, Current Science, 92, p.512-517 26. Yusof, A.M., Nizam, N.A., Malek, N., 2009. Removal of Cr(VI) and As(V) from aqueous solutions by HDTMA-modified zeolite Y, Journal of Hazardous Materials, 162, p.10191024 27. Wang, Y., Guo, Y., Yang, Z., Cai, H., Querol, X., 2003. Synthesis of zeolites using fly ash and their application in removing heavy metals from waters, Science in China (Series D), 46, p.967-976 28. Ostroski, I.C., Barros, M.A.S.D., Silva, E.A., Dantas, J.H., Arroyo, P.A., Lima, O.C.M, 2009. A comparative study for the ion exchange of Fe(III) and Zn(II) on zeolite NaY, Journal of Hazardous Materials, 161, p.1404-1412 29. Lonin, A.Y., Krasnopyorova, A.P., 2005. Influence of different factors on sorption of 90Sr by natural and synthetic zeolites, Problems of atomic science and technology, 6, Series: Nuclear Physics Investigations, 45, p.130-132 30. Querol, X., Umaa, J.C., Plana, F., Alastuey, A., Lopez-Soler, A., Medinaceli, A., Valero, A., Domingo, M.J., Gracia-Rojo, E., 2001. Synthesis of Na zeolites from fly ash in a pilot plant scale: Examples of potential environmental applications, Fuel, 80, p.857-865 31. El-Naggar, M.R., El-Kamash, A.M., El-Dessouky, M.I., Ghonaim, A.K. 2008, Two-step method for preparation of NaA-X zeolite blend from fly ash for removal of cesium ions, Journal of Hazardous Materials, 154, p.963-972 32. 32. Hossein, G.M., Hossein, K., Ali, N.M., Ali, M., Reza, P.M., 2008. Ion Exchange Behavior of Zeolites A and P Synthesized Using Natural Clinoptilolite, Iranian Journal of Chemistry and Cemical Engineering, 27, p.111-117.

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