Share This Article:

Zeolite Synthesis under Insertion of Silica Rich Filtration Residues from Industrial Wastewater Reconditioning

Full-Text HTML Download Download as PDF (Size:6686KB) PP. 120-134
DOI: 10.4236/aces.2014.42015    3,773 Downloads   5,013 Views   Citations


Zeolite synthesis was studied using two silica rich filtration residues (FR 1 and FR 2) as Si-source and sodium aluminate in a direct synthesis at 60°C at strong alkaline conditions (8 M - 16 M NaOH). In addition to these one-pot syntheses, a two-step process was investigated. Here, an alkaline digestion of FR at 60°C was followed by gel precipitation with sodium aluminate and gel crystallization under usual conditions of 80°C - 90°C. The results show that the substitution of chemical reagent sodium silicate by a waste material like FR as Si-source is possible but requires fine tuning of the reaction conditions as zeolite crystallization is a process under kinetic control. The solubility behaviour and impurities of the inserted filtration residues strongly influenced the course of reaction. Thus zeolites like hydrosodalite or intermediate zeolite between cancrinite and sodalite, or zeolite NaA or Z-21 in cocrystallization with hydrosodalite could be observed in the one pot syntheses already in a short time interval between 1 - 4 h depending on the alkalinity. The two step process yield to zeolites NaA and NaX in very good quality. The reaction process of FR in both reaction methods was characterized by chemical analyses, X-ray powder diffraction, Fourier transform infrared spectroscopy as well as scanning electron microscopy. Surface area and water content of selected products were further characterized by the BET-method and by thermogravimetry. Summing up the results, we can show that zeolite formation from filtration residues is possible by several reaction procedures as model cases for a re-use of industrial waste materials. Beside the importance for environmental protection, the reactions are of interest for zeolite chemistry as the re-use of FR is possible under economically conditions of low energy consumption at 60°C and short reaction periods.

Cite this paper

Hartmann, A. , Petrov, V. , Buhl, J. , Rübner, K. , Lindemann, M. , Prinz, C. and Zimathies, A. (2014) Zeolite Synthesis under Insertion of Silica Rich Filtration Residues from Industrial Wastewater Reconditioning. Advances in Chemical Engineering and Science, 4, 120-134. doi: 10.4236/aces.2014.42015.


[1] Barrer, R.M. (1978) Zeolites and Clay Minerals as Sorbents and Molecular Sieves. Academic Press, London.
[2] Breck, D.W. (1984) Zeolite Molecular Sieves: Structure, Chemistry and Use. John Wiley & Sons Inc., New York.
[3] Barrer, R.M. (1982) Hydrothermal Chemistry of Zeolites. Academic Press, London.
[4] Aiello, R., Colella, C., Casey, D.G. and Sand, L.B. (1980) Experimental Zeolite Crystallization in Rhyolitic Ash-Sodium Salt Systems. Proceedings of 5th International Zeolite Conference, London, 1980, 49-55.
[5] Holler, H. and Wirsching, U. (1985) Zeolite Formation from Fly Ash. Fortschr. Miner, 63, 21-43.
[6] Grutzeck, M. and Siemer, D.D. (1997) Zeolites Synthesized from Class F Fly Ash and Sodium Aluminate Slurry. Journal of the American Ceramic Society, 80, 2449-2453.
[7] Maenami, H., Shin, H., Ishida, H. and Mitsuda, T. (2000) Hydrothermal Solidification of Wastes with Formation of Zeolites. Journal of Materials in Civil Engineering, 12, 302-306.
[8] Miyake, M., Tamura, C. and Matsuda, M. (2002) Resource Recovery of Waste Incinerator fly Ash: Synthesis of Zeolites A and P. Journal of Materials in Civil Engineering, 85, 1873-1875.
[9] Murayama, N., Yamamoto, H. and Shibata, J. (2002) Zeolite Synthesis from Coal Fly Ash by Hydrothermal Reaction Using Various Alkali Sources. Journal of Chemical Technology and Biotechnology, 77, 280-286.
[10] Anuwattana, R. and Khummongkol, P. (2009) Conventional Hydrothermal Synthesis of Na-A Zeolite from Cupola Slag and Aluminium Sludge. Journal of Hazardous Materials, 166, 227-232.
[11] Di Renzo, F., Fajula, F., Figueras, F., Nicolas, S. and Des Courieres, T. (1989) Are the General Laws of Crystal Growth Applicable to Zeolite Synthesis? In: Jacobs, P.A. and van Santen, R.A., Eds., Zeolites: Facts, Figures, Future, Studies in Surface Science and Catalysis, Vol. 49, Part A, Elsevier, Amsterdam, 119-132.
[12] Daniels, R.H., Kerr, G.T. and Rollmann, L.D. (1978) Cationic Polymers as Templates in Zeolite Crystallization. Journal of the American Chemical Society, 100, 3097-3100.
[13] Weigel, S.J., Gabriel, J.C., Puebla, E.G., Bravo, A.M., Henson, N.J., Bull, L.M. and Sheetham, A.K. (1996) Structure-Directing Effects in Zeolite Synthesis: A Single-Crystal X-ray Diffraction, Si-29 MAS NMR, and Computational Study of the Competitive Formation of Siliceous Ferrierite and Dodecasil-3C (ZSM-39). Journal of the American Chemical Society, 118, 2427-2435.
[14] Hadan, M. and Fischer, F. (1992) Synthesis of Fine Grained NaA-Type Zeolites from Superalkaline Solutions. Crystal Research and Technology, 27, 343-350.
[15] Fischer, F., Hadan, M. and Fiedrich, G. (1992) Zeolite Syntheses from Superalkaline Reaction Mixtures. Collection of Czechoslovak Chemical Communications, 57, 788-793.
[16] Fischer, F., Hadan, M. and Horn, A. (1991) Investigations to the Synthesis of zeolite Na A for Using in Detergents from Superalkaline Solutions. Chem. Tech, 43, 191-195.
[17] JCPDS (1997-2004) International Centre for Diffraction Data, 12 Campus Boulevard, Newton Square.
[18] Flanigen, Khatami, H. and Szymanski, H.A. (1971) Infrared Structural Studies of Zeolite Frameworks. Advances in Chemistry, 101, 201-228.
[19] Weidlein, J., Müller, U. and Dehnicke, K (1981) Schwingungsfrequenzen. G. Thieme Verlag, Stuttgart.
[20] G. Hermeler, J.-Ch. Buhl and W. Hoffmann (1991) The Influence of Carbonate on the Synthesis of an Intermediate Phase between Sodalite and Cancrinite. Catalysis Today, 8, 415-426.
[21] Grader, C. and Buhl, J.-C. (2013) The Intermediate Phase between Sodalite and Cancrinite: Synthesis of Nano-Crystals in the Presence of Na2CO3/TEA and Its Thermal- and Hydrothermal Stability. Microporous and Mesoporous Materials, 171, 110-117.
[22] Gossner, B. and Mussgnug, F. (1930) über Davyn und seine Beziehung zu Hauyn und Cancrinit. Zeitschrift für Kristallographie, 73, 52-60.
[23] Baerlocher, C., Meier, W.M. and Olson, D.H. (2001) Atlas of Zeolite Framework Types. 5th Edition, Elsevier, Amsterdam.
[24] Jarchow, O. (1962) Zur Struktur des Cancrinits. Fortschr. Mineralogie, 40, 55-56.
[25] Jarchow, O. (1965) Atomanordnung und Strukturverfeinerung von Cancrinit. Zeitschrift für Kristallographie, 122, 407-422.
[26] Pauling, L. (1930) The Structure of Sodalite and Helvite. Zeitschrift für Kristallographie, 74, 213-225.
[27] Lons, J. and Schulz, H. (1967) Strukturverfeinerung von Sodalith Na8Si6Al6O24Cl2. Acta Crystallographica, 23, 434-436.
[28] Felsche, J. and Luger, S. (1987) Phases and Thermal-Decomposition Characteristics of Hydro-Sodalites
Na8[AlSiO4]6(OH)x.nH2O. Thermochimica Acta, 118, 35-55.
[29] Engelhardt, G., Felsche, J. and Sieger, P. (1992) The Hydrosodalite System Na6+x[SiAlO4]6(OH)x.nH2O Formation, Phase Composition and Dehydration and Rehydration Studied by 1H, 23N and 29Si MAS-NMR Spectroscopy in Tandem with Thermal Analysis X-Ray Diffraction and IR Spectroscopy. Journal of the American Chemical Society, 114, 1173-1182.
[30] Barrer, R.M. and Beaumont, R. (1974) Characterization of the Synthetic Zeolite (Na, Me4N)-V. Journal of the Chemical Society, Dalton Transactions, 4, 405-407.
[31] Moenke, H. (1966) Mineralspektren. Akademie Verlag, Berlin.
[32] Buhl, J.-C. (1991) Synthesis and Characterization of the Basic and Non-Basic Members of the Cancrinite-Natrodavyne Family. Thermochimica Acta, 178, 19-31.
[33] Kriven, W.M., Bell, J.L., Gordon, M. and Wen, G. (2005) Geopolymers: More than Just Cements, Geopolymer, Green Chemistry and Sustainable Development Solutions. In: Davidovits, J., Ed., World Congress Geopolymer, 2005, The Geopolymer Institute, St. Quentin.

comments powered by Disqus

Copyright © 2018 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.