Ion exchange of heavy metals with zeolites is important in terms of different application areas. Industrial wastewater treatment and antibacterial applications are two essential areas that have taken great attention. While silver, zinc and copper are well known for their toxicity, they are also used as antibacterial agents in zeolites. The objective of this study is to investigate the single and multicomponent ion exchange behavior of zeolite 4A for silver, zinc, copper and sodium ions. For this purpose Ag+-Na+, Zn2+-Na+, Cu2+-Na+ binary systems and Ag+-Zn2+-Na+, Ag+-Cu2+-Na+, Cu2+-Zn2+-Na+ ternary systems were investigated in batch systems at 25&deg / C and 0.1 N. Binary ion exchange isotherms indicate that zeolite 4A has high selectivity for silver, zinc and copper with respect to sodium. All exchange isotherms lie above the diagonal over the whole range. Using the equilibrium data, the thermodynamic analysis of the binary systems were carried out. The thermodynamic equilibrium constants and the standard free energies of exchange were calculated as 340.9 and -14.5 kJ/mol for silver-sodium system, 40.5 and -4.6 kJ/mol for zinc-sodium system, and 161.2 and -6.3 kJ/mol for copper-sodium system, respectively. From these values, selectivity sequence of zeolite 4A was determined as Ag+ &gt / Cu2+ &gt / Zn2+. This selectivity sequence was also verified by the results of ternary ion exchange experiments. The experimental data were compared with the Langmuir and Freundlich isotherms. While Freundlich model gives a better correlation for Ag+-Na+ and Zn2+-Na+ exchange, Langmuir model represents a better fit to the experimental data of Cu2+-Na+ exchange.

In this study binary and ternary ion exchange on Zeolite NaA using silver and cadmium ions were investigated. Ion exchange were conducted at constant temperature (25oC) and normality (0.1N) in a batch system for both binary and ternary experiments. Zeolite weights were varied between 0.1 and 1 g for binary experiments. Thermodynamic analysis of binary ion exchange between Cd2+-Na+ and Ag+-Na+ were examined and thermodynamic equilibrium constant and Gibbs free energy were calculated. Thermodynamic equilibrium constants were found as respectively 28.2 and 300.4 for Cd2+-Na+ and Ag+-Na+ binary system. Standart free energy of Cd2+-Na+ and Ag+-Na+ binary exchange were calculated as -4.1 kJ/mol and -14.1 kJ/mol respectively. In literature Ay (2008) calculated the Gibbs free energy for Ag+-Na+ binary system as -14.4 kJ/mol and Biskup and Subotic (2010) and Gal et al. (1970) calculated the Gibbs free energy for Cd2+-Na+ binary system as -3.7 kJ/mol and -4.4 kJ/mol respectively. It is concluded Zeolite 4A has higher affinity to silver than cadmium and selectivity sequence was found as / Ag+&gt / Cd2+&gt / Na+. Langmuir and Freundlich isotherms were drawn to describe experimental data. As compared the R2 of isotherms, it is clearly seen that Freundlich isotherm provides better fit for Cd2+-Na+ binary ion exchange and Ag+-Na+ binary ion exchange. The ternary ion exchange isotherms were plotted using equivalent fraction of three ions (Ag+,Na+,Cd2+) which participated in ion exchange experiments to determine selectivity of zeolite 4A for cadmium and silver. Selectivity sequence was determined as Ag+ &gt / Cd2+ &gt / Na+ for ternary ion exchange.

Developing new membrane morphologies and modifying the existing membrane materials are required to obtain membranes with improved gas separation performances. The incorporation of zeolites and low molecular-weight additives (LMWA) into polymers are investigated as alternatives to modify the permselective properties of polymer membranes. In this study, these two alternatives were applied together to improve the separation performance of a polymeric membrane. The polycarbonate (PC) chain characteristics was altered by incorporating p-nitroaniline (pNA) as a LMWA and the PC membrane morphology was modified by introducing zeolite 4A particles as fillers. For this purpose, pure PC and PC/pNA dense homogenous membranes, and PC/zeolite 4A and PC/pNA/zeolite 4A mixed matrix membranes (MMM) were prepared by solvent-evaporation method using dichloromethane as the solvent. The pNA and zeolite 4A concentrations in the casting solutions were changed between 1-5% (w/w) and 5-30% (w/w), respectively. Membranes were characterized by SEM, DSC, and single gas permeability measurements of N2, H2, O2, CH4 and CO2. They were also tested for their binary gas separation performances with CO2/CH4, CO2/N2 and H2/CH4 mixtures at different feed gas compositions. DSC analysis of the membranes showed that, incorporation of zeolite 4A particles into PC/pNA increased the glass transition temperatures, Tg, but incorporation of them to pure PC had no effect on the Tg, suggesting that pNA was a necessary agent for interaction between zeolite 4A and PC matrix. The ideal selectivities increased in the order of pure PC, PC/zeolite 4A MMMs and PC/pNA/zeolite 4A MMMs despite a loss in the permeabilities with respect to pure PC. A significant improvement was achieved in selectivities when the PC/pNA/zeolite 4A MMMs were prepared with pNA concentrations of 1 % and 2 % (w/w) and with a zeolite loading of 20 % (w/w). The H2/CH4 and CO2/CH4 selectivities of PC/pNA (1%)/zeolite 4A (20%) membrane were 121.3 and 51.8, respectively, which were three times higher than those of pure PC membrane. Binary gas separation performance of the membranes showed that separation selectivities of pure PC and PC/pNA homogenous membranes were nearly the same as the ideal selectivities regardless of the feed gas composition. On the other hand, for PC/zeolite 4A and PC/pNA/zeolite 4A MMMs, the separation selectivities were always lower than the respective ideal selectivities for all binary gas mixtures, and demonstrated a strong feed composition dependency indicating the importance of gas-membrane matrix interactions in MMMs. For CO2/CH4 binary gas mixture, when the CO2 concentration in the feed increased to 50 %, the selectivities decreased from 31.9 to 23.2 and 48.5 to 22.2 for PC/zeolite 4A (20%) and PC/pNA (2%)/zeolite 4A (20%) MMMs, respectively. In conclusion, high performance PC based MMMs were prepared by blending PC with small amounts of pNA and introducing zeolite 4A particles. The prepared membranes showed promising results to separate industrially important gas mixtures depending on the feed gas compositions.

Les exploitations d’argiles kaoliniques réfractaire d’Água Limpa/Brésil et de kaolins de couchage de Rio Capim/Brésil laissent des résidus d’exploitation en très grands tonnages. Dans la perspective d’une valorisation plus complète assurant un développement durable de l’industrie extractive, on a envisagé d’utiliser ces argiles résiduelles dans la fabrication de zéolites. On a obtenue dès une durée de synthèse de 24h, une zéolite 4A très proche de sa définition théorique. Le rendement de synthèse est meilleur avec les produits de Rio Capim. Le volume nanoporeux de la zéolite 4A est inaccessible à l’azote mais accessible à la molécule d’eau. Les zéolites synthétisées ont été testées comme adsorbants cationiques pour le cuivre, le plomb, le cadmium, le zinc, le magnésium, potassium et mercure. La rétention a voisine 60% du remplissage théorique pour toutes les espèces testées, sauf pour le cuivre où elle dépasse la capacité théorique et pour le mercure où elle est très faible. / Working Kaolinic refractory clays from Água Limpa (Minas Gerais) and paper coating kaolins from Rio Capim (Pará) - Brazil throw over very large amounts of mining residues. With the outlook of a more complete beneficiation, aiming at a sustainable development of mineral industry, the use of these residual clays has been considered for manufacturing zeolites. For a synthesis time of only 24h, a zeolite 4A very close to its theoretical definition is obtained.The nano-porous volume of the zeolite 4A is inaccessible to nitrogen molecules, but accessible to water molecules. Synthesised zeolites have been tested as cationic adsorbents of Cu, Pb, Cd, Zn, Mg, K and Hg. The retention is better for materials derived from Rio Capim Kaolins. The retention is close to 60% of the theoretical completion of the exchange capacity in all cases, except for copper for which the retention exceeds the capacity, and mercury for which the retention is very low.

Gegenstand dieser Arbeit ist es, die Temperaturbeständigkeit von bikontinuierlichen Kompositmembranen bestehend aus Zeolith 4A und Visiomer HEMATMDI zu überprüfen und das Verhalten ihrer Permeanz im Verlauf der Temperaturerhöhung zu untersuchen. Weiterhin wird ihre Verwendbarkeit für technisch und industriell relevante Prozesse der Gastrocknung nachgewiesen. Zunächst wird thermogravimetrisch untersucht, bei welcher Temperatur Zersetzungserscheinungen an der polymeren Komponente auftreten. Anschließend wird thermogravimetrisch der Wassergehalt von Zeolith 4A im Bereich dieser Temperatur bestimmt. Hierauf folgen Permeationsmessungen mit Sauerstoff und Stickstoff an der bikontinuierlichen Kompositmembran. Die Temperatur wird hierbei schrittweise bis knapp unter die Zersetzungstemperatur des Polymers erhöht. Die Eignung der Membranen zur Gastrocknung wird exemplarisch an der Trocknung von Erdgas gezeigt. Es werden die Permeanzen für Wasserdampf und Methan als Hauptbestandteil von Erdgas mittels Einzelgasmessungen experimentell bestimmt. Aus diesen Permeanzen errechnet sich die ideale Selektivität der bikontinuierlichen Kompositmembran von Wasserdampf gegenüber Methan. Mit ihrer Hilfe lässt sich die Eignung der Membran zur Trocknung von Erdgas abschätzen. / The aim of this work is to study the temperature resistance of bicontinuous composite membranes, composed zeolite 4A and Visiomer HEMATMDI, and their permeances with rising temperatures. Furthermore their suitability for gas drying is investigated.