Removal of ammonium ion from aqueous solution using natural Turkish clinoptilolite
Introduction
The ammonia sources, which are municipal, agricultural and industrial, contribute to accelerated eutrophication of lakes and rivers, dissolved oxygen depletion and fish toxicity in receiving water. Complete removal of ammonia from process or waste effluents is required due to its extreme toxicity to most fish species. A variety of biological and physicochemical methods and technologies have been proposed for the removal of ammonia from the environment and industrial water systems [1]. The traditional method for ammonium removal from municipal and industrial wastewaters is based on biological treatments. Since biological methods (nitrification–denitrification) do not respond well to shock loads of ammonia, unacceptable peaks may appear in the effluent ammonium concentration. As discharge limits of various pollutants becomes more stringent, ion exchange and adsorption become more interesting as possible treatment methods. Ion exchange with natural zeolites is more competitive because of its low cost and relative simplicity of application and operation. The use of natural zeolite for the removal of ammonia from water and wastewater appears to have potential due to the advantages and peculiarities over some conventional and expensive ion-exchange resins [2], [3].
Natural clinoptilolite (zeolite) has a three-dimensional crystal structure and its typical unit cell formula is given either as Na6[(AlO2)6(SiO2)30]·24H2O or (Na2, K2, Ca, Mg)3 [(AlO2)6(SiO2)30]·24H2O [4], [5]. Three-dimensional crystal structure of zeolite contains two-dimensional channels [6], which embody some ion exchangeable cations such as Na, K, Ca and Mg. These exchangeable cations give rise to the ion-exchange properties of the material [7], [8]. Such sorptive properties have been utilized for a variety of purposes such as adsorption of ammonia by natural clinoptilolite [9], [10], [11], [12], removal of metal ions [13], [14], [15] and dye contaminants [16], [17], [18]. However, little investigation has been conducted to determine the kinetics of ammonium exchange using natural zeolite. The main objective of this paper is to describe the characteristics of a natural clinoptilolite from Turkey (Esen Foreign Trade Co.), to investigate the kinetics and the equilibrium of ammonium ion removal by clinoptilolite and to determine the factors controlling the rate of process.
Section snippets
Material and methods
Sample of clinoptilolite was obtained from the Esen Foreign Trade Co. in Western Anatolia, Turkey. Samples were crushed and classified to a size range of 1.0–1.4 mm. Clinoptilolite was washed to remove the water soluble residues and other undesirable material, and dried in an oven at 100 ± 5 °C for 24 h. Chemical and physical properties of sample was supplied by the producer. Mineralogical content of 85% is clinoptilolite, 10% is feldspar and 5% is clay. Cation exchange capacity and bulk density of
Effect of initial ammonium concentration
Ammonium exchange by natural clinoptilolite was studied at different initial NH4+ concentrations in the range of 25–150 mg/L. As shown in Fig. 1, ammonium exchange capacity increased with increasing of initial NH4+ concentration and this is the result of an increase in the driving force. The rate of sorption to the surface should be proportional to a driving force times an area. The driving force is the concentration of the solution and the area is the amount of bare surface [19]. For lower
Conclusions
Ammonium exchange by the natural Turkish clinoptilolite was studied in batch mode and found to be strongly dependent on initial concentration and contact time, and low temperature favors the ammonium uptake on the clinoptilolite. Langmuir model yield a much better (R2 = 0.927–0.969) fit than that of the Freundlich model (R2 = 0.878–0.952). RL value from Langmuir isotherm and n from Freundlich isotherm indicates that the removal of NH4+ ions on the clinoptilolite is favorable.
The pseudo second-order
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