Kinetics and thermodynamics of copper ions removal from wastewater by use of zeolite

Natural Bulgarian zeolite was tested for its ability to remove Cu2+ from model wastewater. Influence of process variables was investigated. It was found that the optimum wastewater to zeolite ratio is 100:1 and the optimum pH value of water to be treated is 5.5 to 7.5. Zeolite with finer particles shows a higher uptake capacity. The simultaneous presence of Ca2+ and Mg2+ in concentrations similar to their concentrations in Bulgarian natural water does not significantly influence the uptake of Cu2+. Zeolite modification by treating it with NaCl, CH3COONa and NaOH increases its uptake ability. Copper ions are strongly immobilized by modified zeolite and secondary pollution of water caused by its contact with preloaded zeolite is very low (1.5–2.5% of Cu2+ preliminary immobilized have been released back into acidified water). Contacting with 2 mol dm−3 NaCl can easily regenerate loaded zeolite; best results were obtained for zeolite modified with NaCl. Requirements of Bulgarian standards for industrial wastewater can be met by a one-stage process for an initial Cu2+ concentration of 10 mg dm−3, and by a two stage process for an initial Cu2+ concentration of 50 mg dm−3. Uptake of Cu2+ by zeolite from neutral wastewater has proved to be as effective as Cu2+ removal by precipitation of copper hydroxide. The process of Cu2+ uptake by natural zeolite is best described by the kinetic equation for adsorption. This fact, together with the correlation found between the Cu2+ uptake and the amount of Na+, Ca2+ and K+ released into solution by zeolite shows that the ion exchange sorption plays the basic role in Cu2+ uptake by natural zeolite. The value obtained for the apparent activation energy (26.112 kJ mol−1) implies that the process can be easily carried out with a satisfactory rate. The uptake equilibrium is best described by the Langmuir adsorption isotherm, with Langmuir constants KL=6.4×10−2 dm3 mg−1 and M= 6.74 mg g−1. The apparent equilibrium constant found shows moderate affinity of zeolite for Cu2+. Values of ΔG° and ΔH° found show the spontaneous and endothermic nature of the process of Cu2+ uptake by natural zeolite.