Aminopolycarboxylic Acids-Functionalized Chitosan-Based Composite Cryogels as Valuable Heavy Metal Ions Sorbents: Fixed-Bed Column Studies and Theoretical Analysis

Over the years, a large number of sorption experiments using the aminopolycarboxylic acid (APCA)-functionalized adsorbents were carried out in batch conditions, but prospective research should also be directed towards column studies to check their industrial/commercial feasibility. In this context, sorption studies of five-component heavy metal ion (HMI) solutions containing Zn(2+), Pb(2+), Cd(2+), Ni(2+), and Co(2+) in equimolar concentrations were assessed in fixed-bed columns using some APCA-functionalized chitosan-clinoptilolite (CS-CPL) cryogel sorbents in comparison to unmodified composite materials. The overall sorption tendency of the APCA-functionalized composite sorbents followed the sequence Co(2+) < Zn(2+) < Cd(2+) ≤ Pb(2+) < Ni(2+), meaning that Co(2+) ions had the lowest affinity for the sorbent’s functional groups, whereas the Ni(2+) ions were strongly and preferentially adsorbed. To get more insights into the application of the composite microbeads into continuous flow set-up, the kinetic data were described by Thomas and Yoon–Nelson models. A maximum theoretical HMI sorption capacity of 145.55 mg/g and a 50% breakthrough time of 121.5 min were estimated for the column containing CS(EDTA)-CPL cryogel sorbents; both values were much higher than those obtained for the column filled with pristine CS-CPL sorbents. In addition, desorption of HMIs from the composite microbeads in dynamic conditions was successfully achieved using 0.1 M HCl aqueous solution. Moreover, a theoretical analysis of APCA structures attached to composite adsorbents and their spatial structures within the complex combinations with transition metals was systematically performed. Starting from the most stable conformer of EDTA, coordinative combinations with HMIs can be obtained with an energy consumption of only 1 kcal/mole, which is enough to shift the spatial structure into a favorable conformation for HMI chelation.