Chitosan, natural organic polymer, has been applied in water treatment as adsorbent due to non-toxic for human being. The amino group as functional group, can interacts with cation and anion at the same time. The prepared chitosan bead (HCB) was crosslinked to increase chemical stability (HCB-G) and both HCB and HCB-G were prepared to increase physical strength by drying referred to DCB and DCB-G, respectively. The adsorption effect for crosslinking and drying for four types of chitosan bead was tested using pseudo fist order (PFO), pseudo second order (PSO), and intraparticle diffusion model (ID). Regardless of PFO and PSO, the order of K, rate constant, is as followed: HCB > HCB-G > DCB > DCB-G for Cu(II) and phosphate. Drying leading to contraction of bead significantly reduced adsorption rate due to reduce the porosity of chitosan. In addition, crosslingking also negatively effect on adsorption rate. When compared with Cu(II) using hydrogel bead, phosphate showed higher value than Cu(II) for PFO and PSO. The application of ID showed that both hydrogel beads (HCB and HCB-G) obtained a very low R2 ranging to 0.37 to 0.81, while R2 can be obtained to over 0.9 for DCB and DCB-G, indicting ID is appropriate for low adsorption rate.
2 (Langmuir, Freundlich, Elovich, Temkin, and Dubinin-Radushkevich) and 3 (Sips and Redlich-Peterson)-parameter isotherm models were applied to evaluated for the applicability of adsorption of Cu(II) and/or phosphate isotherm using chitosan bead. Non-linear and linear isotherm adsorption were also compared on each parameter with coefficient of determination (R2). Among 2-parameter isotherms, non-linear Langmuir and Freundlich isotherm showed relatively higher R2 and appropriate maximum uptake (qm) than other isotherm equation although linear Dubinin-Radushkevich obtained highest R2. 3-parameter isotherm model demonstrated more reasonable and accuracy results than 2-parmeter isotherm in both non-linear and linear due to the addition of one parameter. The linearization for all of isotherm equation did not increase the applicability of adsorption models when error experiment data was included.
Batch adsorption tests were performed to evaluate the applicability of adsorption kinetic model by using hydrogel chitosan bead crosslinked with glutaraldehyde (HCB-G) for Cu(II) as cation and/or phosphate as anion. Pseudo first and second order model were applied to determine the sorption kinetic property and intraparticle and Boyd equation were used to predict the diffusion of Cu(II) and phosphate at pore and boundary-layer, respectively. According to the value of theoretical and experimental uptake of Cu(II) and phosphate, pseudo second order is more suitable. On comparison with the value of adsorption rate constant (k), phosphate kinetic was 2-4 times faster than that of Cu(II) at any experimental condition indicating the electrostatic interaction between NH3 + and phosphate is dominated at the presence of single component. However, when Cu(II) and phosphate simultaneously exist, the value of k for phosphate was sharply decreased and then the difference was not significant. Both diffusion models confirmed that the sorption rate was controlled by film mass transfer at the beginning time (t < 3 hr) and pore diffusion at next time section (t > 6 hr).
Cu(II) can cause health problem for human being and phosphate is a key pollutant induces eutrophication in rivers and ponds. To remove of Cu(II) and phosphate from solution, chitosan as adsorbent was chosen and used as a form of hydrogel bead. Due to the chemical instability of hydrogel chitosan bead (HCB), the crosslinked HCB by glutaraldehyde (GA) was prepared (HCB-G). HCB-G maintained the spherical bead type at 1% HCl without a loss of chitosan. A variety of batch experiment tests were carried out to determine the removal efficiency (%), maximum uptake (Q, mg/g), and reaction rate. In the single presence of Cu(II) or phosphate, the removal efficiency was obtained to 17 and 16%, respectively. However, the removal efficiency of Cu(II) and phosphate was increased to 50~55% at a mixed solution. The maximum uptake (Q) for Cu(II) and phosphate was enhanced from 11.3 to74.4 mg/g and from 3.34 to 36.6 mg/g, respectively. While the reaction rate of Cu(II) and phosphate was almost finished within 24 and 6 h at single solution, it was not changed for Cu(II) but was retarded for phosphate at mixed solution.