Synthesis and utilization of chitin–humic acid hybrid as sorbent for Cr(III)

Abstract

New types of hybrid material have been synthesized by using four different methods of immobilization of humic acid (HA) on chitin. The most stable hybrid material toward the change of medium acidity was then utilized as sorbent for Cr(III). The HA was extracted from peat soil of Gambut District, South Kalimantan, Indonesia, using the recommended procedure of International Humic Substances Society (IHSS), while the chitin was isolated from crab shell waste through deproteination using 3.5% (w/v) NaOH and followed by removal of inorganic impurities using 1 M HCl. The four methods of immobilization of HA on chitin were (i) Method A: chitin powder (4 g) was gently poured into the stirred solution of 0.4 g HA in 40 mL of 0.01 M NaOH. After overnight stirring, the solid was separated, washed with water, and dried in oven at 70 °C. (ii) Method B: gelatinous chitin (40 g) in 250 mL of 0.5 M HCl was reacted with HA (4 g) in 500 mL of 0.5 M NaOH and aged for 24 h. The product was washed with water and dried. (iii) Method C: HA powder (0.5 g) was mixed with the stirred gel of chitin (2.5 g) in 60 mL of CaCl 2 saturated methanol and the mixture was then washed with the mixed solution of 25 mL of 2 M sodium citrate and ethylene glycol 1:1. The solid was separated, washed with water, and dried. (iv) Method D: the solution of HA (0.056 g) in 10 mL of 0.01 M NaOH was reacted with the gel of chitin (0.2 g) in 10 mL of CaCl 2 saturated methanol. After 24 h stirring, the solid was separated from the reaction medium, washed with the mixed solution of 2 M sodium citrate and ethylene glycol 1:1, and followed by washing with water and drying. Parameters investigated in this study consisted of the stability test of the immobilized HA, as well as the rate constant ( k 1), capacity ( b), and energy ( E) of sorption as well as the rate constant of desorption ( k −1). The k 1 and k −1 were determined according to a kinetic model of first order sorption reaching equilibrium, while the b and E were determined according to the Langmuir isotherm model. Compared to HA, Methods, A, C, and D; Method B produced the most stable immobilization of HA on chitin. The hybrid material (Chitin–HA) synthesized through Method B was stable in the acidity range that equivalent to pH 2.0–11.0. At the acidity giving maximum sorption, i.e. pH 5, the presence of immobilized HA on the Chitin–HA enhanced more than three times the k 1 and k −1, i.e. from 0.057 min −1 and 8.51 × 10 −4 (min −1) (mol/L) for chitin to 0.183 min −1 and 3.27 × 10 −3 (min −1) (mol/L) for the Chitin–HA. On the contrary, the presence of HA on Chitin–HA only gave small increase on b and small decrease on E. The values of b and E for Cr(III) on chitin were 1.45 × 10 −2 mol/g and 23.12 kJ/mol, respectively, while those on Chitin–HA were 1.78 × 10 −2 mol/g and 19.95 kJ/mol, respectively.