RESUMO
The clinoptilolite natural zeolites (NZs) posses low herbicide adsorption capacity demanding acid-, alkali-, or salt chemical modifications that enhance its adsorption. However, this may affect the material structure and charge distribution. Alternatively, zeolites may be synthesized at a high cost and time-consuming process. Consequently, new methods, such as the hydrothermal method, for NZ modification needs to be studied. In this sense, a novel surface-modified zeolite (SMZ), using hexadecyltrimethylammonium bromide (CTAB), in acid media was produced by the hydrothermal method and applied for the adsorption of Atrazine (ATZ), Diuron (DIU) and 2,4-D. Commercial NZ and SMZ were characterized by SEM, XRD, TGA, FT-IR, AA spectroscopy, pHPZC, Zeta potential and N2-physisorption. The SMZ chosen for the adsorption experiments was the one with the highest modification yield and adsorption capacity obtained from a complete design of experiments (CTAB=0.74 ; D=12 Mesh; HCl=0.1 M; t=6 h and T=205 ºC). The adsorption experiments revealed that the SMZ adsorption capacity for the herbicide 2,4-D (qmax=9.02 mg/g) was greater than that obtained for ATZ (qmax=2.11 mg/g) and DIU (qmax=1.85 mg/g), which was explained by the presence of the hydroxyl group and by geometric characteristics of the 2,4-D. Adsorption models' fitting showed that the adsorption of 2,4-D onto SMZ were best described by pseudo-second order kinetic (k2=0.005-0.006 g/mg.min; qe,exp=7.122-8.614 mg/g) and Langmuir isothermal model (KL=0.283-0.499 L/mg; qm=7.167-7.995 mg/g). These results indicate that the hydrothermal method is a viable alternative to enable the use of NZs for the adsorption of emerging contaminants from wastewater.
Assuntos
Herbicidas , Zeolitas , Zeolitas/química , Adsorção , Espectroscopia de Infravermelho com Transformada de Fourier , Cetrimônio , Tensoativos/química , Diurona , Cinética , Ácido 2,4-DiclorofenoxiacéticoRESUMO
The sol-gel route was used to synthesize a biophenolic resin from a blend of Kraft black liquor and condensed tannin. The biobased resin has an amorphous structure and diversified surface functional groups. The biomaterial thermal stability was improved by Kraft black liquor, which increased the fixed carbon yield by 19.78% in an oxidant medium and 9.07% in an inert medium. Moreover, the presence of fixed carbon and char is positively related to the material flame retardant property. Additionally, impedance measurements were used to understand the physical phenomena occurring at the polymeric matrix's interface and the material's final properties. The biobased resin characterization and the considerable increase in the presence of micropollutants in surface and water bodies suggest the new biomaterial application in the adsorption process. Thus, its adsorption capacity toward several organic and inorganic micropollutants and its effectiveness in complex water matrices were evaluated. Methylene blue was used as a model compound to assess the influence of the resin composition on the adsorption capacity, and the type H isotherm indicates the high affinity of the biobased resin toward the micropollutant. The adsorption occurs in multilayer by intermolecular interaction and electrostatic forces. The amount of Kraft black liquor favored the adsorption, and the adsorption capacity was greater than 1250 mg g-1. When inorganic compounds were evaluated, the carboxyl and phenol groups favor the biomaterial affinity toward metal ions. Cu2+ and Ni2+ were completely removed from the contaminated water, and the adsorption capacity of the other inorganic compounds was: Pb2+ (36.97 mg g-1), Al3+ (22.17 mg g-1), Ba2+ (12.76 mg g-1), Ag1+ (33.85 mg g-1), and Fe2+ (19.44 mg g-1). In contrast, the adsorption capacity of the organic micropollutants was: 2,4-D (3.09 mg g-1), diuron (5.89 mg g-1), atrazine (2.71 mg g-1), diclofenac (2.04 mg g-1), caffeine (5.79 mg g-1), acetaminophen (4.80 mg g-1), methylene Blue (106.66 mg g-1), and methyl orange (30.48 mg g-1). The results pointed that the adsorption efficiency of organic micropollutants increases with the distribution coefficient (logD), indicating the biobased resin affinity toward more lipophilic compounds and ionized species.