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Fixed-Bed Modification of Zeolitic Tuffs and Their Application for Cr(VI) Removal.

ABSTRACT: Natural clinoptilolite tuff (CL) and chabazite-clinoptilolite tuff (CH) were modified in fixed-bed column by immobilization of hexadecyltrimethylammonium bromide (HDTMA-Br), then investigated as a sorbent for inorganic anions of Cr(VI). The proposed modification technique combined with surfactant solution batching allows minimizing the surfactant loses through foaming and crystallization and creation of stable organic coverage. The HDTMA loading depended on the mineral composition of the zeolitic tuff, the topology of its external surface, and process conditions. The maximum surface coverage was obtained by gradually dosing surfactant solution in the smallest volume of batches and corresponded up to 100% and 182% of external cation exchange capacity (ECEC) for mono and double layer coverage, respectively. In case of mono layer coverage, modification proceeds until the exhaustion of surfactant in supply solution, while in the double layer one, until equilibrium of HDTMA concentration in both zeolitic and liquid phases was established. The efficiency of Cr(VI) uptake by prepared surface modified zeolites (SMZs) increased with increasing of HDTMA loading. In the case of mono layer SMZs, the capacities of CH-HDTMA and CL-HDTMA were 10.3 and 5.4 mg/g, respectively, while in the case of double layer SMZs, the amount of Cr uptake on CH-HDTMA and CL-HDTMA were 16.8 and 15 mg/g, respectively. Ion exchange is the predominant mechanism of Cr(VI) sorption but it takes place only if modification resulted in at least partial double layer coverage. The XPS analysis reveals Cr(VI) reduction to a less-toxic Cr(III) by the electron donating N-containing groups and by reaction with Fe⁺² ions on the zeolite external surface.

SUBMITTER: Warchol JK

PROVIDER: S-EPMC8621222 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The efficient removal of toxic metals ions from chemical industry wastewater is considered problematic due to the existence of pollutants as mixtures in the aqueous matrix, thus development of advanced and effective treatment method has been identified as a panacea to the lingering problems of heavy metal pollution. In this study, KIAgNPs decorated MWCNTs nano adsorbent was developed using combination of green chemistry protocol and chemical vapor deposition techniques and subsequently characterized using UV-Vis, HRTEM, HRSEM, XRD, FTIR and XPS. The adsorptive efficiency of MWCNTs-KIAgNPs for the removal of Cr(VI), Ni(II), Fe(II), Cd(II) and physico-chemical parameters like pH, TDS, COD, BOD, nitrates, sulphates, chlorides and phosphates from chemical industrial wastewater was examined in both batch and fixed bed systems. The result exhibited successful deposition of KIAgNPs on the surface of MWCNTs as confirmed by the microstructures, morphology, crystalline nature, functional groups and elemental characteristics of the MWCNTs-KIAgNPs. Optimum batch adsorption parameters include; pH (3 for Cr(VI) and 6 for Ni(II), Fe(II) and Cd(II) ions), contact time (60 min), adsorbent dosage (40 mg) and temperature (318 K). The binding capacities were obtained as follows; Cr6+ (229.540 mg/g), Ni2+ (174.784 mg/g), Fe2+ (149.552) and Cd2+ (121.026 mg/g), respectively. Langmuir isotherm and pseudo-second order kinetic model best described the experimental data in batch adsorption, while the thermodynamic parameters validated the chemisorption and endothermic nature of the adsorption process. In continuous adsorption, the metal ions were effectively removed at low metal influent concentration, low flow rate and high bed depth, whereby the experimental data were designated by Thomas model. The high physico-chemical parameters in the wastewater were successfully treated in both batch and fixed bed systems to fall within WHO permissible concentrations. The adsorption/desorption study illustrated over 80% metal removal by MWCNTs-KIAgNPs even after 8th adsorption cycle. This study demonstrated excellent performance of MWCNTs-KIAgNPs for chemical industry wastewater treatment.

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Fixed-Bed Modification of Zeolitic Tuffs and Their Application for Cr(VI) Removal.

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