Muniyappan Rajiv Gandhi

Removal of copper(II) using chitin/chitosan nano-hydroxyapatite composite

Polymeric composites made up of nano-hydroxyapatite (n-HAp) with chitin and chitosan have been prepared and studied for the removal of Cu(II) ions from the aqueous solution. The sorption capacity (SC) of n-HAp, n-HAp/chitin (n-HApC) composite and n-HAp/chitosan (n-HApCs) composite were found to be 4.7, 5.4 and 6.2 mg/g respectively with a minimum contact time of 30 min. Batch adsorption studies were conducted to optimize various equilibrating conditions like contact time, pH and selectivity of metal ion. The sorbents were characterized by FTIR, TEM, XRD and SEM with EDAX analysis. The sorption process was explained with Freundlich and Langmuir isotherms respectively. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated to understand the nature of sorption. A suitable mechanism for copper sorption was established and the selectivity of the metal ions for the composites was identified.

Sorption of chromium(VI) using modified forms of chitosan beads

Modified forms of chitosan beads were prepared and used for chromium removal from the aqueous solution. The prepared chitosan beads viz., protonated chitosan beads (PCB), carboxylated chitosan beads (CCB) and grafted chitosan beads (GCB) possess enhanced chromium sorption capacities (SCs) of 3239, 3647 and 4057 mg/kg respectively than the raw chitosan beads (CB) which possess the SC of 1298 mg/kg with a minimum contact time of 10min. The sorption experiments were carried out in batch mode to optimize various influencing parameters viz., contact time, pH, common ions and temperature. The sorbents were characterized by FTIR and SEM with EDAX analysis. The modified chitosan beads remove chromium by means of electrostatic adsorption coupled reduction and complexation. The adsorption data was fitted with Freundlich and Langmuir isotherms. The calculated values of thermodynamic parameters indicate the nature of chromium sorption. A field trial was carried out with water collected from a nearby industrial area.

Preparation and characterization of silica gel/chitosan composite for the removal of Cu(II) and Pb(II)

Silica gel/chitosan composite (SiCS) was prepared via., sol-gel method by mixing silica gel and chitosan and cross-linked with bifunctional cross-linker glutaraldhyde. The SiCS composite was characterized using FT-IR, SEM-EDAX, XRD and BET methods. The sorption of copper and lead ions onto SiCS has been investigated. The SiCS composite was found to have excellent metal sorption capacity than the silica gel (Si) and chitosan (CS). The sorption experiments were carried out in batch mode to optimize various parameters viz., contact time, pH, initial metal ion concentration, co-ions and temperature that influence the sorption. Langmuir, Freundlich and Dubinin-Radushkevich adsorption isotherm models were applied to describe isotherm constants. Equilibrium data agreed well with the Freundlich isotherm model. Thermodynamic studies revealed that the nature of sorption is spontaneous and endothermic. The SiCS removes metals by means of adsorption and complexation. Sorption capacity of SiCS is compared with other sorbents which suggest that this composite was useful for removing copper and lead from aqueous solution.

Preparation and application of alumina/chitosan biocomposite.

A new chitosan based biocomposite was prepared using alumina and used for the removal of chromium from the aqueous solution. The synthesized alumina/chitosan (AlCs) composite possesses an enhanced chromium sorption capacity (SC) of 8.62 mg/g than the original alumina and chitosan flakes that possess the SCs of 3.7 and 0.67 mg/g respectively, with a minimum contact period of 30 min. The sorption experiments were carried out in batch mode to optimize various parameters viz., contact time, initial chromium concentration, pH, co-ions and temperature that influence the sorption. The sorbents were characterized by FTIR, AFM, BET and SEM with EDAX analysis. The composite removes chromium by means of electrostatic adsorption coupled reduction and complexation. The adsorption data were fitted with Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherms. The calculated values of thermodynamic parameters indicate the nature of chromium sorption. The dynamic studies demonstrate that the sorption process follows pseudo-second-order and intraparticle diffusion models.

Preparation and characterization of La(III) encapsulated silica gel/chitosan composite and its metal uptake studies

Lanthanum loaded silica gel/chitosan composite (LaSiCS) was prepared by mixing silica gel, LaCl(3) · 7H(2)O and chitosan which was then cross-linked with glutaraldhyde. The LaSiCS composite was characterized using FT-IR, SEM-EDAX, XRD and BET. The adsorption of chromium(VI) ions onto LaSiCS composite has been investigated. The LaSiCS composite was found to have excellent chromium adsorption capacity than the silica gel/chitosan composite (SiCS), silica gel (Si) and chitosan (CS). The sorption experiments were carried out in batch mode to optimize various parameters viz., contact time, pH, initial chromium ion concentration, co-ions and temperature that influence the sorption. Langmuir and Freundlich adsorption models were applied to describe isotherm constants. Equilibrium data agreed very well with the Langmuir model. Thermodynamic studies revealed that the nature of chromium sorption was spontaneous and endothermic. The LaSiCS composite removes chromium by electrostatic adsorption coupled reduction/ion-exchange.

Preparation of amino terminated polyamidoamine functionalized chitosan beads and its Cr(VI) uptake studies

Chitosan beads, functionalized by amino terminated hyperbranched dendritic polyamidoamine (up to 3rd generation) were prepared by Michael addition of methyl acrylate to amino groups on the chitosan surface and amidation of terminal ester groups by ethylene diamine. All the three generation chitosan beads were used for chromium removal along with raw chitosan beads. However, the 3rd generation polyamidoamine chitosan beads (3ACB) have been protonated using HCl (3ACBP)/loaded with zirconium using ZrOCl(2)·8H(2)O (3ACBZr) to enhance the sorption capacity towards Cr(VI). The zirconium loaded chitosan beads showed higher Cr(VI) sorption than the other modified chitosan beads. The zirconium loaded chitosan beads were characterized using SEM, EDAX, FT-IR, XRD, DSC and TGA. The system variables studied include agitation time, initial concentration of sorbate, pH, co-ions in the medium and temperature on the sorption of chromium. The chromium uptake onto 3ACBZr obeys the Freundlich isotherm. Thermodynamic studies revealed that the nature of chromium sorption is spontaneous and endothermic. The mechanism of chromium sorption onto the sorbent was established.

Preparation and metal uptake studies of modified forms of chitin

Chitin (C), a biopolymer which showed moderate sorption capacity (SC) towards Cu(II) and Fe(III) was suitably modified to enhance the SC. Three types of modifications viz., protonated chitin (PC), carboxylated chitin (CC) and grafted chitin (GC) were carried out to increase the SC. The modified forms of chitin showed enhanced SC for both Cu(II) and Fe(III) than the raw chitin. These sorbents were characterized by the FTIR and SEM with EDAX analysis. The various influencing parameters viz., contact time, pH and the interference of common anions during the sorption have been investigated. The sorption data was reasonably explained using Freundlich and Langmuir isotherms. The calculated values of thermodynamic parameters indicated that, the sorption is spontaneous and endothermic in nature. The order of selectivity of Cu(II) and Fe(III) on modified chitin was found to be Fe(III)>Cu(II). The suitability of modified chitin has been tested with the field samples collected in a near by industrial area. The suitable mechanism for the respective metal removal has been established.

Preparation of Modified Chitin for the Removal of Chromium(VI)

ABSTRACT Chitin was chemically modified into various forms for enhancing chromium sorption. The modified forms of chitin, viz., protonated chitin (PC), carboxylated chitin (CC), and grafted chitin (GC), possessed enhanced chromium sorption capacities (SCs) of 2812, 3010, and 3770 mg/kg, respectively, than the raw chitin (C), which showed the SC of 2316 mg/kg. The sorption experiments were carried out in batch mode to optimize various influencing parameters, viz., contact time, pH, common ions, and temperature. The sorbents were characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The modified forms of chitin removes chromium by means of electrostatic adsorption coupled reduction and complexation. The adsorption data were fitted with Freundlich and Langmuir isotherms. The calculated values of thermodynamic parameters indicate the nature of chromium sorption. The dynamic studies demonstrated that the sorption process follows pseudo-second-order and intraparticle diffusion models. The suitability of these modified chitin has been tested with field sample collected from a nearby industrial area.

Rapid and selective extraction of Pd(II) ions using the SCS type pincer ligand 1,3-bis(dimethylthiocarbamoyloxy)benzene, and its Pd(II) extraction mechanism

We report the salient metal complexation properties of the SCS pincer ligand 1,3-bis(dimethylthiocarbamoyloxy)benzene (1), and its Pd(II) extraction properties in liquid–liquid extraction. Rapid and selective extraction by 1 of >99% Pd(II) ions from an automotive catalyst leach liquor containing Rh, Pd, Pt, Zr, Ce, Ba, Al, La, and Y in Cl− media was observed. The extractability (E%) of 1 toward Pd was higher than that of the analogous compounds 1,4-bis(dimethylthiocarbamoyloxy)benzene (2), 1,4-bis(dimethylthiocarbamoyloxy)2,5-di-tert-butylbenzene (3), and 1,2-bis(dimethylthiocarbamoyloxy)benzene (4), and the commercial Pd(II) extractant di-n-hexyl sulfide (DHS). In o-dichlorobenzene diluent, 1 showed a high E%Pd (99.9–97.0%) in Cl− media (0.1–8.0 M) in 30 min, and excellent Pd(II) extraction and good phase separation were obtained with the various diluents studied. Pd(II) ions were stripped from the extractants using 0.1 M thiourea in 1.0 M HCl, enabling the reuse of 1. Loading capacity measurements revealed a Pd/extractant 1 ratio of 1. Palladation is promoted at the benzene ring and dimethylthiocarbamoyl moieties via formation of stable fused six-membered chelate rings. The extractant 1–Pd(II) complex was characterized using FT-IR spectroscopy, NMR spectroscopy, elemental analysis, single-crystal XRD study, and MALDI-TOF MS analysis. Extractant 1 displayed a high E%Pd (99%) even after five extraction cycles, indicating that it is very stable in acidic media and may be useful for the rapid and selective recovery of Pd(II) from catalyst solutions in platinum group metal refineries.

Feasibility Studies on Palladium Extraction from Leach Liquors of Automotive Catalysts Using p-Diethylphosphonomethylthiacalix[6]arene

Feasibility studies for the recovery of Pd(II) from leach liquors of automotive catalysts using p-diethylphosphonomethylthiacalix[6]arene (1) and p-tert-butylthiacalix[6]arene (2) were conducted. Compound 1 was found to be a more efficient extractant than 2 for Pd(II) ions, indicating selective extraction of Pd(II) ions [E% = 98.4%] from the leach liquors. The majority of other metal ions present in the leached solution were not extracted except Zr(IV) ions [E% = 22%]. Stripping of the Pd(II) ions from the extractants was performed using acidic thiourea, thereby enabling the recycling of the extractants.