ABSTRACT
Freely suspended and porous basket restrained granules of palladium nanoparticles supported on polymer-grafted Macadamia nutshell biomass (Pd@Polym-MNS) composite were used for the treatment chromium(VI)-containing water. In the presence of formic acid, the Pd@Polym-MNS demonstrated its activity in the adsorption-reduction-based conversion of noxious chromium(VI) to less toxic chromium(III) with a low activation energy of 13.4 kJ mol-1, ΔH0 (+ 10.8 kJ mol-1), ΔS0 (-270.0 J mol-1 K-1), and ΔG0 (+ 91.3 to + 98.0 kJ mol-1) indicated the exothermic, endergonic and non-spontaneous nature of the catalytic redox reaction. In addition to facilitating easy recovery, rinsing, and reuse, restraining the Pd@Polym-MNS in the basket reactor helped maintain the integrity of the catalysts by preventing violent collisions of suspended granules with the mixing apparatus and the walls of the reaction vessel. Whereas the pseudo-first-order rate constant was recorded as 0.157 min-1 upon initial use, values of the mean and relative standard deviation for the second, third and fourth consecutive uses were found to be 0.219 min-1 and 1.3%, respectively. According to a response surface methodological approach to batch experimentation, the initial concentration of chromium(VI) and catalyst dosage had the greatest impact on the redox reaction rate, accounting for 85.7% and 11.6% of the variability in the value of the pseudo-first-order rate constant, respectively. Mutually beneficial effects of the combinations of high formic acid and low chromium(VI) concentration, high temperature and catalyst dosage as well as high formic acid and catalyst dosage were recorded.
ABSTRACT
Electroplating and metalworking industries produce enormous amounts of waste containing heavy metals in their effluents, leading to potential threats to biotic and abiotic life. According to regulation, heavy metal contamination must be kept within the regulated standard of a few parts per million, which has led to a recent pique in interest in the utilization of nanofiltration technology for metal recovery. The effect of feed pH, pressure, metal concentration, and oxidation of metal on the rejection of heavy metal ions using three commercial nanofiltration membranes (NF, NF90, and NF270) were explored. To begin, studies of electrolyte salts, contact angle, and water permeability were employed to characterize the nanofiltration membranes. A dead-end module was used to test the permeation and retention capacities of the nanofiltration membranes. The results showed an increase in salt rejection for all metals examined irrespective of the membrane, at a pH below the isoelectric point. For divalent cations, the NF90 membrane achieved recovery capacities of 97% and 85% at 200 ppm and 20 ppm respectively, as compared to the recovery observed for Ni2+, Cu2+, and Pd2+ ions by NF and NF270. At a pH 2, 20 ppm and 5 bar, the NF90 membrane had the highest percent recovery, but at a pH 3, the recovery was at 95%. Mono and divalent stable Ag+ and Ni2+ ions showed a comparatively high percent recovery as compared to Pd2+ and Cu2+, which have high molecular weight and charge effect. In the presence of chelating agents, the membrane surface area is increased, resulting in high divalent ion recovery capacities due to favourable interaction with the polyamide functional group of the membranes. This study establishes the significance of oxidation in high removal efficiency cation in varying experimental conditions.
ABSTRACT
Membrane separation processes tender a capable option for energy-demanding separation processes. Nanofiltration (NF) and reverse osmosis (RO) membranes are among the most explored, with a latent use in the chemical industry. In this study, four commercial membranes (NF90, NF270, BW30, and XLE) were investigated for their applicability based on the key structural performance characteristics in the recycling of Pd-based catalysts from Heck coupling post-reaction mixture. Pure water and organic solvent permeabilities, uncharged solute permeability, swelling, and catalyst rejection studies of the membranes were conducted as well as the morphological characterization using Fourier transform infrared, field emission gun scanning electron microscopy, and atomic force microscopy. Characterization results showed trends consistent with the manufactures' specifications. Pure water and organic solvent fluxes generally followed the trend NF270 > NF90 > BW30 > XLE, with the solvent choice playing a major role in the separation process. Pd(PPh3)2Cl2 was well rejected by almost all membranes in 2-propanol; however, XLE rejects Pd(OAc)2 better at high pressure in acetonitrile. Our study, therefore, revealed that the separation and reuse of the two catalysts by NF90 at 10 bar resulted in 97% and 49% product yields with 52% and 10% catalyst retention for Pd(OAc)2 while Pd(PPh3)2Cl2. gave 87% and 6% yields with 58% and 36% catalyst retention in the first and second cycles, respectively. Considering, the influence of membrane-solute interactions in Pd-catalyst rejection, a careful selection of the polymeric membrane and solvent, a satisfactory separation, and recovery can be achieved.
ABSTRACT
Driven by the need for sustainably sourced catalysts and the use of reaction systems that generate environmentally benign by-products, the present study aimed to deposit stable, dispersed palladium (Pd) nanoparticles on the modified surfaces of granular macadamia nutshell (MNS) biomass for catalytic reduction of hexavalent chromium (Cr(VI)) to trivalent chromium (Cr(III)). Through wet impregnation with Pd(II) ions and subsequent hydrazine-mediated reduction to Pd(0), Pd nanoparticles were embedded in a scaffold of polyethyleneimine grafted on bleached MNS previously coated with a chemically bound layer of polyglycidyl methacrylate. Imagery from scanning electron microscopy showed the formation of different layers of the polymeric coating and dispersed palladium resulting from surface modification and palladium nanoparticle synthesis, respectively. X-ray diffraction analysis confirmed the formation of Pd on the modified MNS surface and suggested an estimated crystallite size of 5.0 nm. The supported nanoparticles exhibited catalytic activity in formic acid-mediated Cr(VI) reduction and showed promising stability with consecutive reuse. These findings set the stage for advanced studies into performance optimization.
