Ni removal from aqueous solutions by chemical reduction: Impact of pH and pe in the presence of citrate.

The chemical precipitation of Ni ions from industrial wastewater at alkaline pH values creates waste chemical sludge (e.g., Ni(OH)2). We herein focused on Ni removal via chemical reduction using dithionite, by converting Ni(II) to its elemental or other valuable forms. Without the presence of a chelator (e.g., citrate), the nickel reduction efficiency increased with increasing dithionite:Ni molar ratio, reaching ∼99% at ratios above 3:1. The effect of pH on Ni reduction was in agreement with the standard redox potentials (pe0) of dithionite, which became more negative with an increase in pH leading to greater Ni reduction efficiencies. With the formation of Ni-citrate chelates, however, the Ni reduction deteriorated. Elevated pH and temperature improved nickel reduction, due to the greater reducing power of dithionite. The optimal pH value for Ni(II) reduction was found to be ∼8. Injecting Cu seed particles enhanced the rate and amount of Ni reduced. NiS and Ni3S2 were identified in the crystal of the resulting solids by X-ray crystallography, and the presence of elemental Ni was explained by X-ray photoelectron spectroscopy. The chemical reduction of actual printed circuit board wastewater with the dithionite:Ni(II) molar ratio dose of 12:1 retrieved ∼99% nickel after 30-min reaction at 40°C.

Recovery of Cu(II) by chemical reduction using sodium dithionite: effect of pH and ligands.

Wastewaters containing Cu(II) and ligands are ubiquitous in various industrial sectors, and efficacy of copper removal processes, especially precipitation, is greatly compromised by ligands. Chemical reduction, being commonly employed for production of metal nanoparticles, is also effective for metal removal. Adjustment of pH and addition of ligands are important to control the particle size in metallic nanoparticle production. Exploiting the fact that ligands and metals coexist in many wastewaters, chemical reduction was employed to treat ligand-containing wastewater in this study. The experimental result shows that depending on pH, type of ligands, and copper:ligand molar ratio, copper could be removed by either the reduction or precipitation mechanism. Almost complete copper removal could be achieved by the reduction mechanism under optimal condition for solutions containing either EDTA (ethylenediaminetetraacetic acid) or citrate ligands. For solutions containing ammonia, depending on pH and Cu:ammonia molar ratio, copper was removed by both precipitation and reduction mechanisms. At pH of 9.0, formation of nano-sized particles, which readily pass through a 0.45 µm filter used for sample pretreatment before residual copper analysis, results in the lowest copper removal efficiency. Both cuprous oxide and metallic copper are identified in the solids produced, and the possible explanations are provided.

Integration of polyelectrolyte enhanced ultrafiltration and chemical reduction for metal-containing wastewater treatment and metal recovery.

Chemical reduction was firstly employed to treat synthetic wastewaters of various compositions prepared to simulate the retentate stream of polyelectrolyte enhanced ultrafiltration (PEUF). With fixed Cu:polyethylenimine (PEI) monomer:dithionite molar ratio, increasing copper concentration increases copper removal efficiency. Under fixed Cu:dithionite molar ratio and fixed Cu concentration, increasing PEI monomer:copper molar ratio decreases copper removal efficiency. The formation of nano-sized copper particles, which readily pass through 0.45 µm filter used for sample pretreatment before residual copper analysis, might be the reason behind the decreasing copper removal efficiency observed. Particle size analysis shows that the size of copper particles, which are formed through reduction reaction, increases with decreasing pH value and increasing reaction time. As ultrafiltration is capable of removing these nano-sized particles, integration of chemical reduction and PEUF is proposed to simultaneously achieve regeneration of polyelectrolyte and recovery of copper in one process. Results show that the proposed process could achieve almost complete copper removal without being affected by reaction pH.

Recovery of Cu(II) by chemical reduction using sodium dithionite.

Wastewaters containing Cu(II) along with ligands are ubiquitous in various industrial sectors. Efficacy of treatment processes for copper removal, especially precipitation, is greatly debilitated by ligands. Chemical reduction being commonly employed for production of metal nanoparticles has also been used for removing copper. Addition of ammonia was reported to be essential for improving copper reduction efficiency by increasing copper solubility at alkaline pH values. In this study, chemical reduction was employed to treat ligand-containing wastewater, exploiting the fact that ligands and metals are coexisted in many wastewaters. Result shows that copper ions were removed by either reduction or precipitation mechanisms depending on pH, type of ligands, and mixing condition. Complete copper reduction/removal was achieved under optimal condition. The lowest removal efficiency observed at pH 9.0 for ammonia system is due to formation of nano-sized particles, which are readily to pass through 0.45µm filter used for sample pretreatment before copper analysis. Instead of producing metallic copper, cuprous and copper oxide are identified in the samples collected from ammonia system and EDTA system, respectively. Re-oxidation of metallic copper particles by atmospheric oxygen during sample handling or incomplete reduction of Cu(II) ions during reduction process might be the cause. Finally, reduction process was applied to treat real wastewater, achieving complete removal of copper but only 10% of nickel.

Comparison of high pressure and ambient pressure aerobic granulation sequential batch reactor processes.

Due to granule size, substrate and oxygen become limited in the core of granules leading to cell lysis at the core. Loss of granule stability is still a major barrier for practical application of AG. Compared to ambient pressure condition (AP), operation of AG under high pressure (HP) is a favorable condition for formation and stability of granules. Experimental results show that granulation was facilitated under HP condition. MLSS and size of granules under AP system are higher than those under HP system. However, SS of effluent in AP is higher than those in HP and is consisted mainly of flocculent sludge. Longer SRT and lower biomass yield are obtained in HP system, indicating that less sludge will be produced in HP system. HP system can operate at high nitrogen loading. Complete nitrification was observed earlier in HP, indicating that the growth of NOB was facilitated under high dissolved oxygen.