High-value utilisation of PGM-containing residual oil: Recovery of inorganic acids, potassium, and PGMs using a zero-waste approach.

Residual oil containing platinum group metals (PGMs), which is under-researched, can easily pose resource waste and environmental risks. PGMs feature as scarce strategic metals, and inorganic acids and potassium salts are also considered valuable. An integrated process for the harmless treatment and recovery of useful resources from residual oil is proposed herein. This work developed a zero-waste process based on the study of the main components and characteristics of the PGM-containing residual oil. The process consists of three modules: pre-treatment for phase separation, liquid-phase resource utilisation, and solid-phase resource utilisation. Separating the residual oil into liquid and solid phases allows for the maximum recovery of valuable components. However, concerns about the accurate determination of valued components emerged. Findings revealed that Fe and Ni are highly susceptible to spectral interference in the PGMs test when using the inductively coupled plasma method. After studying 26 PGM emission lines, Ir 212.681 nm, Pd 342.124 nm, Pt 299.797 nm, and Rh 343.489 nm were reliably identified. Finally, formic acid (81.5 g/t), acetic acid (117.2 kg/t), propionic acid (291.9 kg/t), butyric acid (3.6 kg/t), potassium salt (553.3 kg/t), Ir (27.8 g/t), Pd (10960.0 g/t), Pt (193.1 g/t), and Rh (109.8 g/t) were successfully obtained from the PGM-containing residual oil. This study provides a helpful reference for the determination of PGM concentrations and high-value utilisation of PGM-containing residual oil.

Enhanced metal bioleaching mechanisms of extracellular polymeric substance for obsolete LiNixCoyMn1-x-yO2 at high pulp density.

Harmful chemicals present in electric vehicle Li-ion batteries (EV LIBs) can limit the pulp density of bioleaching processes using Acidithiobacillus sp. to 1.0% (w/v) or lower. The strong enhancing mechanisms of extracellular polymeric substances (EPS) on the bioleaching of metals from spent EV LIBs at high pulp density (4% w/v) were studied using bio-chemical, spectroscopic, surface structure imaging and bioleaching kinetic methods. Results demonstrated that the added EPS significantly improved bioleaching efficiency of Ni, Co and Mn improved by 42%, 40% and 44%, respectively. EPS addition boosted the growth of cells under adverse conditions to produce more biogenic H+ while Fe3+ and Fe2+ were adsorbed by the biopolymer. This increased Li extraction by acid dissolution and concentrated the Fe3+/Fe2+ cycle via non-contact mechanisms for the subsequent contact bioleaching of Ni, CO and Mn at the EV LIB-bacteria interface. During the leaching process, added EPS improved adhesion of the bacterial cells to the EV LIBs, and the resultant strong interfacial reactions promoted bioleaching of the target metals. Hence, a combination of non-contact and contact mechanisms initiated by the addition of EPS enhanced the bioleaching of spent EV LIBs at high pulp density.

Indirect bioleaching recovery of valuable metals from electroplating sludge and optimization of various parameters using response surface methodology (RSM).

Electroplating sludge contains amounts of valuable/toxic metals as a typical hazardous solid waste, but existing technology is hard to simultaneously gain the high recovery of valuable metals and its convert into general solid waste. In this study, indirect bioleaching process was optimized by using RSM for high recovery of four valuable metals (Ni, Cu, Zn and Cr) from electroplating sludge and its shift into general waste. The results showed that the maximum leaching rate respectively was 100% for Ni, 96.5% for Cu, 100% for Zn and 76.1% for Cr at the optimal conditions. In particular, bioleaching saw a much better performance than H2SO4 leaching in removal of highly toxic Cr (76.1% vs. 30.2%). The extraction efficiency of Cr by H2SO4 leaching sharply rose to 72.6% in the presence of 9.0 g/L Fe3+, suggesting that Fe3+ played an important role in the bioleaching of Cr. Based on bioleaching dynamics analysis, it was speculated that Fe3+ passes through the solid shell and enter inside the sludge to attack Cr assisting by extracellular polymeric substances (EPS), leading to high extraction and low residue of Cr. Meanwhile, due to high-efficient release and removal of valuable/toxic metals by bioleaching, the bioleached residues successfully degraded into general based on TCLP test and can be reused as construction material safely.

Controlled Biosynthesis of ZnCdS Quantum Dots with Visible-Light-Driven Photocatalytic Hydrogen Production Activity.

The development of visible-light-responsive photocatalysts with high efficiency, stability, and eco-friendly nature is beneficial to the large-scale application of solar hydrogen production. In this work, the production of biosynthetic ternary ZnCdS photocatalysts (Eg = 2.35-2.72 eV) by sulfate-reducing bacteria (SRB) under mild conditions was carried out for the first time. The huge amount of biogenic S2- and inherent extracellular proteins (EPs) secreted by SRB are important components of rapid extracellular biosynthesis. The ternary ZnCdS QDs at different molar ratios of Zn2+and Cd2+ from 15:1 to 1:1 were monodisperse spheres with good crystallinity and average crystallite size of 6.12 nm, independent of the molar ratio of Cd2+ to Zn2+. All the ZnCdS QDs had remarkable photocatalytic activity and stability for hydrogen evolution under visible light, without noble metal cocatalysts. Especially, ZnCdS QDs at Zn/Cd = 3:1 showed the highest H2 production activity of 3.752 mmol·h-1·g-1. This excellent performance was due to the high absorption of visible light, the high specific surface area, and the lower recombination rate between photoexcited electrons and holes. The adhered inherent EPs on the ZnCdS QDs slowed down the photocorrosion and improved the stability in photocatalytic hydrogen evolution. This study provides a new direction for solar hydrogen production.

Generation behavior of extracellular polymeric substances and its correlation with extraction efficiency of valuable metals and change of process parameters during bioleaching of spent petroleum catalyst.

The vital functions of extracellular polymeric substances (EPS) have been well recognized in bioleaching of sulfide ores. However, no report is available about the role of EPS in bioleaching of spent catalyst. To completely and deeply understand the functions of EPS in bioleaching of spent catalyst, the generation behavior of EPS at various pulp densities during bioleaching was characterized by three-dimensional excitation-emission matrix (3DEEM), and its relevance with bioleaching performance and process parameters were analyzed using mathematical means. The results showed that the EPS contain humus-like substances as main component (>70%) and protein-like substances as minor component (<30%). Both total EPS and humus-like substances mainly keep growing over the whole duration of bioleaching at low pulp density of 5.0% or lower; whereas total EPS and humus-like fraction keep declining at high pulp density of 7.5% or higher. Among the total EPS and its components, humus-like substances only have a positive significant correlation with bioleaching efficiencies of both Co and Mo and affect bioleaching process more greatly due to greater correlation coefficient. Biofilm appears at the spent catalyst surface under 2.5% of pulp density mediated by EPS while no biofilm occurs at 10% of pulp density due to shortage of EPS, accounting for the great difference in bioleaching efficiencies between high and low pulp densities which are 48.3% for Mo and 50.0% for Co at 10% of pulp density as well as 75.9% for Mo and 78.8% for Co at 2.5% of pulp density, respectively.

Improved bioleaching of copper and zinc from brake pad waste by low-temperature thermal pretreatment and its mechanisms.

A considerable amount of brake pad waste which is composed of phenolic resin and a variety of toxic heavy metals is produced both in China and around the world owing to the flourishing automobile industry. The safe, low cost and eco-sound bioleaching was utilized to extract the valuable metals Cu and Zn from the waste. The results showed that although bioleaching is more efficient in the extraction of Cu and Zn than the chemical counterpart, rather low bioleaching yields of 34% for Cu and 72% for Zn were obtained because of the complicated components and refractory nature of the waste. However, a low-temperature thermal pretreatment at 400 °C notably lifted the bioleaching efficiencies of Cu and Zn to 98% and nearly 100%, respectively. The thermal treatment removed the oil substances, transformed the acid insoluble Cu0 into acid soluble CuO and destroyed the chelation/complexation of the phenolic resin to loose Cu and Zn, promoting bioleaching performance of Cu and Zn. The combined processes of low-temperature thermal pretreatment and bioleaching is totally qualified for the extraction of Cu and Zn from the refractory waste.

Functional exploration of extracellular polymeric substances (EPS) in the bioleaching of obsolete electric vehicle LiNixCoyMn1-x-yO2 Li-ion batteries.

As a fairly new concept, the recovery of valuable metals from urban mining by using bioleaching has become a hotspot. However, the function of extracellular polymeric substances (EPS) in the bioleaching of urban mining gains little attention. The current study used spent EV LIBs to represent urban mining products and systematically explored the function and role of EPS in the attachment of cells to the cathodes, formation of aggregates (cell-EPS-cathode), variation in the electrical and surface properties of the aggregates, concentration of both Fe2+ and Fe3+ surrounding the aggregates, electron transfer inside the aggregates and metals released from the aggregates. The results indicated that a strong adhesion of cells to the cathodes occurs mediated by EPS via both hydrophobic force as a main role and electrostatic force as a minor role. Second, the EPS not only adsorb Fe3+ but also more strongly adsorb Fe2+ to concentrate the Fe2+/Fe3+ cycle inside the aggregates, witnessing stronger reductive attack on the high valence state of metals as a contact reductive mechanism. Third, the retention or addition of EPS elevated the electronic potential and reduced the electronic resistance to lift the corrosion electric current, thereby boosting the electron transfer and metal dissolution.