High-rate and -yield continuous fluidized-bed bioconversion of glucose-to-gluconic acid for enhanced metal leaching

Continuous low-cost bulk biolixiviant production remains as one of the main challenges of heterotrophic bioleaching towards large scale application. This study aimed at developing non-aseptic Gluconobacter oxydans-amended fluidized-bed reactor (FBR) process for continuous production of gluconic acid for efficient leaching of rare earth elements (REEs) and base metals from spent nickel-metal-hydride (NiMH) batteries. In preliminary experiments, the FBR became contaminated and massively overgrown by air-borne fungus, Leptobacillium leptobactrum. In a series of batch bioassays, operational conditions were investigated to discourage the fungal activity i.e., an ecologically engineered niche for gluconic acid production. High gluconate concentration (≥100 g/l) and/or low pH (≤2.5) gave a selective preference for G. oxydans growth over L. leptobactrum and controlled the activity of possible contaminants during FBR continuous operation. The highest gluconic acid production rate of 390 g/l∙d with corresponding glucose-to-gluconic acid conversion yield of 94% was obtained at hydraulic retention time (HRT) of 6.3 h and 380 g/l∙d glucose loading rate. Using the FBR effluents as leaching agents, respectively, total base metals and REEs leaching yields of up to 82% and 55% were achieved within 7 days at 1% (w/v) spent battery pulp density. The obtained glucose-to-gluconic acid conversion rates and yields were one of the highest reported for any glucose biotransformation process. The REE leaching yields were higher than those reported for similar high metal-grade REE secondary sources. The high-rate glucose-to-gluconic acid bioconversion in the non-aseptic system utilizing microbial ecology based FBR operation strategy rather than aseptic chemostats indicates industrial feasibility of gluconic acid production and thus, the applicability of heterotrophic bioleaching.publishedVersionPeer reviewe

Low residual dissolved phosphate in spent medium bioleaching enables rapid and enhanced solubilization of rare earth elements from end-of-life NiMH batteries

Successful heterotrophic bioleaching with high metal yields requires an efficient leaching agent production and minimization of secondary reactions such as precipitation of leached metals with growth medium components. In this study, the role of the secondary reactions on bioleaching of spent nickel-metal-hydride batteries was investigated. Substitution of K2HPO4 by yeast extract (YE) reduced precipitation of both base metals and rare earth elements (REEs). REEs were proportionally more affected by precipitation than base metals. Optimizing the ratio of YE to glucose in the growth medium resulted in glucose to gluconic acid conversion yield of 90% by Gluconobacter oxydans. In one-day leaching with YE medium, 28.8% Mn, 52.8% Fe, 22.9% Co, 12.0% Ni, and 19.5% of total REEs were extracted. The leach liquor obtained with the YE medium resulted in leaching of 1.5 and 11.0 times more of total base metals and REEs, respectively, than with phosphate medium. Experimental results were consistent with geochemical modeling results corroborating the benefit of low phosphate concentrations in leaching systems at neutral to moderately acidic pH. In summary, substitution of K2HPO4 with YE in gluconic acid production phase with G. oxydans reduced subsequent base metal and especially REE precipitation during leaching and, thus, enhanced the overall metal extraction.publishedVersionPeer reviewe

Leaching of rare earth elements and base metals from spent NiMH batteries using gluconate and its potential bio-oxidation products

Gluconate is known to mediate metal leaching. However, during bioleaching by e.g., Gluconobacter oxydans, gluconate can be oxidized to 2-ketogluconate and 5-ketogluconate. The impact of bio-oxidation of gluconate on metal leaching has not been investigated. Therefore, the aim of this study was to investigate leaching of rare earth elements (REEs) and base metals from spent nickel-metal-hydride (NiMH) batteries using gluconate, 2-ketogluconate and 5-ketogluconate. Batch leaching assays were conducted under controlled and uncontrolled pH conditions for 14 days using 60 mM of either the individual leaching agents or their various combinations. At target pH of 6.0 ± 0.1 and 9.0 ± 0.1 and without pH control, complexolysis was the dominating leaching mechanism and higher REE leaching efficiency was obtained with gluconate, while 5-ketogluconate enabled more efficient base metal leaching. At target pH of 3.0 ± 0.1, acidolysis dominated, and the base metal and REE leaching yields with all the tested leaching agents were higher than under the other studied pH conditions. The highest base metal and REE leaching yields (%) were obtained using gluconate at target pH of 3.0 ± 0.1 being 100.0 Mn, 90.3 Fe, 89.5 Co, 58.5 Ni, 24.0 Cu, 29.3 Zn and 56.1 total REEs. The obtained results are useful in optimization of heterotrophic bioleaching.publishedVersionPeer reviewe