RESUMEN

Metallurgical wastewaters are characterized by a low pH (<4), high concentrations of sulfate (15 gSO42- L-1), and metal(loid)s. Current treatment requires the consumption of chemicals such as alkali and high levels of waste sludge generation. In this study, we have shown that combining water electrolysis and sulfate reducing bioreactors enables the in-situ generation of base and H2, eliminating the need for base and electron donor addition, resulting in the near-zero treatment of metallurgical wastewater. By extracting cations from the effluent of the system to the bioreactor, the bioreactor pH could be maintained by the in-situ production of alkali. The current for pH control varied between 112-753 mol electrons per m³ wastewater or 5-48 A m-2 electrode area. High concentrations of sulfate in the influent and addition of CO2 increased the current required to maintain a steady bioreactor pH. On the other hand, a high sulfate reduction rate and increased influent pH lowered the current required for pH control. Moreover, the current efficiency varied from 14% to 91% and increased with higher pH and cation (Na+, NH4+, K+, Mg2+, Ca2+) concentrations in the middle compartment of the electrochemical cell. The salinity was lowered from 70-120 mS cm-1 in the influent to 5-20 mS cm-1 in the system effluent. The energy consumption of the electrochemical pH control varied between 10 and 100 kWh m-3 and was affected by the conductivity of the wastewater. Industrial wastewater was treated successfully with an average energy consumption of 39 ± 7 kWh m-3, removing sulfate from 15 g SO42- L-1 to 0.5 ± 0.5 g SO42- L-1 at a reduction rate of 20 ± 1 gSO42- L-1 d-1..Metal(loid)s such as As, Cd, Cu, Pb, Te, Tl, Ni and Zn were removed to levels of 1-50 µg L-1.

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RESUMEN

Precipitation of arsenic as As2S3 produces little waste sludge, has the potential for low chemical consumption and for selective metal(loid) removal. In this study, arsenic removal from acidic (pH 2), metallurgical wastewater was tested in industrially relevant conditions. Sulfides added at a S:As molar ratio of 2.5 and 5 resulted in removal of 99% and 84% of As(III) and As(V). Precipitation of As2S3 from the As(III) and industrial wastewater containing 17% As(V) was nearly instantaneous. For the synthetic As(V) solution, reduction to As(III) was the rate limiting step. At a S:As ratio of 20 and an observed removal rate (k2 = 4.8 (mol L-1) h-1), two hours were required to remove of 93% of arsenic from a 1 g As L-1 solution. In the case of As(V) in industrial samples this time lag was not observed, showing that components in the industrial wastewater affected the removal and reduction of arsenate. Speciation also affected flocculation and coagulation characteristics of As2S3 particles: As(V) reduction resulted in poor coagulation and flocculation. Selective precipitation of arsenic was possible, but depended on speciation, S:As ratio and other metals present.

RESUMEN

With the number of easily accessible ores depleting, alternate primary and secondary sources are required to meet the increasing demand of economically important metals. Whilst highly abundant, these materials are of lower grade with respect to traditional ores, thus highly selective and sustainable metal extraction technologies are needed to reduce processing costs. Here, we investigated the metal leaching potential of biogenic ammonia produced by a ureolytic strain of Lysinibacillus sphaericus on eight primary and secondary materials, comprised of mining and metallurgical residues, sludges and automotive shredder residues (ASR). For the majority of materials, moderate to high yields (30-70%) and very high selectivity (>97% against iron) of copper and zinc were obtained with 1 mol L-1 total ammonia. Optimal leaching was achieved and further refined for the ASR in a two-step indirect leaching system with biogenic ammonia. Copper leaching was the result of local corrosion and differences in leaching against the synthetic (NH4)2CO3 control could be accounted for by pH shifts from microbial metabolism, subsequently altering free NH3 required for coordination. These results provide important findings for future sustainable metal recovery technologies from secondary materials.

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