Bioelectrochemical Recovery of Energy and Metals from Simulated Mining Waters
Sulonen, Mira (2017-09-15)
15.09.2017
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Kuvaus
Peer reviewed
Tiivistelmä
Extremely acidic water with high metal concentrations is often produced during mining and processing of sulfidic ores. Sulfur-oxidizing microorganisms contribute significantly to the acidification of the water streams and oxygen depletion by oxidizing reduced inorganic sulfur compounds (RISCs) — which are released to the mining waters during the processing of sulfide minerals — to sulfuric acid. The acidic water continues leaching metals from minerals and the metal concentrations thus further increase.
Certain metals can be recovered from acidic solutions by using them as the electron acceptor at the cathode of an electrochemical system. The metal ions accept electrons from an electrode and deposit on the surface of the electrode in pure elemental form. The electrical current required for the electrodeposition of metals is conventionally drawn from the oxidation of water. However, with the assist of electroactive microorganisms, biodegradable compounds can be used as the source of the required energy. Electroactive microorganisms oxidize a substrate and donate electrons to an anode electrode. The flow of electrons from anode to cathode creates electrical current, which can be utilized in the electrodeposition of the metals. As mining waters do not usually contain organic compounds, RISCs are promising substrates for the recovery of metals from mining waters — they are present in the same stream and can be oxidized at lower potential than water. In addition, with the electrochemical treatment both metals and RISCs could be removed from the water streams simultaneously.
The aim of this work was to use tetrathionate (S4O62-) as the substrate for bioelectrochemical and electrochemical current generation. The possibility to spontaneously produce electricity from tetrathionate was first studied in microbial fuel cells (Paper I). After successful electricity production was obtained, a tetrathionate-fed microbial fuel cell was monitored for over 740 days to determine the long-term stability of such systems (Paper II). The anode potential was then externally adjusted in order to determine the minimum anode potential required for bioelectrochemical and electrochemical tetrathionate degradation (Paper III). Finally, the external voltage required for the simultaneous removal of tetrathionate and copper was determined (Paper IV).
The experiments were conducted using two-chamber flow through reactors at room temperature (22±5 °C) and highly acidic conditions (pH < 2.5). The initial lag-time for electricity production from tetrathionate was relatively long in bioelectrochemical systems (approximately 100 days), but spontaneous electricity production was proven successful with ferric iron as the cathodic electron acceptor. By optimizing the external resistance, the current density was successfully improved from 80 mA m-2 (1000 Ω) to 225 mA m-2 (100 Ω). In the long-term experiment, biofouling or accumulating reaction products were not observed to limit the electricity production even after 740 days of operation. The minimum anode potential for tetrathionate degradation was observed to be 0.3 V vs. Ag/AgCl in the bioelectrochemical systems and 0.5 V in the abiotic electrochemical systems. Higher tetrathionate degradation rates were obtained in the bioelectrochemical systems (>110 mg L-1 d-1) than in the electrochemical systems (<35 mg L-1 d-1). The reaction products of bioelectrochemical tetrathionate degradation were sulfate and elemental sulfur, while in electrochemical systems only sulfate was detected. For the efficient removal of tetrathionate and copper, applied voltage of above 1.0 V was required. The concentrations of tetrathionate and copper were successfully decreased below the limits set for toxicity (0.5 g S4O62- L-1) and mining effluent discharge (0.3 mg Cu2+ L-1).
This study demonstrates for the first time that tetrathionate can be used the substrate for bioelectrochemical current generation. In bioelectrochemical systems with an efficient catholyte, tetrathionate is degraded and electricity is produced spontaneously, but abiotic electrochemical degradation requires external energy. Both bioelectrochemical and electrochemical systems provided higher current densities than a water-oxidizing control reactor when controlling the anode potential or applying external voltage. The simultaneous removal of tetrathionate and copper shows that bioelectrochemical and electrochemical systems are promising alternatives for the treatment of mining waters.
Certain metals can be recovered from acidic solutions by using them as the electron acceptor at the cathode of an electrochemical system. The metal ions accept electrons from an electrode and deposit on the surface of the electrode in pure elemental form. The electrical current required for the electrodeposition of metals is conventionally drawn from the oxidation of water. However, with the assist of electroactive microorganisms, biodegradable compounds can be used as the source of the required energy. Electroactive microorganisms oxidize a substrate and donate electrons to an anode electrode. The flow of electrons from anode to cathode creates electrical current, which can be utilized in the electrodeposition of the metals. As mining waters do not usually contain organic compounds, RISCs are promising substrates for the recovery of metals from mining waters — they are present in the same stream and can be oxidized at lower potential than water. In addition, with the electrochemical treatment both metals and RISCs could be removed from the water streams simultaneously.
The aim of this work was to use tetrathionate (S4O62-) as the substrate for bioelectrochemical and electrochemical current generation. The possibility to spontaneously produce electricity from tetrathionate was first studied in microbial fuel cells (Paper I). After successful electricity production was obtained, a tetrathionate-fed microbial fuel cell was monitored for over 740 days to determine the long-term stability of such systems (Paper II). The anode potential was then externally adjusted in order to determine the minimum anode potential required for bioelectrochemical and electrochemical tetrathionate degradation (Paper III). Finally, the external voltage required for the simultaneous removal of tetrathionate and copper was determined (Paper IV).
The experiments were conducted using two-chamber flow through reactors at room temperature (22±5 °C) and highly acidic conditions (pH < 2.5). The initial lag-time for electricity production from tetrathionate was relatively long in bioelectrochemical systems (approximately 100 days), but spontaneous electricity production was proven successful with ferric iron as the cathodic electron acceptor. By optimizing the external resistance, the current density was successfully improved from 80 mA m-2 (1000 Ω) to 225 mA m-2 (100 Ω). In the long-term experiment, biofouling or accumulating reaction products were not observed to limit the electricity production even after 740 days of operation. The minimum anode potential for tetrathionate degradation was observed to be 0.3 V vs. Ag/AgCl in the bioelectrochemical systems and 0.5 V in the abiotic electrochemical systems. Higher tetrathionate degradation rates were obtained in the bioelectrochemical systems (>110 mg L-1 d-1) than in the electrochemical systems (<35 mg L-1 d-1). The reaction products of bioelectrochemical tetrathionate degradation were sulfate and elemental sulfur, while in electrochemical systems only sulfate was detected. For the efficient removal of tetrathionate and copper, applied voltage of above 1.0 V was required. The concentrations of tetrathionate and copper were successfully decreased below the limits set for toxicity (0.5 g S4O62- L-1) and mining effluent discharge (0.3 mg Cu2+ L-1).
This study demonstrates for the first time that tetrathionate can be used the substrate for bioelectrochemical current generation. In bioelectrochemical systems with an efficient catholyte, tetrathionate is degraded and electricity is produced spontaneously, but abiotic electrochemical degradation requires external energy. Both bioelectrochemical and electrochemical systems provided higher current densities than a water-oxidizing control reactor when controlling the anode potential or applying external voltage. The simultaneous removal of tetrathionate and copper shows that bioelectrochemical and electrochemical systems are promising alternatives for the treatment of mining waters.
Kokoelmat
- TUNICRIS-julkaisut [19369]