Younggy Kim

Energy Capture from Thermolytic Solutions in Microbial Reverse-Electrodialysis Cells

Waste Not The organic matter in wastewater is a potentially vast and sustainable energy source; however, most wastewater treatment plants consume energy. Cusick et al. (p. 1474, published online 1 March) combined a microbial fuel cell with a reverse-electrodialysis system to boost the voltage output and the power density over a simple microbial fuel cell. The use of ammonium bicarbonate as a fuel for reverse electrodialysis while microorganisms simultaneously turn organic matter into electricity not only allows for the capturing of waste heat, but could eventually produce enough energy to offset the energy used in conventional wastewater treatment systems. Thermally induced salt gradients could augment the electricity generated by microbial fuel cells from wastewater. Reverse electrodialysis allows for the capture of energy from salinity gradients between salt and fresh waters, but potential applications are currently limited to coastal areas and the need for a large number of membrane pairs. Using salt solutions that could be continuously regenerated with waste heat (≥40°C) and conventional technologies would allow much wider applications of salinity-gradient power production. We used reverse electrodialysis ion-exchange membrane stacks in microbial reverse-electrodialysis cells to efficiently capture salinity-gradient energy from ammonium bicarbonate salt solutions. The maximum power density using acetate reached 5.6 watts per square meter of cathode surface area, which was five times that produced without the dialysis stack, and 3.0 ± 0.05 watts per square meter with domestic wastewater. Maximum energy recovery with acetate reached 30 ± 0.5%.

Series assembly of microbial desalination cells containing stacked electrodialysis cells for partial or complete seawater desalination.

A microbial desalination cell (MDC) is a new approach for desalinating water based on using the electrical current generated by exoelectrogenic bacteria. Previously developed MDCs have used only one or two desalination chambers with substantial internal resistance, and used low salinity catholytes containing a buffered or acid solution. Here we show that substantially improved MDC performance can be obtained even with a nonbuffered, saline catholyte, by using an electrodialysis stack consisting of 5 pairs of desalting and concentrating cells. When 4 stacked MDCs were used in series (20 total pairs of desalination chambers), the salinity of 0.06 L of synthetic seawater (35 g/L NaCl) was reduced by 44% using 0.12 L of anode solution (2:1). The resistive loss in the electrodialysis stack was negligible due to minimization of the intermembrane distances, and therefore the power densities produced by the MDC were similar to those produced by single chamber microbial fuel cells (MFCs) lacking desalination chambers. The observed current efficiency was 86%, indicating separation of 4.3 pairs of sodium and chloride ions for every electron transferred through the circuit. With two additional stages (total of 3.8 L of anolyte), desalination was increased to 98% salt removal, producing 0.3 L of fresh water (12.6:1). These results demonstrate that stacked MDCs can be used for efficient desalination of seawater while at the same time achieving power densities comparable to those obtained in MFCs.

Hydrogen production from inexhaustible supplies of fresh and salt water using microbial reverse-electrodialysis electrolysis cells

There is a tremendous source of entropic energy available from the salinity difference between river water and seawater, but this energy has yet to be efficiently captured and stored. Here we demonstrate that H2 can be produced in a single process by capturing the salinity driven energy along with organic matter degradation using exoelectrogenic bacteria. Only five pairs of seawater and river water cells were sandwiched between an anode, containing exoelectrogenic bacteria, and a cathode, forming a microbial reverse-electrodialysis electrolysis cell. Exoelectrogens added an electrical potential from acetate oxidation and reduced the anode overpotential, while the reverse electrodialysis stack contributed 0.5–0.6 V at a salinity ratio (seawater:river water) of 50. The H2 production rate increased from 0.8 to 1.6 m3-H2/m3-anolyte/day for seawater and river water flow rates ranging from 0.1 to 0.8 mL/ min. H2 recovery, the ratio of electrons used for H2 evolution to electrons released by substrate oxidation, ranged from 72% to 86%. Energy efficiencies, calculated from changes in salinities and the loss of organic matter, were 58% to 64%. By using a relatively small reverse electrodialysis stack (11 membranes), only ∼1% of the produced energy was needed for pumping water. Although Pt was used on the cathode in these tests, additional tests with a nonprecious metal catalyst (MoS2) demonstrated H2 production at a rate of 0.8 m3/m3/d and an energy efficiency of 51%. These results show that pure H2 gas can efficiently be produced from virtually limitless supplies of seawater and river water, and biodegradable organic matter.

Capturing power at higher voltages from arrays of microbial fuel cells without voltage reversal

Voltages produced by microbial fuel cells (MFCs) cannot be sustainably increased by linking them in series due to voltage reversal, which substantially reduces stack voltages. It was shown here that MFC voltages can be increased with continuous power production using an electronic circuit containing two sets of multiple capacitors that were alternately charged and discharged (every one second). Capacitors were charged in parallel by the MFCs, but linked in series while discharging to the circuit load (resistor). The parallel charging of the capacitors avoided voltage reversal, while discharging the capacitors in series produced up to 2.5 V with four capacitors. There were negligible energy losses in the circuit compared to 20–40% losses typically obtained with MFCs using DC-DC converters to increase voltage. Coulombic efficiencies were 67% when power was generated via four capacitors, compared to only 38% when individual MFCs were operated with a fixed resistance of 250 Ω. The maximum power produced using the capacitors was not adversely affected by variable performance of the MFCs, showing that power generation can be maintained even if individual MFCs perform differently. Longer capacitor charging and discharging cycles of up to 4 min maintained the average power but increased peak power by up to 2.6 times. These results show that capacitors can be used to easily obtain higher voltages from MFCs, allowing for more useful capture of energy from arrays of MFCs.

Microbial Reverse Electrodialysis Cells for Synergistically Enhanced Power Production

A new type of bioelectrochemical system for producing electrical power, called a microbial reverse-electrodialysis cell (MRC), was developed to increase voltages and power densities compared to those generated individually by microbial fuel cells (MFCs) or reverse electrodialysis (RED) systems. In RED systems, electrode overpotentials create significant energy losses due to thermodynamically unfavorable electrode reactions, and therefore a large number of stacked cells must be used to have significant energy recovery. This results in high capital costs for the large number of membranes, and increases energy losses from pumping water through a large number of cells. In an MRC, high overpotentials are avoided through oxidation of organic matter by exoelectrogenic bacteria on the anode and oxygen reduction on the cathode. An MRC containing only five pairs of RED cells, fed solutions typical of seawater (600 mM NaCl) and river water (12 mM NaCl) at 0.85 mL/min, produced up to 3.6 W/m(2) (cathode surface area) and 1.2-1.3 V with acetate as a substrate. Pumping accounted for <2% of the produced power. A higher flow rate (1.55 mL/min) increased power densities up to 4.3 W/m(2). COD removal was 98% with a Coulombic efficiency of 64%. Power production by the individual components was substantially lower with 0.7 W/m(2) without salinity driven energy, and <0.015 W/m(2) with reduced exoelectrogenic activity due to substrate depletion. These results show that the combination of an MFC and a RED stack synergistically increases performance relative to the individual systems, producing a new type of system that can be used to more efficiently capture salinity driven energy from seawater and river water.

Hydrogen generation in microbial reverse-electrodialysis electrolysis cells using a heat-regenerated salt solution.

Hydrogen gas can be electrochemically produced in microbial reverse-electrodialysis electrolysis cells (MRECs) using current derived from organic matter and salinity-gradient energy such as river water and seawater solutions. Here, it is shown that ammonium bicarbonate salts, which can be regenerated using low-temperature waste heat, can also produce sufficient voltage for hydrogen gas generation in an MREC. The maximum hydrogen production rate was 1.6 m(3) H(2)/m(3)·d, with a hydrogen yield of 3.4 mol H(2)/mol acetate at a salinity ratio of infinite. Energy recovery was 10% based on total energy applied with an energy efficiency of 22% based on the consumed energy in the reactor. The cathode overpotential was dependent on the catholyte (sodium bicarbonate) concentration, but not the salinity ratio, indicating high catholyte conductivity was essential for maximizing hydrogen production rates. The direction of the HC and LC flows (co- or counter-current) did not affect performance in terms of hydrogen gas volume, production rates, or stack voltages. These results show that the MREC can be successfully operated using ammonium bicarbonate salts that can be regenerated using conventional distillation technologies and waste heat making the MREC a useful method for hydrogen gas production from wastes.

Competitive separation of di- vs. mono-valent cations in electrodialysis: effects of the boundary layer properties.

In electrodialysis desalination, the boundary layer near ion-exchange membranes is the limiting region for the overall rate of ionic separation due to concentration polarization over tens of micrometers in that layer. Under high current conditions, this sharp concentration gradient, creating substantial ionic diffusion, can drive a preferential separation for certain ions depending on their concentration and diffusivity in the solution. Thus, this study tested a hypothesis that the boundary layer affects the competitive transport between di- and mono-valent cations, which is known to be governed primarily by the partitioning with cation-exchange membranes. A laboratory-scale electrodialyzer was operated at steady state with a mixture of 10mM KCl and 10mM CaCl(2) at various flow rates. Increased flows increased the relative calcium transport. A two-dimensional model was built with analytical solutions of the Nernst-Planck equation. In the model, the boundary layer thickness was considered as a random variable defined with three statistical parameters: mean, standard deviation, and correlation coefficient between the thicknesses of the two boundary layers facing across a spacer. Model simulations with the Monte Carlo method found that a greater calcium separation was achieved with a smaller mean, greater standard deviation, or more negative correlation coefficient. The model and experimental results were compared for the cationic transport number as well as the current and potential relationship. The mean boundary layer thickness was found to decrease from 40 to less than 10 μm as the superficial water velocity increased from 1.06 to 4.24 cm/s. The standard deviation was greater than the mean thickness at slower water velocities and smaller at faster water velocities.

Enhanced digestion of waste activated sludge using microbial electrolysis cells at ambient temperature.

This study examined the effects of the microbial electrolysis cell (MEC) reactions on anaerobic digestion of waste activated sludge from municipal wastewater treatment under ambient temperature conditions (22-23 °C). Two lab-scale digesters, a control anaerobic digester and an electrically-assisted digester (EAD - equipped with a MEC bioanode and cathode) were operated under three solids retention times (SRT = 7, 10 and 14 days) at 22.5 ± 0.5 °C. A numerical model was also built by including the MEC electrode reactions in Anaerobic Digestion Model No.1. In experiments, the EAD showed reduced concentration of acetic acid, propionic acid, n-butyric acid and iso-butyric acid. This improved performance of the EAD is thought to be achieved by direct oxidation of the short-chain fatty acids at the bioanode as well as indirect contribution of low acetic acid concentration to enhancing beta-oxidation. The VSS and COD removal was consistently higher in the EAD by 5-10% compared to the control digester for all SRT conditions at 22.5 ± 0.5 °C. When compared to mathematical model results, this additional COD removal in the EAD was equivalent to that which would be achieved with conventional digesters at mesophilic temperatures. The magnitude of electric current in the EAD was governed by the organic loading rate while conductivity and acetic acid concentration showed negligible effects on current generation. Very high methane content (∼95%) in the biogas from both the EAD and control digester implies that the waste activated sludge contained large amounts of lipids and other complex polymeric substances compared to primary sludge.

Cadmium (II) removal mechanisms in microbial electrolysis cells

Cadmium is a toxic heavy metal, causing serious environmental and human health problems. Conventional methods for removing cadmium from wastewater are expensive and inefficient for low concentrations. Microbial electrolysis cells (MECs) can simultaneously treat wastewater, produce hydrogen gas, and remove heavy metals with low energy requirements. Lab-scale MECs were operated to remove cadmium under various electric conditions: applied voltages of 0.4, 0.6, 0.8, and 1.0 V; and a fixed cathode potential of -1.0 V vs. Ag/AgCl. Regardless of the electric condition, rapid removal of cadmium was demonstrated (50-67% in 24 h); however, cadmium concentration in solution increased after the electric current dropped with depleted organic substrate under applied voltage conditions. For the fixed cathode potential, the electric current was maintained even after substrate depletion and thus cadmium concentration did not increase. These results can be explained by three different removal mechanisms: cathodic reduction; Cd(OH)2 precipitation; and CdCO3 precipitation. When the current decreased with depleted substrates, local pH at the cathode was no longer high due to slowed hydrogen evolution reaction (2H(+)+2e(-)→H2); thus, the precipitated Cd(OH)2 and CdCO3 started dissolving. To prevent their dissolution, sufficient organic substrates should be provided when MECs are used for cadmium removal.

The yield and decay coefficients of exoelectrogenic bacteria in bioelectrochemical systems

In conventional wastewater treatment, waste sludge management and disposal contribute the major cost for wastewater treatment. Bioelectrochemical systems, as a potential alternative for future wastewater treatment and resources recovery, are expected to produce small amounts of waste sludge because exoelectrogenic bacteria grow on anaerobic respiration and form highly populated biofilms on bioanode surfaces. While waste sludge production is governed by the yield and decay coefficient, none of previous studies have quantified these kinetic constants for exoelectrogenic bacteria. For yield coefficient estimation, we modified McCartys free energy-based model by using the bioanode potential for the free energy of the electron acceptor reaction. The estimated true yield coefficient ranged 0.1 to 0.3 g-VSS (volatile suspended solids) g-COD(-1) (chemical oxygen demand), which is similar to that of most anaerobic microorganisms. The yield coefficient was sensitively affected by the bioanode potential and pH while the substrate and bicarbonate concentrations had relatively minor effects on the yield coefficient. In lab-scale experiments using microbial electrolysis cells, the observed yield coefficient (including the effect of cell decay) was found to be 0.020 ± 0.008 g-VSS g-COD(-1), which is an order of magnitude smaller than the theoretical estimation. Based on the difference between the theoretical and experimental results, the decay coefficient was approximated to be 0.013 ± 0.002 d(-1). These findings indicate that bioelectrochemical systems have potential for future wastewater treatment with reduced waste sludge as well as for resources recovery. Also, the found kinetic information will allow accurate estimation of wastewater treatment performance in bioelectrochemical systems.