Real-time monitoring of a microbial electrolysis cell using an electrical equivalent circuit model.

Efforts in developing microbial electrolysis cells (MECs) resulted in several novel approaches for wastewater treatment and bioelectrosynthesis. Practical implementation of these approaches necessitates the development of an adequate system for real-time (on-line) monitoring and diagnostics of MEC performance. This study describes a simple MEC equivalent electrical circuit (EEC) model and a parameter estimation procedure, which enable such real-time monitoring. The proposed approach involves MEC voltage and current measurements during its operation with periodic power supply connection/disconnection (on/off operation) followed by parameter estimation using either numerical or analytical solution of the model. The proposed monitoring approach is demonstrated using a membraneless MEC with flow-through porous electrodes. Laboratory tests showed that changes in the influent carbon source concentration and composition significantly affect MEC total internal resistance and capacitance estimated by the model. Fast response of these EEC model parameters to changes in operating conditions enables the development of a model-based approach for real-time monitoring and fault detection.

Long-term performance of a microbial electrolysis cell operated with periodic disconnection of power supply.

This study describes a new approach for achieving stable long-term performance and maximizing the removal of chemical oxygen demand (COD) in a Microbial Electrolysis Cell (MEC). In the proposed approach, the MEC power supply is periodically disconnected, e.g. at a frequency of 0.1-0.5 Hz and a duty cycle of 90-95%. To evaluate the impact of such periodic power supply disconnection (on/off mode) on MEC performance, experiments were carried out in two flow-through MECs with activated granular carbon electrodes. The on/off operating strategy was applied to one MEC, while the other one was operated at a fixed voltage (control MEC). Long-term on/off operation resulted in progressive increase in COD removal efficiency (from 80% to 90%) and MEC current over time, while the control MEC showed stable but inferior performance. Furthermore, by changing the operating strategies and applying the on/off approach to the control MEC, its COD removal was increased from 78% to 83% and internal resistance decreased. The proposed on/off mode of operation can be used to develop a high-rate MEC-based wastewater treatment system.

Population analysis of mesophilic microbial fuel cells fed with carbon monoxide.

Electricity generation in a microbial fuel cell (MFC) fed with carbon monoxide (CO) has been recently demonstrated; however, the microbial ecology of this system has not yet been described. In this work the diversity of the microbial community present at the anode of CO-fed MFCs was studied by performing denaturing gradient gel electrophoresis (DGGE) and high-throughput sequencing (HTS) analyses. HTS indicated a significant increase of the archaeal genus Methanobacterium and of the bacterial order Clostridiales, notably including Clostridium species, while in both MFCs DGGE identified members of the bacterial genera Geobacter, Desulfovibrio, and Clostridium, and of the archaeal genera Methanobacterium, Methanofollis, and Methanosaeta. In particular, the presence of Geobacter sulfurreducens was identified. Tolerance of G. sulfurreducens to CO was confirmed by growing G. sulfurreducens with acetate under a 100 % CO atmosphere. This observation, along with the identification of acetogens, supports the hypothesis of the two-step process in which CO is converted to acetate by the carboxidotrophic Bacteria and acetate is then oxidized by CO-tolerant electricigenic bacteria to produce electricity.

Pulse-width modulated external resistance increases the microbial fuel cell power output.

This study describes MFC operation with a pulse-width modulated connection of the external resistor (R-PWM mode) at low and high frequencies. Analysis of the output voltage profiles acquired during R-PWM tests showed the presence of slow and fast dynamic components, which can be described by a simple equivalent circuit model suitable for process control applications. At operating frequencies above 100 Hz a noticeable improvement in MFC performance was observed with the power output increase of 22-43% as compared to MFC operation with a constant external resistance.

Microbial electrolysis cell scale-up for combined wastewater treatment and hydrogen production.

This study demonstrates microbial electrolysis cell (MEC) scale-up from a 50mL to a 10L cell. Initially, a 50mL membraneless MEC with a gas diffusion cathode was operated on synthetic wastewater at different organic loads. It was concluded that process scale-up might be best accomplished using a "reactor-in-series" concept. Consequently, 855mL and 10L MECs were built and operated. By optimizing the hydraulic retention time (HRT) of the 855mL MEC and individually controlling the applied voltages of three anodic compartments with a real-time optimization algorithm, a COD removal of 5.7g L(R)(-1)d(-1) and a hydrogen production of 1.0-2.6L L(R)(-1)d(-1) was achieved. Furthermore, a two MECs in series 10L setup was constructed and operated on municipal wastewater. This test showed a COD removal rate of 0.5g L(R)(-1)d(-1), a removal efficiency of 60-76%, and an energy consumption of 0.9Whperg of COD removed.

The performance of a thermophilic microbial fuel cell fed with synthesis gas.

This study demonstrated electricity generation in a thermophilic microbial fuel cell (MFC) operated on synthesis gas (syngas) as the sole electron donor. At 50°C, a volumetric power output of 30-35 mWL(R)(-1) and a syngas conversion efficiency of 87-98% was achieved. The observed pathway of syngas conversion to electricity primarily consisted of a two-step process, where the carbon monoxide and hydrogen were first converted to acetate, which was then consumed by the anodophilic bacteria to produce electricity. A denaturing gradient gel electrophoresis (DGGE) analysis of the 16S rDNA revealed the presence of Geobacter species, Acetobacter, methanogens and several uncultured bacteria and archaea in the anodic chamber.

Use of silicone membranes to enhance gas transfer during microbial fuel cell operation on carbon monoxide.

Electricity generation in a microbial fuel cell (MFC) using carbon monoxide (CO) or synthesis gas (syngas) as a carbon source has been demonstrated recently. A major challenge associated with CO or syngas utilization is the mass transfer limitation of these sparingly soluble gases in the aqueous phase. This study evaluated the applicability of a dense polymer silicone membrane and thin wall silicone tubing for CO mass transfer in MFCs. Replacing the sparger used in our previous study with the membrane systems for CO delivery resulted in improved MFC performance and CO transformation efficiency. A power output and CO transformation efficiency of up to 18 mW LR(-1) (normalized to anode compartment volume) and 98%, respectively, was obtained. The use of membrane systems offers the advantage of improved mass transfer and reduced reactor volume, thus increasing the volumetric power output of MFCs operating on a gaseous substrate such as CO.

Optimizing the electrode size and arrangement in a microbial electrolysis cell.

This study investigates the influence of anode and cathode size and arrangement on hydrogen production in a membrane-less flat-plate microbial electrolysis cell (MEC). Protein measurements were used to evaluate microbial density in the carbon felt anode. The protein concentration was observed to significantly decrease with the increase in distance from the anode-cathode interface. Cathode placement on both sides of the carbon felt anode was found to increase the current, but also led to increased losses of hydrogen to hydrogenotrophic activity leading to methane production. Overall, the best performance was obtained in the flat-plate MEC with a two-layer 10 mm thick carbon felt anode and a single gas-diffusion cathode sandwiched between the anode and the hydrogen collection compartments.

Multi-population model of a microbial electrolysis cell.

This work presents a multi-population dynamic model of a microbial electrolysis cell (MEC). The model describes the growth and metabolic activity of fermentative, electricigenic, methanogenic acetoclastic, and methanogenic hydrogenophilic microorganisms and is capable of simulating hydrogen production in a MEC fed with complex organic matter, such as wastewater. The model parameters were estimated with the experimental results obtained in continuous flow MECs fed with acetate or synthetic wastewater. Following successful model validation with an independent data set, the model was used to analyze and discuss the influence of applied voltage and organic load on hydrogen production and COD removal.

Electrolysis-enhanced anaerobic digestion of wastewater.

This study demonstrates enhanced methane production from wastewater in laboratory-scale anaerobic reactors equipped with electrodes for water electrolysis. The electrodes were installed in the reactor sludge bed and a voltage of 2.8-3.5 V was applied resulting in a continuous supply of oxygen and hydrogen. The oxygen created micro-aerobic conditions, which facilitated hydrolysis of synthetic wastewater and reduced the release of hydrogen sulfide to the biogas. A portion of the hydrogen produced electrolytically escaped to the biogas improving its combustion properties, while another part was converted to methane by hydrogenotrophic methanogens, increasing the net methane production. The presence of oxygen in the biogas was minimized by limiting the applied voltage. At a volumetric energy consumption of 0.2-0.3 Wh/L(R), successful treatment of both low and high strength synthetic wastewaters was demonstrated. Methane production was increased by 10-25% and reactor stability was improved in comparison to a conventional anaerobic reactor.

The effect of real-time external resistance optimization on microbial fuel cell performance.

This work evaluates the impact of the external resistance (electrical load) on the long-term performance of a microbial fuel cell (MFC) and demonstrates the real-time optimization of the external resistance. For this purpose, acetate-fed MFCs were operated at external resistances, which were above, below, or equal to the internal resistance of a corresponding MFC. A perturbation/observation algorithm was used for the real-time optimal selection of the external resistance. MFC operation at the optimal external resistance resulted in increased power output, improved Coulombic efficiency, and low methane production. Furthermore, the efficiency of the perturbation/observation algorithm for maximizing long-term MFC performance was confirmed by operating an MFC fed with synthetic wastewater for over 40 days. In this test an average Coulombic efficiency of 29% was achieved.

A two-population bio-electrochemical model of a microbial fuel cell.

This work presents a two-population model describing the competition of anodophilic and methanogenic microbial populations for a common substrate in a microbial fuel cell (MFC). Fast numerical solution of the model is provided by using ordinary differential equations to describe biomass growth and retention in the anodic compartment. The model parameters are estimated and validated using experimental results obtained in four continuous-flow air-cathode MFCs operated at various external resistances and organic loads. Model analysis demonstrates the influence of operating conditions on MFC performance and suggests ways to maximize MFC power output. The model is suitable both for process optimization and on-line control applications.

A comparison of analytical techniques for evaluating food waste degradation by anaerobic digestion.

Organic matter contained in food waste was degraded by anaerobic digestion under mesophilic and thermophilic conditions at two hydraulic retention times. Evolution of the digestion process was followed by thermogravimetry analysis, fluorescence spectroscopy and (1)H nuclear magnetic resonance. All analytical methods suggested that longer retention times might be required for food waste stabilization under mesophilic conditions as compared to thermophilic stabilization. All the analytical methods showed that the stabilization process consisted of two steps, where complex organic molecules were formed during initial stabilization and then digested providing sufficient hydraulic retention time. Longer hydraulic retention times were required for food waste stabilization under mesophilic conditions. Overall, thermal and (1)H NMR analyses of the digestate samples might be recommended if more detailed analysis is required, while fluorescence measurements can be used as a fast screening technique, which provides qualitative assessment of the stabilization process.

Electricity generation from carbon monoxide in a single chamber microbial fuel cell.

Electricity production from carbon monoxide (CO) is demonstrated in a single chamber microbial fuel cell (MFC) with a CoTMPP-based air cathode. The MFC was inoculated with anaerobic sludge and continuously sparged with CO as a sole carbon source. Volumetric power output was maximized at a CO flow rate of 4.8LLR(-1)d(-1) reaching 6.4mWLR(-1). Several soluble and gaseous degradation products including hydrogen, methane, and acetate were detected, resulting in a relatively low apparent Coulombic efficiency of 8.7%. Tests also demonstrated electricity production from hydrogen and acetate with the highest and fastest increase in voltage exhibited after acetate injection. It is hypothesized that electricity generation in a CO-fed MFC is accomplished by a consortium of carboxydotrophic and carbon monoxide - tolerant anodophilic microorganisms.

Methane production in an UASB reactor operated under periodic mesophilic-thermophilic conditions.

Methane production was studied in a laboratory-scale 10 L anaerobic upflow sludge bed (UASB) reactor with periodic variations of the reactor temperature. On a daily basis the temperature was varied between 35 and 45 degrees C or 35 and 55 degrees C with a heating period of 6 h. Each temperature increase was accompanied by an increase in methane production and a decrease in the concentration of soluble organic matter in the effluent. In comparison to a reactor operated at 35 degrees C, a net increase in methane production of up to 22% was observed. Batch activity tests demonstrated a tolerance of mesophilic methanogenic populations to short-term, 2-6 h, temperature increases, although activity of acetoclastic methanogens decreased after 6 h exposure to a temperature of 55 degrees C. 16S sequencing of DGGE bands revealed proliferation of temperature-tolerant Methanospirillum hungatii sp. in the reactor.

Anaerobic digestion model No. 1-based distributed parameter model of an anaerobic reactor: II. Model validation.

In this study, an ADM1-based distributed parameter model was validated using experimental results obtained in a laboratory-scale 10 L UASB reactor. Sensitivity analysis of the model parameters was used to select four parameters for estimation by a numerical procedure while other parameters were accepted from ADM1 benchmark simulations. The parameter estimation procedure used measurements of liquid phase components obtained at different sampling points in the reactor and under different operating conditions. Model verification used real time fluorescence-based measurements of chemical oxygen demand and volatile fatty acids at four sampling locations in the reactor. Overall, the distributed parameter model was able to describe the distribution of liquid phase components in the reactor and adequately simulated the effect of external recirculation on degradation efficiency. The model can be used in the design, analysis and optimization of UASB reactors.

Anaerobic digestion model no. 1-based distributed parameter model of an anaerobic reactor: I. Model development.

This work presents a distributed parameter model of the anaerobic digestion process. The model is based on the Anaerobic digestion model no. 1 (ADM1) and was developed to simulate anaerobic digestion process in high-rate reactors with significant axial dispersion, such as in upflow anaerobic sludge bed (UASB) reactors. The model, which was named ADM1d, combines ADM1's kinetics of biomass growth and substrate transformation with axial dispersion material balances. ADM1d uses a hyperbolic tangent function to describe biomass distribution within a one compartment model. A comparison of this approach with a two-compartment, sludge bed - liquid above the bed, model showed similar simulation results while the one-compartment model had less equations. A comparison of orthogonal collocation and finite difference algorithms for numerical solution of ADM1d showed better stability of the finite difference algorithm.

ADM1 application for tuning and performance analysis of a multi-model observer-based estimator.

Anaerobic digestion model no.1 (ADM1) was used for tuning and performance analysis of the multi-model observer based estimator (mmOBE). The mmOBE was based on the variable structure model (VSM) of the anaerobic digestion model, which consists of several local submodels, each of which describes a typical process state. Depending on the hydraulic retention time, ADM1 simulated the methanogenic, organic overload, and acidogenic states of the process. These simulations allowed for optimising tunable parameters of the mmOBE. Owing to relatively slow process dynamics, a data acquisition interval as large as one day was sufficient to obtain acceptable accuracy. The simulations of mmOBE performance showed excellent rate of mmOBE convergence to ADM1 outputs. Moreover, mmOBE successfully estimated key kinetic parameters, such as maximal transformation rates of CODs, VFAs, and methane. These estimations can be used in the development of the advanced knowledge-based process system, which uses both available measurements and estimations of key kinetic parameters for extended diagnosis of failures and process trend analysis.

On-line estimation of kinetic parameters in anaerobic digestion using observer-based estimators and multiwavelength fluorometry.

Observer-based estimators (OBE) were used for estimation of state variables and kinetic parameters in an anaerobic digestion (AD) process. A simplified first-order model with time-varying kinetic parameters was used to design an OBE for kinetic parameter estimation. This approach was validated on a laboratory-scale anaerobic reactor equipped with a multiwavelength fluorometer for on-line measurements of COD and VFA concentrations in the reactor effluent. The proposed estimators provide continuous adjustment of kinetic parameters and can be used for predictions of state variables between samples acquisition and during sensor failure.

Fluorescence-based monitoring of tracer and substrate distribution in an UASB reactor.

In this work, rhodamine-related fluorescence was measured on-line at four reactor heights in order to study hydrodynamics within an upflow anaerobic sludge bed reactor. A linear dependence of the dispersion coefficient (D) on the upflow velocity was observed, while the influence of the organic loading rate (OLR) was insignificant. Furthermore, the Bodenstein number of the reactor loaded with granulated sludge was found to be position-dependent with the largest values measured at the bottom of the sludge bed. This trend was not observed in the reactor without sludge. Chemical oxygen demand (COD) and volatile fatty acid (VFA) concentrations were measured at the same reactor heights as in rhodamine tests using conventional off-line analytical methods and on-line multiwavelength fluorometry. Significant spatial COD and VFA gradients were observed at organic loading rates above 6g COD l(R)(-1)d(-1) and linear upflow velocities below 0.8m h(-1).