Cees J.N. Buisman

Copper Recovery Combined with Electricity Production in a Microbial Fuel Cell

A metallurgical microbial fuel cell (MFC) is an attractive alternative for recovery of copper from copper containing waste streams, as the metal is recovered in its metallic form at the cathode, while the energy for metal reduction can be obtained from oxidation of organic materials at the anode with possible additional production of electricity. We studied the recovery of copper in an MFC using a bipolar membrane as a pH separator. Under anaerobic conditions, the maximum power density was 0.43 W/m(2) at a current density of 1.7 A/m(2). In the presence of oxygen, MFC performance improved considerably to a maximum power density of 0.80 W/m(2) at a current density of 3.2 A/m(2). Pure copper crystals were formed on the cathode, and no CuO or Cu(2)O was detected. Removal efficiencies of >99.88% were obtained. The cathodic recovery of copper compared to the produced electricity was 84% (anaerobic) and 43% (aerobic). The metallurgy MFC with the Cu(2+) reducing cathode further enlarges the application range of MFCs.

Bioelectrochemical Ethanol Production through Mediated Acetate Reduction by Mixed Cultures

Biological acetate reduction with hydrogen is a potential method to convert wet biomass waste into ethanol. Since the ethanol concentration and reaction rates are low, this research studies the feasibility of using an electrode, in stead of hydrogen, as an electron donor for biological acetate reduction in conjunction of an electron mediator. Initially, the effect of three selected mediators on metabolic flows during acetate reduction with hydrogen was explored; subsequently, the best performing mediator was used in a bioelectrochemical system to stimulate acetate reduction at the cathode with mixed cultures at an applied cathode potential of -550 mV. In the batch test, methyl viologen (MV) was found to accelerate ethanol production 6-fold and increased ethanol concentration 2-fold to 13.5 +/- 0.7 mM compared to the control. Additionally, MV inhibited n-butyrate and methane formation, resulting in high ethanol production efficiency (74.6 +/- 6%). In the bioelectrochemical system, MV addition to an inoculated cathode led directly to ethanol production (1.82 mM). Hydrogen was coproduced at the cathode (0.0035 Nm(3) hydrogen m(-2) d(-1)), so it remained unclear whether acetate was reduced to ethanol by electrons supplied by the mediator or by hydrogen. As MV reacted irreversibly at the cathode, ethanol production stopped after 5 days.

Ammonium recovery and energy production from urine by a microbial fuel cell

Nitrogen recovery through NH(3) stripping is energy intensive and requires large amounts of chemicals. Therefore, a microbial fuel cell was developed to simultaneously produce energy and recover ammonium. The applied microbial fuel cell used a gas diffusion cathode. The ammonium transport to the cathode occurred due to migration of ammonium and diffusion of ammonia. In the cathode chamber ionic ammonium was converted to volatile ammonia due to the high pH. Ammonia was recovered from the liquid-gas boundary via volatilization and subsequent absorption into an acid solution. An ammonium recovery rate of 3.29 g(N) d(-1) m(-2) (vs. membrane surface area) was achieved at a current density of 0.50 A m(-2) (vs. membrane surface area). The energy balance showed a surplus of energy 3.46 kJ g(N)(-1), which means more energy was produced than needed for the ammonium recovery. Hence, ammonium recovery and simultaneous energy production from urine was proven possible by this novel approach.

Microbial electrolysis cell with a microbial biocathode.

This study demonstrates, for the first time, the proof-of-principle of an MEC in which both the anodic and cathodic reaction are catalyzed by microorganisms. No expensive chemical catalysts, such as platinum, are needed. Two of these MECs were simultaneously operated and reached a maximum of 1.4 A/m(2) at an applied cell voltage of 0.5 V. At a cathode potential of -0.7 V, the biocathode in the MECs had a higher current density (MEC 1: 1.9 A/m(2), MEC 2: 3.3 A/m(2)) than a control cathode (0.3 A/m(2), graphite felt without biofilm) in an electrochemical half cell. This indicates that hydrogen production is catalyzed at the biocathode, likely by electrochemically active microorganisms. The cathodic hydrogen recovery was 17% for MEC 1 and 21% for MEC 2. Hydrogen losses were ascribed to diffusion through membrane and tubing, and methane formation. After 1600 h of operation, the current density of the MECs had decreased to 0.6 A/m(2), probably caused by precipitation of calcium phosphate on the biocathode. The slow deteriorating effect of calcium phosphate, and the production of methane show the importance of studying the combination of bioanode and biocathode in one electrochemical cell, and of studying long term performance of such an MEC.

Nitrogen and phosphorus removal from municipal wastewater effluent using microalgal biofilms

Microalgal biofilms have so far received little attention as post-treatment for municipal wastewater treatment plants, with the result that the removal capacity of microalgal biofilms in post-treatment systems is unknown. This study investigates the capacity of microalgal biofilms as a post-treatment step for the effluent of municipal wastewater treatment plants. Microalgal biofilms were grown in flow cells with different nutrient loads under continuous lighting of 230 μmol/m(2)/s (PAR photons, 400-700 nm). It was found that the maximum uptake capacity of the microalgal biofilm was reached at loading rates of 1.0 g/m(2)/day nitrogen and 0.13 g/m(2)/day phosphorus. These maximum uptake capacities were the highest loads at which the target effluent values of 2.2 mg/L nitrogen and 0.15 mg/L phosphorus were still achieved. Microalgal biomass analysis revealed an increasing nitrogen and phosphorus content with increasing loading rates until the maximum uptake capacities. The internal nitrogen to phosphorus ratio decreased from 23:1 to 11:1 when increasing the loading rate. This combination of findings demonstrates that microalgal biofilms can be used for removing both nitrogen and phosphorus from municipal wastewater effluent.

Analysis and Improvement of a Scaled-Up and Stacked Microbial Fuel Cell

Scaling up microbial fuel cells (MFCs) is inevitable when power outputs have to be obtained that can power electrical devices other than small sensors. This research has used a bipolar plate MFC stack of four cells with a total working volume of 20 L and a total membrane surface area of 2 m(2). The cathode limited MFC performance due to oxygen reduction rate and cell reversal. Furthermore, residence time distribution curves showed that bending membranes resulted in flow paths through which the catholyte could flow from inlet to outlet, while leaving the reactants unconverted. The cathode was improved by decreasing the pH, purging pure oxygen, and increasing the flow rate, which resulted in a 13-fold power density increase to 144 W m(-3) and a volumetric resistivity of only 1.2 mOmega m(3) per cell. Both results are major achievements compared to results currently published for laboratory and scaled-up MFCs. When designing a scaled-up MFC, it is important to ensure optimal contact between electrodes and substrate and to minimize the distances between electrodes.

Biological formation of caproate and caprylate from acetate: fuel and chemical production from low grade biomass

This research introduces an alternative mixed culture fermentation technology for anaerobic digestion to recover valuable products from low grade biomass. In this mixed culture fermentation, organic waste streams are converted to caproate and caprylate as precursors for biodiesel or chemicals. It was found that acetate, as the main intermediate of anaerobic digestion, can be elongated to medium chain fatty acids with six and eight carbon atoms. Mixed microbial communities were able to produce 8.17 g l−1 caproate and 0.32 g l−1 caprylate under methanogenesis-suppressed conditions in a stable batch reactor run. The highest production rate was 25.6 mM C caproate per day with a product yield of 0.6 mol C per mol C. This elongation process occurred with both ethanol and hydrogen as electron donors, demonstrating the flexibility of the process. Microbial characterization revealed that the microbial populations were stable and dominated by relatives of Clostridium kluyveri.

Effect of the type of ion exchange membrane on performance, ion transport, and pH in biocatalyzed electrolysis of wastewater

Previous studies have shown that the application of cation exchange membranes (CEMs) in bioelectrochemical systems running on wastewater can cause operational problems. In this paper the effect of alternative types of ion exchange membrane is studied in biocatalyzed electrolysis cells. Four types of ion exchange membranes are used: (i) a CEM, (ii) an anion exchange membrane (AEM), (iii) a bipolar membrane (BPM), and (iv) a charge mosaic membrane (CMM). With respect to the electrochemical performance of the four biocatalyzed electrolysis configurations, the ion exchange membranes are rated in the order AEM > CEM > CMM > BPM. However, with respect to the transport numbers for protons and/or hydroxyl ions (t(H/OH)) and the ability to prevent pH increase in the cathode chamber, the ion exchange membranes are rated in the order BPM > AEM > CMM > CEM.

Autotrophic nitrogen removal from low strength waste water at low temperature.

Direct anaerobic treatment of municipal waste waters allows for energy recovery in the form of biogas. A further decrease in the energy requirement for waste water treatment can be achieved by removing the ammonium in the anaerobic effluent with an autotrophic process, such as anammox. Until now, anammox has mainly been used for treating warm (>30 °C) and concentrated (>500 mg N/L) waste streams. Application in the water line of municipal waste water treatment poses the challenges of a lower nitrogen concentration (<100 mg N/L) and a lower temperature (≤ 20 °C). Good biomass retention and a short HRT are required to achieve a sufficiently high nitrogen loading rate. For this purpose a 4.5 L gaslift reactor was inoculated with a small amount of anammox granules and operated for 253 days at 20 °C. The synthetic influent contained (69 ± 5) mg (NH(4)(+) + NO(2)(-))/L and 20 vol.% of anaerobically stabilised effluent. Results showed a clear increase in nitrogen loading rate (NLR) up to 0.31 g (NH(4) + NO(2))-N/(L × d) at a hydraulic retention time (HRT) of 5.3 h. A low effluent concentration of 0.03-0.17 mg (NH(4)(+)+NO(2)(-))-N/L could be achieved. Anammox biomass was retained as granules and as a biofilm on the reactor walls, which contributed 54 and 46%, respectively, towards total activity. The biomass was further characterised by an estimated net growth rate of 0.040 d(-1) and an apparent activation energy of 72 kJ/mol. The results presented in this paper showed that anammox bacteria can be applied for autotrophic nitrogen removal from the water line at a municipal waste water treatment plant. Combining direct anaerobic treatment with autotrophic nitrogen removal opens opportunities for energy-efficient treatment of municipal waste waters.

Removal of micropollutants from aerobically treated grey water via ozone and activated carbon

Ozonation and adsorption onto activated carbon were tested for the removal micropollutants of personal care products from aerobically treated grey water. MilliQ water spiked with micropollutants (100-1600 μgL(-1)) was ozonated at a dosing rate of 1.22. In 45 min, this effectively removed (>99%): Four parabens, bisphenol-A, hexylcinnamic aldehyde, 4-methylbenzylidene-camphor (4MBC), benzophenone-3 (BP3), triclosan, galaxolide and ethylhexyl methoxycinnamate. After 60 min, the removal efficiency of benzalkonium chloride was 98%, tonalide and nonylphenol 95%, octocrylene 92% and 2-phenyl-5-benzimidazolesulfonic acid (PBSA) 84%. Ozonation of aerobically treated grey water at an applied ozone dose of 15 mgL(-1), reduced the concentrations of octocrylene, nonylphenol, triclosan, galaxolide, tonalide and 4-methylbenzylidene-camphor to below limits of quantification, with removal efficiencies of at least 79%. Complete adsorption of all studied micropollutants onto powdered activated carbon (PAC) was observed in batch tests with milliQ water spiked with 100-1600 μgL(-1) at a PAC dose of 1.25 gL(-1) and a contact time of 5 min. Three granular activated carbon (GAC) column experiments were operated to treat aerobically treated grey water. The operation of a GAC column with aerobically treated grey water spiked with micropollutants in the range of 0.1-10 μgL(-1) at a flow of 0.5 bed volumes (BV)h(-1) showed micropollutant removal efficiencies higher than 72%. During the operation time of 1728 BV, no breakthrough of TOC or micropollutants was observed. Removal of micropollutants from aerobically treated grey water was tested in a GAC column at a flow of 2 BVh(-1). Bisphenol-A, triclosan, tonalide, BP3, galaxolide, nonylphenol and PBSA were effectively removed even after a stable TOC breakthrough of 65% had been reached. After spiking the aerobically treated effluent with micropollutants to concentrations of 10-100 μgL(-1), efficient removal to below limits of quantification continued for at least 1440 BV. Both ozonation and adsorption are suitable techniques for the removal of micropollutants from aerobically treated grey water.