Xiuping Zhu

Advanced treatment of biologically pretreated coking wastewater by electrochemical oxidation using boron-doped diamond electrodes.

Electrochemical oxidation is a promising technology to treatment of bio-refractory wastewater. Coking wastewater contains high concentration of refractory and toxic compounds and the water quality usually cannot meet the discharge standards after conventional biological treatment processes. This paper initially investigated the electrochemical oxidation using boron-doped diamond (BDD) anode for advanced treatment of coking wastewater. Under the experimental conditions (current density 20-60mAcm(-2), pH 3-11, and temperature 20-60 degrees C) using BDD anode, complete mineralization of organic pollutants was almost achieved, and surplus ammonia-nitrogen (NH(3)-N) was further removed thoroughly when pH was not adjusted or at alkaline value. Moreover, the TOC and NH(3)-N removal rates in BDD anode cell were much greater than those in other common anode systems such as SnO(2) and PbO(2) anodes cells. Given the same target to meet the National Discharge Standard of China, the energy consumption of 64kWhkgCOD(-1) observed in BDD anode system was only about 60% as much as those observed in SnO(2) and PbO(2) anode systems. Further investigation revealed that, in BDD anode cell, organic pollutants were mainly degraded by reaction with free hydroxyl radicals and electrogenerated oxidants (S(2)O(8)(2-), H(2)O(2), and other oxidants) played a less important role, while direct electrochemical oxidation and indirect electrochemical oxidation mediated by active chlorine can be negligible. These results showed great potential of BDD anode system in engineering application as a final treatment of coking wastewater.

Microbial Community Composition Is Unaffected by Anode Potential

There is great controversy on how different set anode potentials affect the performance of a bioelectrochemical system (BES). It is often reported that more positive potentials improve acclimation and performance of exoelectrogenic biofilms, and alter microbial community structure, while in other studies relatively more negative potentials were needed to achieve higher current densities. To address this issue, the biomass, electroactivity, and community structure of anodic biofilms were examined over a wide range of set anode potentials (-0.25, -0.09, 0.21, 0.51, and 0.81 V vs a standard hydrogen electrode, SHE) in single-chamber microbial electrolysis cells. Maximum currents produced using a wastewater inoculum increased with anode potentials in the range of -0.25 to 0.21 V, but decreased at 0.51 and 0.81 V. The maximum currents were positively correlated with increasing biofilm biomass. Pyrosequencing indicated biofilm communities were all similar and dominated by bacteria most similar to Geobacter sulfurreducens. Differences in anode performance with various set potentials suggest that the exoelectrogenic communities self-regulate their exocellular electron transfer pathways to adapt to different anode potentials.

Palm oil mill effluent treatment using a two-stage microbial fuel cells system integrated with immobilized biological aerated filters.

An integrated system of two-stage microbial fuel cells (MFCs) and immobilized biological aerated filters (I-BAFs) was used to treat palm oil mill effluent (POME) at laboratory scale. By replacing the conventional two-stage up-flow anaerobic sludge blanket (UASB) with a newly proposed upflow membrane-less microbial fuel cell (UML-MFC) in the integrated system, significant improvements on NH(3)-N removal were observed and direct electricity generation implemented in both MFC1 and MFC2. Moreover, the coupled iron-carbon micro-electrolysis in the cathode of MFC2 further enhanced treatment efficiency of organic compounds. The I-BAFs played a major role in further removal of NH(3)-N and COD. For influent COD and NH(3)-N of 10,000 and 125 mg/L, respectively, the final effluents COD and NH(3)-N were below 350 and 8 mg/L, with removal rates higher than 96.5% and 93.6%. The GC-MS analysis indicated that most of the contaminants were satisfactorily biodegraded by the integrated system.

Destination of organic pollutants during electrochemical oxidation of biologically-pretreated dye wastewater using boron-doped diamond anode.

Electrochemical oxidation of biologically-pretreated dye wastewater was performed in a boron-doped diamond (BDD) anode system. After electrolysis of 12h, the COD was decreased from 532 to 99 mg L(-1) (<100 mg L(-1), the National Discharge Standard of China). More importantly, the destination of organic pollutants during electrochemical oxidation process was carefully investigated by molecular weight distribution measurement, resin fractionation, ultraviolet-visible spectroscopy, HPLC and GC-MS analysis, and toxicity test. As results, most organic pollutants were completely removed by electrochemical oxidation and the rest was primarily degraded to simpler compounds (e.g., carboxylic acids and short-chain alkanes) with less toxicity, which demonstrated that electrochemical oxidation of biologically-pretreated dye wastewater with BDD anode was very effective and safe. Especially, the performance of BDD anode system in degradation of large molecular organics such as humic substances makes it very promising in practical applications as an advanced treatment of biologically-pretreated wastewaters.

Effect of Sb dopant amount on the structure and electrocatalytic capability of Ti/Sb-SnO2 electrodes in the oxidation of 4-chlorophenol

Ti/Sb-SnO2 anodes were prepared by thermal decomposition to examine the influence of the amount of Sb dopant on the structure and electrocatalytic capability of the electrodes in the oxidation of 4-chlorophenol. The physicochemical properties of the Sb-SnO2 coating were markedly influenced by different amounts of Sb dopant. The electrodes, which contained 5% Sb dopant in the coating, presented a much more homogenous surface and much smaller mud-cracks, compared with Ti/Sb-SnO2 electrodes containing 10% or 15% Sb dopant, which exibited larger mud cracks and pores on the surface. However, the main microstructure remained unchanged with the addition of the Sb dopant. No new crystal phase was observed by X-ray diffraction (XRD). The electrochemical oxidation of 4-chlorophenol on the Ti/SnO2 electrode with 5% Sb dopant was inclined to electrochemical combustion; while for those containing more Sb dopant, intermediate species were accumulated. The electrodes with 5% Sb dopant showed the highest efficiency in the bulk electrolysis of 4-chlorophenol at a current density of 20 mA/cm2 for 180 min; and the removal rates of 4-chlorophenol and COD were 51.0% and 48.9%, respectively.

Comparison of Nonprecious Metal Cathode Materials for Methane Production by Electromethanogenesis.

In methanogenic microbial electrolysis cells (MMCs), CO2 is reduced to methane using a methanogenic biofilm on the cathode by either direct electron transfer or evolved hydrogen. To optimize methane generation, we examined several cathode materials: plain graphite blocks, graphite blocks coated with carbon black or carbon black containing metals (platinum, stainless steel or nickel) or insoluble minerals (ferrihydrite, magnetite, iron sulfide, or molybdenum disulfide), and carbon fiber brushes. Assuming a stoichiometric ratio of hydrogen (abiotic):methane (biotic) of 4:1, methane production with platinum could be explained solely by hydrogen production. For most other materials, however, abiotic hydrogen production rates were insufficient to explain methane production. At −600 mV, platinum on carbon black had the highest abiotic hydrogen gas formation rate (1600 ± 200 nmol cm–3 d–1) and the highest biotic methane production rate (250 ± 90 nmol cm–3 d–1). At −550 mV, plain graphite (76 nmol cm–3 d–1) performed similarly to platinum (73 nmol cm–3 d–1). Coulombic recoveries, based on the measured current and evolved gas, were initially greater than 100% for all materials except platinum, suggesting that cathodic corrosion also contributed to electromethanogenic gas production.

Controlling the occurrence of power overshoot by adapting microbial fuel cells to high anode potentials

Power density curves for microbial fuel cells (MFCs) often show power overshoot, resulting in inaccurate estimation of MFC performance at high current densities. The reasons for power overshoot are not well understood, but biofilm acclimation and development are known factors. In order to better explore the reasons for power overshoot, exoelectrogenic biofilms were developed at four different anode potentials (-0.46 V, -0.24 V, 0 V, and 0.50 V vs. Ag/AgCl), and then the properties of the biofilms were examined using polarization tests and cyclic voltammetry (CV). The maximum power density of the MFCs was 1200±100 mW/m(2). Power overshoot was observed in MFCs incubated at -0.46 V, but not those acclimated at more positive potentials, indicating that bacterial activity was significantly influenced by the anode acclimation potential. CV results further indicated that power overshoot of MFCs incubated at the lowest anode potential was associated with a decreasing electroactivity of the anodic biofilm in the high potential region, which resulted from a lack of sufficient electron transfer components to shuttle electrons at rates needed for these more positive potentials.

Using single-chamber microbial fuel cells as renewable power sources of electro-Fenton reactors for organic pollutant treatment

Electro-Fenton reactions can be very effective for organic pollutant degradation, but they typically require non-sustainable electrical power to produce hydrogen peroxide. Two-chamber microbial fuel cells (MFCs) have been proposed for pollutant treatment using Fenton-based reactions, but these types of MFCs have low power densities and require expensive membranes. Here, more efficient dual reactor systems were developed using a single-chamber MFC as a low-voltage power source to simultaneously accomplish H2O2 generation and Fe(2+) release for the Fenton reaction. In tests using phenol, 75 ± 2% of the total organic carbon (TOC) was removed in the electro-Fenton reactor in one cycle (22 h), and phenol was completely degraded to simple and readily biodegradable organic acids. Compared to previously developed systems based on two-chamber MFCs, the degradation efficiency of organic pollutants was substantially improved. These results demonstrate that this system is an energy-efficient and cost-effective approach for industrial wastewater treatment of certain pollutants.

Scale-up of BDD anode system for electrochemical oxidation of phenol simulated wastewater in continuous mode

Scale-up of boron-doped diamond (BDD) anode system is significant to the practical application of electrochemical oxidation in bio-refractory wastewater treatment. In this study, the performance of a smaller BDD anode (24 cm(2)) system in continuous mode electrochemical oxidation of phenol simulated wastewater was first investigated and well described by the response surface methodology (RSM). Furthermore, the RSM was extended to examine the scale-up feasibility of BDD anode systems with similar configurations. It was demonstrated that both COD degradation efficiency and specific energy consumption could be expected at the same level even as the system was enlarged over 100 times, which implied that BDD anode system could be successfully scaled up through controlling the same retention time, current density, initial COD, and conductivity conditions. Based on this study, a larger BDD anode (2904 cm(2)) system was constructed and systematic measurements were made on its performance in electrochemical oxidation of phenol simulated wastewater. Very good agreement was found between measured and predicted results by RSM. At the optimized conditions, the larger BDD anode system could easily reduce the COD of phenol simulated wastewater from 633 mg L(-1) to 145 mg L(-1) (<150 mg L(-1), National Discharge Standard of China) during 80 min with specific energy consumption only 31 kWh kgCOD(-1).

Comparative electrochemical degradation of phthalic acid esters using boron-doped diamond and Pt anodes.

Phthalic acid esters (PAEs) are a group of endocrine disruptors commonly used as plasticizers. The present study compares the electrochemical oxidation of PAEs at boron-doped diamond (BDD) anode with that at Pt anode. Both the degradation and the mineralization processes of PAEs became much slower when using the Pt anode compared with that using the BDD anode. Moreover, the degradation rates of PAEs decreased at the BDD anode but increased at the Pt anode with increasing alkyl chain length. This was attributed to the different oxidation mechanisms at the two anodes. The BDD electrode has an inert surface that holds a large amount of strong oxidants as free hydroxyl radicals ((*)OH), causing electrophilic attack by (*)OH to be the main reaction. Therefore, degradation of PAEs became slower on the BDD anode due to there being less available electronic energy as the alkyl chain length increased. However, adsorbed oxidants (PtO(x)(+1)) with low oxidation ability tended to form on the surface of the active Pt anode. Therefore, PAEs with longer alkyl chains promote faster degradation owing to their stronger hydrophobicity. Detection of intermediates in the GC/MS tests confirmed the above conclusion, in which oxidation of dimethyl phthalate on BDD occurred on the aromatic ring at first, while the alkyl chain was preferentially attacked on the Pt anode.