Electricity production and phosphorous recovery as struvite from synthetic wastewater using magnesium-air fuel cell electrocoagulation.

This research was based on the investigation of a major principle, regarding the effects of NaCl and KH2PO4 concentrations on struvite recovery, with electricity production using magnesium-air fuel cell electrocoagulation, in accordance with the concentration of phosphorous and chloride. The weight ratio of N:P in the synthetic wastewater was in the range of 1.2-21. The concentration of NH4Cl was fixed at 0.277 M (approximately 3888 ppm as NH3-N and 5000 ppm as NH4), while PO4-P was in the range of 0.006-0.1 M. In addition, the concentrations of NaCl as electrolyte were 0, 0.01, and 0.1 M. Phosphate removal increased linearly with the Mg:P ratio, up to approximately 1.1 mol mol-1, irrespective of the initial concentrations of phosphate and NaCl. The one-to-one reaction as mole ratio between phosphate and the dissolved Mg ions resulted in phosphate removal, with the production of a one-to-one magnesium/phosphate mineral, such as struvite. The average removal rate of phosphorous in experiments without a dose of NaCl was 4.19 mg P cm-2 h-1, which was lower than the relative values of 5.35 and 4.77 mg P cm-2 h-1, in experiments with 0.01 and 0.1 M NaCl. The dissolution rate of Mg with electro-oxidation determined the rate of phosphorous removal with struvite recovery. The average removal rates of phosphorous with dose concentrations of 0.006, 0.01 and 0.02 M KH2PO4 were 4.02, 5.54, 6.9 mg P cm-2 h-1, respectively, which increased with the increase in KH2PO4 dose. However, in experiments with a dose of 0.05 and 0.1 M KH2PO4, the average removal rates of phosphorous decreased to 4.84 and 2.51, respectively. The maximum power densities in the electrolyte mixture of 0.05 M KH2PO4/0.277 M NH4Cl, 0.01 M NaCl/0.05 M KH2PO4/0.277 M NH4Cl, and 0.1 NaCl/0.05 KH2PO4/0.277 M NH4Cl were 25.1, 26.4, and 33.2 W/m2, respectively. The increase in the NaCl dose concentration resulted in an increase in the maximum power density and current density. A dose above 0.05 M KH2PO4 resulted in the decrease of the maximum power densities. However, when the dose was below 0.05 M KH2PO4, the maximum power density increased with the increase in KH2PO4 dose.

Treatment of synthetic arsenate wastewater with iron-air fuel cell electrocoagulation to supply drinking water and electricity in remote areas.

Electrocoagulation with an iron-air fuel cell is an innovative arsenate removal system that can operate without an external electricity supply. Thus, this technology is advantageous for treating wastewater in remote regions where it is difficult to supply electricity. In this study, the possibility of real applications of this system for arsenate treatment with electricity production was verified through electrolyte effect investigations using a small-scale fuel cell and performance testing of a liter-scale fuel cell stack. The electrolyte species studied were NaCl, Na2SO4, and NaHCO3. NaCl was overall the most effective electrolyte for arsenate treatment, although Na2SO4 produced the greatest electrical current and power density. In addition, although the current density and power density were proportional to the concentrations of NaCl and Na2SO4, the use of concentrations above 20 mM of NaCl and Na2SO4 inhibited arsenate treatment due to competition effects between anions and arsenate in adsorption onto the iron hydroxide. The dominant iron hydroxide produced at the iron anode was found to be lepidocrocite by means of Raman spectroscopy. A liter-scale four-stack iron-air fuel cell with 10 mM NaCl electrolyte was found to be able to treat about 300 L of 1 ppm arsenate solution to below 10 ppb during 1 day, based on its 60-min treatment capacity, as well as produce the maximum power density of 250 mW/m2.

Performance of a continuous flow microbial reverse-electrodialysis electrolysis cell using a non-buffered substrate and catholyte effluent addition.

A continuous flow microbial reverse-electrodialysis electrolysis cell (MREC) was operated under non-buffered substrate with various flow rates of catholyte effluent into anode chamber to investigate the effects on the hydrogen gas production. Adding the catholyte effluent to the anolyte influent resulted in increased salt concentration in the anolyte influent. The increasing anolyte influent salt concentration to 0.23M resulted in improved hydrogen gas production, Coulombic recovery, yield, and hydrogen production rate to 25±1.4mL, 83±5%, 1.49±0.15mol-H2/mole-COD, 0.91±0.03m3-H2/m3-Van/day, respectively. These improvements were attributed to the neutral pH rather than increase in anolyte conductivity as there was no significant improvement in the reactor performance when the NaCl was directly added to the reactor. These results show that addition of catholyte effluent into the anode chamber improved the MREC performance.

Arsenic treatment and power generation with a dual-chambered fuel cell with anionic and cationic membranes using NaHCO3 anolyte and HCl or NaCl catholyte.

Dual-chambered fuel cells with an iron anode and an air-carbon cathode separated by an ion exchange membranes have been used to treat arsenate during power production. To select an effective catholyte, the dual-chambered fuel cell consisted 90 mL of 0.1 M HCl or 0.5 M NaCl as the catholyte and 1 L of 0.1 M NaHCO3 as the anolyte at an initial pH 5. The 0.1 M HCl was an effective catholyte, with which 1 ppm arsenate in 1 L of anolyte was reduced to 5 ppb in 1 h, and the maximum power density was about 6.3 w/m2 with an anion exchange membrane fuel cell (AEM_FC) and 4.4 w/m2 with a cation exchange membrane fuel cell (CEM_FC). Therefore, 90 mL of 0.1 M HCl was used as a catholyte to treat 20 L of 0.1 M NaHCO3 anolyte containing 1 ppm arsenate at an initial pH of 5 or 7. The arsenate level at pH 5 decreased to less than 5 ppb in 4 h, and the maximum power density was 5.9 W/m2 and 4.7 W/m2 with AEM_FC and CEM_FC, respectively. When using 0.01 M NaHCO3 as the anolyte at pH 5, arsenate was reduced to less than 5 ppb in 8 and 24 h for AEC_FC and CEM_FC, respectively. However, when using an anolyte at pH 7, arsenate could not be effectively removed in 24 h. Therefore, when using carbonate as an anolyte, the solution should be adjusted to a weakly acidic pH in order to remove arsenate.

Hydrogen production in microbial reverse-electrodialysis electrolysis cells using a substrate without buffer solution.

The aim of this work was to use substrate without buffer solution in a microbial reverse-electrodialysis electrolysis cell (MREC) for hydrogen production under continuous flow condition (10 cell pairs of RED stacks, HRT=5, 7.5, and 15h). Decreasing in the HRT (increasing in the organic matter) made cell current stable and increased. Hydrogen gas was produced at a rate of 0.61m(3)-H2/m(3)-Van/d in H-MREC, with a COD removal efficiency of 81% (1.55g/L/d) and a Coulombic efficiency of 41%. This MREC system without buffer solution could successfully produce hydrogen gas at a consistent rate.

Scaled-up dual anode/cathode microbial fuel cell stack for actual ethanolamine wastewater treatment.

The aim of this work was to develop the scale-up microbial fuel cell technology for actual ethanolamine wastewater treatment, dual anode/cathode MFC stacks connected in series to achieve any desired current, treatment capacity, and volume capacity. However, after feeding actual wastewater into the MFC, maximum power density decreased while the corresponding internal resistance increased. With continuous electricity production, a stack of eight MFCs in series achieved 96.05% of COD removal and 97.30% of ammonia removal at a flow rate of 15.98L/d (HRT 12h). The scaled-up dual anode/cathode MFC stack system in this research was demonstrated to treat actual ETA wastewater with the added benefit of harvesting electricity energy.

The enhancement of ammonium removal from ethanolamine wastewater using air-cathode microbial fuel cells coupled to ferric reduction.

A microbial fuel cell (MFC) with biological Fe(III) reduction was implemented for simultaneous ethanolamine (ETA) degradation and electrical energy generation. In the feasibility experiment using acetate as a substrate in a single-chamber MFC with goethite and ammonium at a ratio of 3.0(mol/mol), up to 96.1% of the ammonium was removed through the novel process related to Fe(III). In addition, the highest voltage output (0.53V) and maximum power density (0.49Wm(-2)) were obtained. However, the ammonium removal and electrical performance decreased as acetate was replaced with ETA. In the long-term experiment, the electrical performance markedly decreased where the voltage loss increased due to Fe deposition on the membranes.

Continuous phosphorus removal from water by physicochemical method using zero valent iron packed column.

Excessive phosphorus in aquatic systems causes algal bloom resulting in eutrophication. To treat wastewater including effluent of wastewater treatment plant containing various amounts of phosphorus, a series of continuous experiments on removal of phosphorus from water were performed by using an electrochemical method. The spherical type of zero valent iron (ZVI) and silica sand were packed at appropriate volume ratio of 1:2 in a cylindrical column. An electric potential was applied externally, which can be changed as per the operational requirement. The results indicate that optimum hydraulic retention time of 36 min was required to meet the effluent standards with our laboratory-scale experimental setup. Lower amounts of phosphorus were removed by precipitation due to contact with iron, and additional electric potential was not required. In order to remove high amounts of phosphorus (around 150 mg/L as phosphate), external electric potential of 600 V was applied to the reactor. As the precipitation of phosphate mainly occurs at neutral pH, it is likely that FeHPO4 will be the main phosphorus-containing compound. Through the results of the large-scale experiments, the ZVI packed reactor can be used as a filter for removal of phosphorus of less than 10 mg/L as phosphate concentration.

As³âº removal by Ca-Mn-Fe3O4 with and without H2O2: effects of calcium oxide in Ca-Mn-Fe3O4.

As(3+) removal by Ca-Mn-Fe3O4 composites, which contained various wt% of Ca, are investigated. Immobilization of Ca (i.e. as crystalline forms including CaO2) and Mn (i.e. as an amorphous hydrous manganese oxide) on Fe3O4 were identified, and it was revealed that the co-immobilization of Ca and Mn (i.e. especially the wt% ratio of Ca:Mn:Fe=2:3:1) provided higher Ca wt% with greater surface area. The increasing Ca wt% (i.e. 6, 14, 17, and 19%) gradually increased the reactivity of H2O2 to oxidize As(3+) to As(5+). Moreover, it is suggested that superoxide anion produced from the catalytic decomposition of H2O2 reduces Mn(4+) to Mn(2+), which is further released into solution. On the other hand, As(3+) adsorption was decreased with the highest Ca wt% in Ca-Mn-Fe3O4. It was concluded that the increasing Ca wt% positively affected As(3+) oxidation but an excess Ca wt% negatively affected As(3+) adsorption. The higher As(3+) adsorption was observed when Ca wt% was 17 (i.e. the wt% ratios of Ca:Mn:Fe=2:3:1). Without H2O2, As(3+) was adsorbed and oxidized by Ca-Mn-Fe3O4 itself. It is suspected that As(3+) oxidation is due to H2O2 produced from CaO2. Mechanisms for As(3+) removal by Ca-Mn-Fe3O4 with and without H2O2 are proposed.

Performance comparison between mesophilic and thermophilic anaerobic reactors for treatment of palm oil mill effluent.

The anaerobic digestion of palm oil mill effluent (POME) was carried out under mesophilic (37°C) and thermophilic (55°C) conditions without long-time POME storage in order to compare the performance of each condition in the field of Sumatra Island, Indonesia. The anaerobic treatment system was composed of anaerobic hybrid reactor and anaerobic baffled filter. Raw POME was pretreated by screw decanter to reduce suspended solids and residual oil. The total COD removal rate of 90-95% was achieved in both conditions at the OLR of 15kg[COD]/m(3)/d. The COD removal in thermophilic conditions was slightly better, however the biogas production was much higher than that in the mesophilic one at high OLR. The organic contents in pretreated POME were highly biodegradable in mesophilic under the lower OLRs. The biogas production was 13.5-20.0l/d at the 15kg[COD]/m(3)/d OLR, and the average content of carbon dioxide was 5-35% in both conditions.

New and effective multi-element alpha-hematite systems for reduction of trichloroethylene.

The reactivity of different alpha-hematite (alpha-Fe203) systems for dechlorination of trichloroethylene (TCE) in the presence of Fe(II) and CaO was investigated. Initially different experiments were conducted to investigate the reactivity of pure and doped alpha-Fe203. It was found that the presence of elements such as Si, Cu, and Mn in alpha-Fe203 had a significant effect on TCE reduction potential of alpha-Fe203; however, the reduction potential was less than that of alpha-Fe203 (Bayferrox- 110 M, used in a previous study). Further studies were carried out and alpha-Fe203 was synthesized in a manner similar to that of Bayferrox-110 M. This synthetic alpha-Fe203 showed improved reactivity and was found to follow pseudo-first-order kinetics when used in TCE reduction experiments. The preliminary end products analysis showed that TCE degradation was probably via beta-elimination pathway. Detailed investigations ofa-Fe203 systems were carried out using X-ray diffraction, X-ray fluorescence, and scanning electron microscopy with energy-dispersive spectrometry. The results demonstrated that the TCE reduction capacity of alpha-Fe203 was strongly dependent on the other elements present in iron powder used to synthesize alpha-Fe203. It was suspected that these multi-elements in alpha-Fe203 helped to improve its conduction property. Current findings suggest that alpha-Fe203 not in the pure but combined with other elements could be thought as a potential system for TCE reduction.

Role of sol with iron oxyhydroxide/sodium dodecyl sulfate composites on Fenton oxidation of sorbed phenanthrene in sand.

In situ Fenton oxidation has been recently used to oxidize sorbed organic contaminants in soil. The objective of present contribution was to study the role of sodium dodecyl sulfate (SDS) as anionic surfactant and sol with iron oxyhydroxide/SDS for Fenton oxidation of sorbed phenanthrene in sand. The most effective experimental condition for phenanthrene oxidation was the Fenton-like reaction system with 0.35% H2O2, 30 mM SDS, and 4 mM FeCl2. The Fenton-like reactions under these experimental conditions resulted in the production and sustenance of a stable sol with iron oxyhydroxide/SDS composites over 24 h. The formation of iron oxyhydroxide/SDS composites resulted in stabilization of H2O2, and then the Fenton-like reactions were sustained over 24 h. Furthermore, the sol of iron oxyhydroxide/SDS composites gave suitable sites to sustain oxidations of dissolved phenanthrene over a prolonged reaction span, which is required for in situ chemical oxidation.

Dechlorination of liquid wastes containing chlorinated hydrocarbons by a binder mixture of cement and slag with Fe(II).

Iron-based degradative solidification/stabilization (DS/S-Fe(II)) is a modification of conventional solidification/stabilization (S/S) that incorporates degradative processes for organic contaminant destruction with immobilization. This study investigated the effectiveness of a binder mixture of Portland cement and slag in a DS/S-Fe(II) system to treat trichloroethylene (TCE), 1,1-dichloroethylene (1,1-DCE), vinyl chloride (VC), trichloromethane (CF), and dichloromethane (MC), which are major chlorinated hydrocarbons contained in waste oils and waste organic solvents. For TCE, 1,1-DCE, and VC, degradation experiments were conducted using three different binder combinations with Fe(II) (cement/Fe(II), slag/Fe(II), and cement/slag/Fe(II)). When cement and slag were mixed at a 1:1 ratio (% wt), the TCE and 1,1-DCE dechlorination rate was enhanced compared to that when cement or slag was used alone with Fe(II). Also, batch experiments were conducted in the solid phase consisting of cement, slag, sand, and Fe(II) to treat liquid wastes that contain chlorinated compounds at high concentrations. TCE was completely removed after 5 days in the cement/slag/sand/Fe(II) system, in which the initial TCE concentration was 11.8mM, with Fe(II) concentration of 565 mM. While the CF concentration was decreased by 95% after 5 days when the initial CF and Fe(II) concentration was 0.25 mM and 200 mM, respectively. However, MC was not degraded with the cement/slag/Fe(II) system.

Anaerobic treatment of palm oil mill effluent using combined high-rate anaerobic reactors.

Combined system of high-rate anaerobic reactors for treating palm oil mill effluent (POME) was developed and investigated in this study. The system composed of one common primary hybrid reactor which was shared by two different secondary filter reactors. An overall COD removal efficiency of 93.5% was achieved in both systems. The secondary reactors contributed not only in enhancing the COD removal efficiency, but also ensured the performance stability of the entire system. Biomass remained intact in the secondary reactor in contrast to the primary reactor in which occasional washout of biomass was observed. The pH of POME was adjusted at the beginning of the operation, as the process continued POME did not require the external pH adjustment as the pH was maintained in desired range. The biogas was produced up to 110 l/d with the yield of 0.171-0.269 l [CH4]/g [COD removed] and 59.5-78.2% content of methane.

Stabilization of hydrogen peroxide using phthalic acids in the Fenton and Fenton-like oxidation.

The stabilization of hydrogen peroxide was evaluated in Fenton reaction with phthalic acid as a stabilizer. The stabilization effect was high at a low pH

Properties of synthetic monosulfate as a novel material for arsenic removal.

Monosulfate was examined as a novel material for As(V) removal since its layered double hydroxide structure was expected to possess a high capacity for anion exchange. Phase-pure monosulfate was synthesized by hydration at 80-90°C for 36 h using a stoichiometric mixture of tricalcium aluminate (calcined at 1300°C) and gypsum. The analyses of PXRD, WDXRF, and FE-SEM confirmed the successful synthesis of highly pure monosulfate with a negligible impurity of ettringite. Batch experiments were carried out to investigate the kinetics of As(V) removal by monosulfate. A close relationship between As(V) uptake and sulfate release was observed. The intercalation of arsenate in the interlayer of monosulfate was confirmed by PXRD and FT-IR analyses. From a series of equilibrium batch experiments, it is seen that initial sorption of As(V) on monosulfate follows Langmuir isotherm, whereas further injection of As(V) caused transformation of monosulfate to ettringite, which was confirmed by FE-SEM micrographs. However, after the transformation, the solid phases in the equilibrium experiments were found to significantly lose their ability to take up As(V) in exchange for sulfate. A possible explanation for this result was hypothesized and discussed in the context of the literature.

Electrochemical removal of nitrate using ZVI packed bed bipolar electrolytic cell.

The present study investigates the performance of the zero valent iron (ZVI, Fe(0)) packed bed bipolar electrolytic cell for nitrate removal. The packing mixture consists of ZVI as electronically conducting material and silica sand as non-conducting material between main cathode and anode electrodes. In the continuous column experiments for the simulated groundwater (initial nitrate and electrical conductivity of about 30 mg L(-1) as N and 300 µS cm(-1), respectively), above 99% of nitrate was removed at the applied potential of 600 V with the main anode placed on the bottom of reactor. The influx nitrate was converted to ammonia (20% to maximum 60%) and nitrite (always less than 0.5 mg L(-1) as N in the effluent). The optimum packing ratio (v/v) of silica sand to ZVI was found to be 1:1-2:1. Magnetite was observed on the surface of the used ZVI as corrosion product. The reduction at the lower part of the reactor in acidic condition and adsorption at the upper part of the reactor in alkaline condition are the major mechanism of nitrate removal.

Effect of pH on Fenton and Fenton-like oxidation.

The lifetime of H2O2 is an important factor in the feasibility of Fenton's reaction for soil and groundwater remediation. The lifetime of H2O2 was evaluated in Fenton's reaction and Fenton-like reactions with haematite and magnetite. H2O2 was more stable in the Fenton-like reaction than in the Fenton's reaction. The lifetime of H2O2 was also highly affected by the solution pH, and a pH buffered acidic condition was preferred. Fenton's reaction and Fenton-like reaction were tested for phenanthrene adsorbed on sand. Fenton-like reaction and acidic condition showed better degradation rates in comparing with those of Fenton's reaction and unbuffered systems. The dissolved iron species were measured in the Fenton's reaction, and Fenton-like reaction with haematite as a function of pH. In the presence of H2O2, ferric iron was the major dissolved iron species and the pH buffered to acidic condition maintained relatively high levels of dissolved iron in the aqueous solution. The higher iron concentration in the solution contributed to effective production of hydroxyl radical and degradation of organic contaminants.

Comparison of hematite/Fe(II) systems with cement/Fe(II) systems in reductively dechlorinating trichloroethylene.

Reactive reductants of cement/Fe(II) systems in dechlorinating chlorinated hydrocarbons are unknown. This study initially evaluated reactivities of potential reactive agents of cement/Fe(II) systems such as hematite (alpha-Fe(2)O(3)), goethite (alpha-FeOOH), lepidocrocite (gamma-FeOOH), akaganeite (beta-FeOOH), ettringite (Ca(6)Al(2)(SO(4))(3)(OH)(12)), Friedel's salt (Ca(4)Al(2)Cl(2)(OH)(12)), and hydrocalumite (Ca(2)Al(OH)(6)(OH).3H(2)O) in reductively dechlorinating trichloroethylene (TCE) in the presence of Fe(II). It was found that a hematite/Fe(II) system shows TCE degradation characteristics similar to those of cement/Fe(II) systems in terms of degradation kinetics, Fe(II) dose dependence, and final products distribution. It was therefore suspected that Fe(III)-containing phases of cement hydrates in cement/Fe(II) systems behaved similarly to the hematite. CaO, which was initially introduced as a pH buffer, was observed to participate in or catalyze the formation of reactive reductants in the hematite/Fe(II) system, because its addition enhanced the reactivities of hematite/Fe(II) systems. From the SEM (scanning electron microscope) and XRD (X-ray diffraction) analyses that were carried out on the solids from hematite/Fe(II) suspensions, it was discovered that a sulfate green rust with a hexagonal-plate structure was probably a reactive reductant for TCE. However, SEM analyses conducted on a cement/Fe(II) system showed that hexagonal-plate crystals, which were presumed to be sulfate green rusts, were much less abundant in the cement/Fe(II) than in the hematite/Fe(II) systems. It was not possible to identify any crystalline minerals in the cement/Fe(II) system by using XRD analysis, probably because of the complexity of the cement hydrates. These observations suggest that major reactive reductants of cement/Fe(II) systems may differ from those of hematite/Fe(II) systems.

Cement paste column for simultaneous removal of fluoride, phosphate, and nitrate in acidic wastewater.

Cement paste, a cured mixture of cement and water, was reported to have considerable capacity for fluoride removal. In this study, heavily mixed fluoric acid wastewater from a semiconductor fabrication plant was applied to a column packed with cement paste granules to evaluate its capacity for the removal of fluoride and three other contaminants, phosphate, nitrate, and sulfate, as well as to investigate the interactions between these contaminants and cement components. The column reduced fluoride to remarkably low levels since fluorite was formed at highly elevated concentrations of calcium and the residual fluoride was further sorbed into the amorphous calcium phosphate that precipitated the entire amount of phosphate until breakthrough. The simultaneous removal of sulfate in the earlier stage was followed by significant removal of nitrate in exchange with the gradual release of sulfate. This behavior was explained by the co-precipitation of sulfate with calcium phosphate or calcium aluminate solids and the subsequent substitution of nitrate for the interlayer sulfate of monosulfate. However, the overall removal capacity of cement paste was reduced due to the high effluent loss of calcium and competition for calcium between fluoride and phosphate.