On-site formation of hypochlorite for indigo oxidation – Scale-up and full scale operation of an electrolyser for denim bleach processes

On-site production of hypochlorite for denim bleach was investigated using undivided unipolar electrolysers. The current efficiency of the electrolysis process was studied at laboratory scale with up to 20 A cell current and at the technical scale using a 1200 A electrolyser. NaCl solutions in the concentration range 0.236–0.944 M NaCl (13.8–55.2 g l⁻¹) were used. Anodic current densities up to 400 A m⁻² were used. Hypochlorite solutions with active chlorine concentration c(Cl)=0.10–0.12 M were obtained with current efficiency of 58–70%. For denim bleach processes a concentration of active chlorine up to c(Cl)=0.12 M is required. This corresponds to approximately 30 ml l⁻¹ of commercial hypochlorite solution. Electrical energy consumption calculated per kg of active chlorine formed ranges from 5.7 to 8.6 kWh kg⁻¹. By coupling the electrolyser to a commercial 30 kg capacity drum washing machine the electrochemically prepared oxidant was successfully used in bleach processes. The technique overcomes problems of insufficient reproducibility of bleach, chemical costs and released wasted water due to the use of commercial NaOCl solution.     

Nitrification and sludge characteristics in a submerged membrane bioreactor on synthetic inorganic wastewater

A submerged membrane bioreactor (SMBR) treating ammonia-bearing synthetic inorganic wastewater withoutsludge purge was studied in respect to nitrification and microbial parameters over a period of 210 days. The reactor was operated at a hydraulic retention time (HRT) of 24 h, and the NH_4-N volumetric loading rate increased from 0.18 to 1.30 kg NH₄⁺-N m⁻³d⁻¹ by increasing influent NH₄⁺-N from 180 mg/l⁻¹ to 1300 mg/l⁻¹. With the exception of a short period after the failure of pH control, the NH₄⁺-N⁺ removal rate, was constantly above 99%. Due to the influent characteristics and the interception of the membrane module, the mixed liquor suspended solids (MLSS) varied from 3000 to 5000 mg/l⁻¹ and the nitrifying bacteria were dominant in the SMBR. The numbers of ammonia oxidizers and nitrite oxidizers in the mixed liquor increased from 0.9×10⁸ ml⁻¹ and 1.0×10⁸ ml to 1.6×10⁸ ml⁻¹ and 9×10⁸ ml⁻¹ respectively, and the specific nitrification rate from 0.27 to 0.56 g NH₄⁺-N g⁻¹ SS⁻¹ d⁻¹. An increasing occurrence of extracellular polymeric substances (EPS) around microbial clusters with operation time was clearly observed on scanning electron micrographs (SEM). The pressure difference of the membrane module was not over 0.01 mPa over the whole operation period. Present results show that SMBR can be operated efficiently and stably as a high-rate nitrifying technology.     

Hg detection by measuring thiol groups with a highly sensitive screen-printed electrode modified with a nanostructured carbon black film

A sensor based on a screen-printed electrode (SPE) modified with a stable dispersion of commercially available carbon black (CB) N220 was optimised and challenged with several thiol-containing compounds. This probe showed a significantly enhanced electrochemical activity respect to a bare SPE when tested with thiocholine, cysteine, glutathione and cysteamine. When challenged in amperometric batch mode, the response was stable and showed a linear dependence up to 1 × 10⁻⁵ mol l⁻¹ for thiocholine and cysteine. The very high sensitivity towards these thiols (299 mA mol⁻¹ l cm⁻² for thiocholine and 441 mA mol⁻¹ l cm⁻² for cysteine) was then used as the basis for developing an analytical method for mercury ion detection since a non electroactive complex (thiol–Hg) is formed in the presence of the metal. By selecting an appropriate concentration of thiocholine, a concentration of mercury as low as 5 × 10⁻⁹ mol l⁻¹ (1 ppb) was detected. Satisfactory recovery was obtained when the system was tested on drinking water samples.     

Influence of COD:N:P ratio on dark greywater treatment using a sequencing batch reactor

The recycling of greywater is an integral part of a water management system owing to the scarcity of fresh water resources. This article explores the effectiveness of an aerobic sequencing batch reactor in treating nutrient‐deficit and nutrient‐spiked dark greywater for agricultural reuse. The dark greywater in the present investigation had a COD:N:P ratio of 100:1.82:0.76, while the preferred ratio for biological oxidation is 100:5:1 (COD, chemical oxygen demand). The aerobic oxidation of nutrient‐deficit and nutrient‐spiked dark greywater with a COD:N:P ratio of 100:2.5:0.5; 100:3.5:0.75 and 100:5:1 resulted in outlet COD values of 64; 35; 15 and 12 mg L^?1, with a corresponding BOD₅ value of 37; 22; 10 and 8 mg L^?1 at 36 h hydraulic retention time (HRT). Hence treatment of nutrient‐added dark greywater at a COD:N:P ratio 100:3.5:0.75 and 100:5:1 for 36 h HRT complied with the Malaysian discharge standards for agricultural activities. Treated greywater has the potential for consideration as a resource, since it can be used as a supplement or replacement for potable water in landscape irrigation and other agricultural activities in rural and urban areas. Moreover, the level of greywater treatment is dictated by the final water quality requirement. Copyright © 2008 Society of Chemical Industry     

Greywater recycling in Vietnam — Application of the HUBER MBR process

Greywater is the part of domestic wastewater that is free of faeces. The volume and concentration of this separately collected wastewater flow depend on the consumer behaviour and vary according to its source. The average amount of greywater produced per day in a German household is 70 l per person, which is more than 50% of the total wastewater production [5]. This figure corresponds with the average figures provided for Chinese households (80 l per person/day, GB/T 50331-2002), but significantly exceeds the South African average of 20 l per person and day [1].Compared to domestic wastewater, greywater generally contains less organic pollutants, less nutrients but a high amount of tensides. The effluent from bath tubs, showers or wash hand basins contains for example a by approx. two decimal orders lower number of total and faecal coliform bacteria (Escherichiacoli) [2] and [6].Due to its relatively low content of pollutants, greywater is easy to treat with MBRs. The pollutants contained are decomposed by the bacteria of the activated sludge tank. The following membrane filtration unit separates the treated greywater from the activated sludge. The treated greywater is of high quality and hygienically safe so that it can be reused, alone or combined with rain water, for toilet flushing water, laundry washing or for irrigation purposes.Within the scope of the SANSED II research project HUBER has been successful in adapting the MBR system for greywater treatment to the specific conditions in Vietnam and testing the system in operation in a small city in the Mekong delta, South Vietnam. The wastewater from kitchen sinks and the bathrooms of a dormitory on the campus of Can Tho University was clarified in the HUBER GreyUse^® plant over a period of three months. The project aim was the production of high quality service water from greywater for safe reuse as toilet flush water.     

Scale-up of B-doped diamond anode system for electrochemical oxidation of phenol simulated wastewater in batch mode

Scale-up of boron-doped diamond (BDD) anode system is critical to the practical application of electrochemical oxidation in bio-refractory organic wastewater treatment. In this study, the scale-up of BDD anode system was investigated on batch-mode electrochemical oxidation of phenol simulated wastewater. It was demonstrated that BDD anode system was successfully scaled up by 121 times without performance deterioration based on the COD and specific energy consumption (E_sp) models in bath mode. The COD removal rate and E_sp for the scaled-up BDD anode system through enlarging the total anode area while keeping similar configuration, remained at the similar level as those before being scaled up, under the same area/volume value, current density, retention time and wastewater characteristics. The COD and E_sp models used to describe the smaller BDD anode system satisfactorily predicted the performance of the scaled-up BDD anode system. Under the suitable operating conditions, the COD of phenol simulated wastewater was reduced from 540 mg l⁻¹ to 130 mg l⁻¹ within 3 h with an E_sp of only 34.76 kWh m⁻³ in the scaled-up BDD anode system. These results demonstrate that BDD anode system is very promising in practical bio-refractory organic wastewater treatment.     

Kinetic study of hydrogen sulfide absorption in aqueous chlorine solution

Hydrogen sulfide (H₂S) is currently removed from gaseous effluents by chemical scrubbing using water. Chlorine is a top-grade oxidant, reacting with H₂S with a fast kinetic rate and enhancing its mass transfer rate. To design, optimize and scale-up scrubbers, knowledge of the reaction kinetics and mechanism is requested. This study investigates the H₂S oxidation rate by reactive absorption in a mechanically agitated gas–liquid reactor. Mass transfer (gas and liquid sides mass transfer coefficients) and hydrodynamic (interfacial area) performances of the gas–liquid reactor were measured using appropriated physical or chemical absorption methods. The accuracy of these parameters was checked by modeling the H₂S absorption in water without oxidant. A sensitivity analysis confirmed the robustness of the model. Finally, reactive absorption of H₂S in chlorine solution for acidic or circumneutral pH allowed to investigate the kinetics of reaction. The overall oxidation mechanism could be described assuming that H₂S is oxidized irreversibly by both hypochlorite anion ClO⁻ (k = 6.75 × 10⁶ L mol⁻¹ s⁻¹) and hypochlorous acid ClOH (k = 1.62 × 10⁵ L mol⁻¹ s⁻¹).     

Fenton's process for simultaneous removal of TOC and Fe from acidic waste liquor

The potential of Fenton's reagent for the removal of organic substrates and ferrous ions, which are the main pollutants in acidic waste liquor, was assessed. The optimum molar ratio of for the removal of Fe²⁺ was 72-76, which could be indicated by variations of ORP. Under optimal H₂O₂ dose, the minimum Fe²⁺ concentration (12-13 mg/l-⁻¹) appeared at 45 min under a pH of 327-450. Under an H202 dose of 95 mg/l⁻¹, nearly 80% of TOC removal was caused by adsorption for a total TOC removal of 49%, and the contribution of oxidation was not over 20%. At 380 mg/l⁻¹ H₂0₂, more than 76% of TOC removal was contributed by oxidation, for a total TOC removal of 65%.     

Removal and recovery of copper via a galvanic cementation system part II: batch-recycle reactor

This paper describes a batch-recycle galvanic reactor, operated in the flow-by configuration, for the removal of copper from dilute industrial effluents. A three-dimensional cathode, 80 ppi reticulated vitreous carbon, was used for this purpose. Mass transfer studies show that the average mass transfer coefficient was proportional to the Reynolds number, Re^f, where f=0.68, which was independent of the concentration of reactant species under the experimental conditions. A comparison of the performance between a single-pass and a batch-recycle reactor was also conducted with an initial copper concentration of 10 mg l^–1, 100 mg l^–1 and 500 mg l^–1. A 500 ml feed of 74.2 mg l^–1 of copper in electroplating rinse water with a low conductivity of 1.2 mS cm^–1 was reduced to less than 1.0 mg l^–1 in 150 min at a flow rate of 500 ml min^–1.     

Evaluation of the photoelectrocatalytic method for oxidizing chloride and simultaneous removal of microcystin toxins in surface waters

The production of chlorine was investigated in the photoelectrocatalytic oxidation of a chloride-containing solution using a TiO₂ thin-film electrode biased at current density from 5 to 50 mA cm⁻² and illuminated by UV light. Such parameters as chloride concentrations from 0.001 to 0.10 mol L⁻¹, pH 2-12, and interfering salts were varied in this study in order to determine their effect on this oxidation process. At an optimum condition this photoelectrocatalytic method can produce active chlorine at levels compatible to water disinfections processes using a chloride concentration higher than 0.010 mol L⁻¹ at a pH of 4 and a current density of 30 mA cm⁻². The method was successfully applied to treat surface water collected from a Brazilian river. After 150 min of photoelectrocatalytic oxidation, we obtained a 90% reduction in total organic carbon removal, a 100% removal of turbidity, a 93% decrease in colour and a chemical oxygen demand (COD) removal of around 96% (N = 3). The proposed technology based on photoelectrocatalytic oxidation was also tested in treating 250 mL of a solution containing 0.05 mol L⁻¹ NaCl and 50 μg L⁻¹ of Microcystin aeruginosa. The bacteria is completely removed after 5 min of photoelectrocatalysis following an initial rate constant removal of −0.260 min⁻¹, suggesting that the present method could be considered as a promising alternative to chlorine-based disinfections.     

Phosphorus fertigation of trickle-irrigated potato

A 3-year field study, on Pellic Vertisol, investigated the response of trickle-irrigated potato (Solanum tuberosum L.) to four P levels applied with the irrigation water. Waters supplied with 130 and 120 mg l^–1 of N and K, respectively, and with P levels of 0, 20, 40 and 60 mg l^–1, were applied when the soil water potential was between 0.03 and 0.04 MPa. The water applied at each irrigation was equivalent to 0.8 of pan evaporation from a screened USWB Class A pan. With the application of 40 mg P l^–1 no P accumulation deeper in the soil profile occurred, whereas P in petioles was at levels recommended for high yield of good quality. At this P concentration in irrigation water, removal of P from soil by tubers was 22 kg/ha/year. The highest yield of good quality was obtained at 40 mg P l^–1.     

The physical–chemical properties and electrocatalytic performance of iridium oxide in oxygen evolution

An IrO₂ anode catalyst was prepared by using the Adams method for the application of a solid polymer electrolyte (SPE) water electrolyzer. The effect of calcination temperature on the physical–chemical properties and the electrochemical performance of IrO₂ were examined to obtain a low loading and a high catalytic activity of oxygen evolution at the electrode. The physical–chemical properties were studied via thermogravimetry–differential scanning calorimetry (TG–DSC), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The electrochemical activity was investigated by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronopotentiometry in 0.1 mol L⁻¹ H₂SO₄ at room temperature. The optimum condition was found to be at the calcination temperature of 500 °C, where the total polarization reached a minimum at high current densities (>200 mA cm⁻²). The optimized catalyst was also applied to a membrane electrode assembly (MEA) and stationary current–potential relationships were investigated. With an optimized catalytic IrO₂ loading of 1.5 mg cm⁻² and a 40% Pt/C loading of 0.5 mg cm⁻², the terminal applied potential difference was 1.72 V at 2 A cm⁻² and 80 °C in a SPE water electrolysis cell.     

Development of an experimental system for greywater reuse

Greywater reuse promotes a significant reduction in potable water consumption and sewage production, once the water is used a second time for non potable purposes prior of being discharged to the sewer system. However, its quality must assure the user's safety and thus a treatment system is necessary.The present article presents a study on a low cost and easy maintenance experimental system for greywater reuse with a collection tank and a treatment system composed of a pump, filter and UV disinfection. The objectives of this study include analysis of the treatment efficiency and assessment of the quality potential of treated greywater. For this study, raw greywater was collected from washing basins of public and exclusive access toilets as well as from showers of a changing room.The experimental treatment system showed potential for greywater recovery, because of the simple, low-cost and easy maintenance features, and also because it provides high reduction of SS, COD and BOD. More significantly, no total or fecal coliforms were detected in all treated greywater samples. However, concentrations of SS and BOD after treatment were not low enough to reach the limits presented in legal and reference documents, hence further improvement procedures are suggested.     

A novel perforated electrode flow through cell design for chlorine generation

Chlorination remains a predominant method for disinfecting drinking water. Electrogeneration of chlorine has the potential to become the favoured method of chlorine production if costs can be lowered and chlorine generation efficiencies can be improved. A novel perforated electrode flow through (PEFT) cell design has been developed to address these problems. The electrodes were made from low-cost graphite sheets and stainless steel mesh and separated by a non-conducting fabric membrane. This electrode configuration allows reduction of electrode separation to 0.1 mm or less, minimizing cell resistance and increasing electrical efficiency. The new PEFT configuration generates hypochlorite from a 0.5 mol L⁻¹ brine at a current efficiency of better than 60%. As an inline in situ device, it produces chlorine concentrations known to be sufficient to disinfect water, from chloride concentrations as low as 0.004 mol L⁻¹ (available in most natural waters) by a single pass of the water through the cell operating at 11 V. The possibility of a portable device operated by a 12-V battery is indicated.     

Photoinducedly electrochemical preparation of Prussian blue film and electrochemical modification of the film with cetyltrimethylammonium cation

This work presents a photoinducedly electrochemical preparation of Prussian blue from a single sodium nitroprusside and insertion of cetyltrimethylammonium cations into Prussian blue as counter ions. The product of photoinducedly electrochemical reactions has a couple of voltammetric peaks at E° = 0.266 V in 0.2 mol l⁻¹ KCl solution, the measurements of X-ray powder diffraction and FT-IR spectroscopy show that it is Prussian blue (PB). The formation mechanism of a pre-photochemical reaction and subsequent electrochemical reaction is suggested. The cyclic voltammetric treatment of the freshly as-prepared PB film in 1.0 mmol l⁻¹ cetyltrimethylammonium (CTA) bromide solution leads to the insertion of cetyltrimethylammonium cations into the channels of Prussian blue, which substitutes for potassium ions as counter ions in Prussian blue. The Prussian blue containing CTA counter ions shows two couples of voltammetric peaks at E° = −0.106 V and E° = 0.249 V in 0.2 mol l⁻¹ KCl solution containing 1.0 mmol l⁻¹ cetyltrimethylammonium bromide. Compared with the electrochemical behaviors of KFeFe(CN)₆ in 0.1 mol l⁻¹ KOH alkali solution, CTAFeFe(CN)₆ shows relatively durable voltammetric currents due to the hydrophobic effects of cetyltrimethylammonium. The diffusion coefficients for CTA and potassium cations were estimated to be D_CTA 1.25 × 10⁻¹² cm² s⁻¹, D_K 2.59 × 10⁻¹² cm² s⁻¹, respectively. The peak current of electro-catalytic oxidization on hydrogen peroxide showed a linear dependence from 6.59 × 10⁻⁶ to 2.20 × 10⁻⁴ mol l⁻¹ with R = 0.99947 (n = 8). The linear regression equation was I_p (mA) = 0.82949 + 0.00594C (μmol l⁻¹) with errors of ±7.92833 × 10⁻⁵ for the slope and ±0.01085 for the intercept with the detection limit of 1.46 × 10⁻⁶ mol l⁻¹. Thus, it is expected to find its application in neutral or weak alkali medium for biosensors.     

Cobalt(II) porphyrin complex immobilized on the binary oxide SiO2/Sb2O3: electrochemical properties and dissolved oxygen reduction study

In this work, SiO₂/Sb₂O₃ prepared by the sol-gel processing method, having a specific surface area, S_BET, of 790 m² g⁻¹, an average pore diameter of 1.9 nm and 4.7 wt.% of Sb, was used as substrate base for immobilization of the 5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H,23H-porphine ion. Cobalt(II) ion was inserted into the porphyrin ring with a yield of complex bonded to the substrate surface of 59.4 μ mol g⁻¹. A carbon paste electrode of this material was used to study, by linear sweeping voltammetric and chronoamperometric techniques, the electrocatalytic reduction of dissolved oxygen. The reduction, at the electrode solid-solution interface, occurred at −0.25 V versus SCE in 1.0 mol l⁻¹ KCl solution, pH 5.5, by a four electron mechanism. The electrode response was invariant under various oxidation-reduction cycles showing that the system is chemically very stable. Such characteristics allowed the study of the electrode response towards various dissolved oxygen concentrations using the chronoamperometry technique. The cathodic peak current intensities plotted against O₂ concentrations, between 1.0 and 12.8 mg l⁻¹, showed a linear correlation. The electrode response time was very fast, i.e. about 1 s. This study was extended using the electrode to determine the concentration of dissolved oxygen in sea water samples.     

A nano-structured Ni(II)–ACDA modified gold nanoparticle self-assembled electrode for electrocatalytic oxidation and determination of tryptophan

A nano-structured Ni (II)/ACDA (2-amino-1-cyclopentene-1-dithiocarboxylic acid) film was electrodeposited on a gold nanoparticle–cysteine–gold electrode. The formation of Ni (II)/ACDA film and electrocatalytic oxidation of tryptophan on the surface of the modified electrode were investigated with cyclic voltammetric and chronoamperometric techniques. The hydrodynamic amperometry at rotating modified electrode was used for determination of tryptophan in the range of 0.085–43.0 μmol l⁻¹. The detection limit was found to be 23 nmol l⁻¹. The rate constant, transfer coefficient for the catalytic reaction and the diffusion coefficient of tryptophan in the solution were found to be 9.1 × 10² M⁻¹ S⁻¹, 0.52 and 1.09 × 10⁻⁵ cm² s⁻¹ respectively. It is worth noting that the as formed matrix in our work possesses a 3D porous network structure with a large effective surface area and high catalytic activity and behaves like microelectrode ensembles. The modified electrode indicated reproducible behavior and a high level stability during the experiments, making it particularly suitable for the analytical purposes.     

Simultaneous voltammetric determination of ascorbic acid, dopamine and uric acid by methylene blue adsorbed on a phosphorylated zirconia-silica composite electrode

This paper describes the preparation, characterization and application of a composite electrode based on methylene blue adsorption to phosphorylated zirconia-silica mixed oxide particles prepared by a sol-gel process. This electrode electrocatalytically oxidizes ascorbic acid (AA), dopamine (DA) and uric acid (UA), allowing their simultaneous voltammetric detection. Well-defined and -separated oxidation peaks were observed by differential pulse voltammetry in a 0.35 mol l⁻¹ Tris-HCl buffer solution (pH 7.4) containing 0.5 mol l⁻¹ KCl. The anodic peak currents observed at −74, 94 and 181 mV increased with increasing concentrations of AA, DA and UA, respectively. Linear calibration plots were obtained over the range of 100-1600 μmol l⁻¹ for ascorbic acid, 6-100 μmol l⁻¹ for dopamine and 22-350 μmol l⁻¹ for uric acid with detection limits of 8.3 ± 0.1, 1.7 ± 0.1 and 3.7 ± 0.2 μmol l⁻¹, respectively. DA and UA concentrations could also be determined under conditions of excess AA (1 mmol l⁻¹).     

o-Phenylenediamine adsorbed onto silica gel modified with niobium oxide for electrocatalytic NADH oxidation

A study of a modified carbon paste electrode employing o-phenylenediamine (PDA) adsorbed onto silica gel modified with niobium oxide (SN) for electrocatalytic oxidation of nicotinamide adenine dinucleotide (NADH) is described. The species adsorbed on SN was used to prepare a modified carbon paste electrode to investigate its electrochemical properties. The formal potential (E^0′) of the adsorbed PDA was −140 mV vs. SCE (saturated calomel electrode). The electrochemical behavior of the adsorbed PDA, compared to that of PDA dissolved in aqueous solution, was completely different. In solution, pH between 3.0 and 8.0, E^0′ remained almost constant and the response was very stable. A linear response range for NADH between 4.0×10⁻⁵ and 8.0×10⁻⁴ mol l⁻¹, at pH 7.0, was observed for the electrode, with an applied potential of −50 mV vs. SCE. The formation of an intermediate charge transfer complex is proposed for the charge transfer reaction between NADH and adsorbed PDA. The heterogeneous electron transfer rate, k_obs, was 5480 mol⁻¹ l s⁻¹ and the apparent Michaelis-Menten constant, 1.04×10⁻⁴ mol l⁻¹ at pH 7.0, evaluated with rotating disk electrode (RDE) experiments with an electrode with a coverage of PDA of 5.7×10⁻⁹ mol cm⁻². The slight increase in the reaction rate with the solution pH was assigned to the thermodynamic driving force.     

Electrochemical behaviour of the chloride/chlorine system at platinum electrodes in acetonitrile solutions

The electrochemical behaviour of chlorine and chloride solutions in acetonitrile at platinum electrodes has been studied. The rotating disk electrode technique was applied in a temperature range of −6 to 30 ± 0·1°C. The over-all reaction Cl₂ + 2 e⁻ ? 2 Cl⁻ undergoes a two-electron exchange per mol of chlorine and only one anodic and one cathodic wave are found.