Chemical Oxygen Demand Oxidation Research Articles

Chemical oxygen demand oxidation via sustained-release persulfate balls: a rate-compatibility study of flow velocity, releasing, and oxidation

Chemical oxygen demand oxidation via sustained-release persulfate balls: a rate-compatibility study of flow velocity, releasing, and oxidation

Nitrate increases the capacity of an aerobic moving-bed biofilm reactor (MBBR) for winery wastewater treatment.

We used bench-scale tests and mathematical modeling to explore chemical oxygen demand (COD) removal rates in a moving-bed biofilm reactor (MBBR) for winery wastewater treatment, using either urea or nitrate as a nitrogen source. With urea addition, the COD removal fluxes ranged from 34 to 45 gCOD/m2-d. However, when nitrate was added, fluxes increased up to 65 gCOD/m2-d, twice the amount reported for aerobic biofilms for winery wastewater treatment. A one-dimensional biofilm model, calibrated with data from respirometric tests, accurately captured the experimental results. Both experimental and modelling results suggest that nitrate significantly increased MBBR capacity by stimulating COD oxidation in the deeper, oxygen-limited regions of the biofilm. Our research suggests that the addition of nitrate, or other energetic and broadly used electron acceptors, may provide a cost-effective means of covering peak COD loads in biofilm processes for winery or another industrial wastewater treatment.

Performance of pilot-scale membrane aerated biofilm reactors integrated with anoxic nano-biotechnological reactor for domestic wastewater treatment

Membrane-aerated biofilm reactors (MABRs) have aroused increasing attention due to their excellent performance in treating wastewater, where the membranes behave as bio-carriers for microorganisms and bubbleless air diffusers. The MABR technology has not been fully commercialized due to reactor design and low total nitrogen (TN) removal efficiency at short hydraulic retention times (HRT). In this study, a hybrid system of MABR 1 integrated with an anoxic nano-biotechnological reactor filled with Granulated Nanoscale Oxyhydroxides of Fe (GNOF) media was evaluated to assess the improvement in nitrogen removal performance at 12, 10, and 4 h of HRTs. At the same time, another MABR (MABR 2) was operated individually at 12, 10, 8, 6, 4, and 2 h of HRTs to assess the influence of HRT on nitrogen removal performance. An enhancement in removal performance was reported in the hybrid MABR-GNOF, achieving the highest removal efficiencies of 74.3 ± 3.1% for ammonium nitrogen (NH4+-N), 69.8 ± 2.1% for total nitrogen (TN), and 90.9 ± 1.7% for chemical oxygen demand (COD), at 12 h HRT. The hybrid MABR-GNOF system attained 18% higher nitrogen removal than the MABR-only system at 12 h of HRT. A simultaneous anoxic nitrification-denitrification and COD oxidation might be developed for the removal of COD, NH4+-N, and TN from domestic wastewater by using GNOF as an electron acceptor in the hybrid MABR-GNOF unit. The findings in this study confirmed the possibility of integration of GNOF and MABR on a pilot scale and are promising for the application of this hybrid system on a full scale.

Treating High COD Dyeing Wastewater via a Regenerative Sorption-Oxidation Process Using a Nano-Pored Activated Carbon.

Nowadays, the structural complexity of dyes used in the textile industry and the widely adopted water-saving strategy in the dyeing processes often fail plants’ biological wastewater treatment units due to chemical oxygen demand (COD) overload. To alleviate this problems, this study investigated a regenerable adsorption–oxidation process to treat dyeing wastewater with COD around 10,000 mg/dm3 using a highly nano-pored activated carbon (AC) as a COD adsorbent, followed by its regeneration using hydrogen peroxide as an oxidizing reagent. In addition to studying AC’s COD adsorption and oxidation performance, its operational treatment conditions in terms of temperature and pH were assessed. The results firstly demonstrated that about 50–60% of the COD was consistently adsorbed during the repeated adsorption operation before reaching AC’s maximum adsorption capacity (qmax) of 0.165 g-COD/g-AC. The optimal pH and temperature during adsorption were 4.7 and 25 °C, respectively. Secondly, AC regeneration was accomplished by using an initial peroxide concentration of 2.5% (by wt %) and EDTA-Fe of 2.12 mmole/dm3. The reuse of the regenerated ACs was doable. Surprisingly, after the first AC regeneration, the COD adsorption capacity of the regenerated AC even increased by ~7% with respect to the virgin AC. Thirdly, the results of a five-consecutive adsorption–regeneration operation showed that a total of 0.3625 g COD was removed by the 5 g AC used, which was equivalent to an adsorption capacity (q) of 0.0725 (= 0.3625/5) g-COD/g-AC during each adsorption stage. Based on the obtained results, a regenerable COD adsorption–oxidation process using a nano-pored AC to treat the high-textile-COD wastewater looks promising. Thus, a conceptual treatment unit was proposed, and its potential benefits and limitations were addressed.

Hybrid Photo-Fenton oxidation and biosorption for petroleum wastewater treatment and optimization using Box–Behnken Design

This study investigates the treatment of petroleum wastewater (PWTP) effluent using hybrid techniques (photo-Fenton oxidation and adsorption) to remove organic pollutants such as chemical oxygen demand (COD) and phenol. All the experiments were carried out in batch mode. The effects of pH, ferrous salt (Fe 2＋ ), and H 2 O 2 oxidation factors on the photo-Fenton process were studied. The response surface methodology (RSM) approach for experiment design and optimization yielded maximum COD and phenol removal at Fe 2＋ , H 2 O 2 , pH of 20 mM, 400 mM, and 3.8, respectively. In this optimal scenario, phenol reduction from the initial value of COD 12654.6 mg/L, phenol 213.0 mg/L was accomplished by 69.97% and 95.66%, respectively. Response surface methodology (RSM) photofenton based modeling and optimization was done using a Box–Behnken. The high coefficient of regression R 2 = 0 . 97 and 0.98 for COD and phenol oxidation is suggested by variance analysis (ANOVA). The PWTP effluent treated by Fenton oxidation with COD 4139.1 mg/L and phenol 70.1 mg/L was treated with Phragmites australis. Phragmites australis was chosen as an adsorbent. Phragmites australis was analyzed and characterized using several techniques, including Fourier transform infrared spectroscopy, Scanning Electron Microscopy, Zeta potential, and particle size distribution. The adsorption process step followed the photo-Fenton treatment process. The adsorption process achieved 69.04 % and 95.80% for COD and phenol removal. Kinetic studies showed that the statistics match very well in the nonlinear pseudo-first and second-order models based on the correlation coefficients (R 2 = 0 .999) and (R 2 = 0 .996), respectively, for COD and phenol removal in the adsorption phase. The severe adsorption potential for COD and phenol removal is 14421.97 mg/g and 374.90 mg/g, respectively. Finally, as a natural material, P. australis is a promising adsorbent material. • Box–Behnken Experimental Design (BBD) was used to determine the optimal removal efficiency for both COD and phenol for the photo-Fenton process. • Statistical analysis of the data indicated that H 2 O 2 significantly affected COD, phenol degradation for petroleum wastewater. • The optimum conditions for pH, Fe +2 , H 2 O 2 are 3.8, 20 mM, 400 mM for 69.97% COD, and 95.66% Phenol. • Phragmites australis was used as an adsorbent in the adsorption step. P. australis showed remarkable surface characteristics and adsorption ability. • The maximum adsorption capacity to remove COD and phenol of 14421.97, 374.90 mg/g, removal ratio 69.04%, and 95.80%, and the data fits very well in the nonlinear pseudo-first and second-order models.

Microbial Electrochemical Oxidation of Anaerobic Digestion Effluent From Treating HTC Process Water

Hydrothermal carbonization (HTC) is a promising technology for chemical and material synthesis. However, HTC produces not only valuable solid coal-materials but also yields process water (PW) with high chemical oxygen demand (COD) that requires extensive treatment. Anaerobic digestion (AD) has been used for initial treatment of HTC-PW, but the AD effluent is still high in COD and particles. Here, we show that microbial electrochemical technologies (MET) can be applied for COD removal from AD effluent of HTC-PW. Bioelectrochemical systems (BES) treating different shares of AD effluent from HTC-PW exhibited similar trends for current production. Thereby, maximum current densities of 0.24 mA cm−2 and COD removal of 65.4 ± 4.4% were reached (n = 3). Microbial community analysis showed that the genus Geobacter dominated anode biofilm and liquid phase of all reactors indicating its central role for COD oxidation and current generation.

Ammonium Recovery and Biogas Upgrading in a Tubular Micro-Pilot Microbial Electrolysis Cell (MEC).

Here, a 12-liter tubular microbial electrolysis cell (MEC) was developed as a post treatment unit for simultaneous biogas upgrading and ammonium recovery from the liquid effluent of an anaerobic digestion process. The MEC configuration adopted a cation exchange membrane to separate the inner anodic chamber and the external cathodic chamber, which were filled with graphite granules. The cathodic chamber performed the CO2 removal through the bioelectromethanogenesis reaction and alkalinity generation while the anodic oxidation of a synthetic fermentate partially sustained the energy demand of the process. Three different nitrogen load rates (73, 365, and 2229 mg N/Ld) were applied to the inner anodic chamber to test the performances of the whole process in terms of COD (Chemical Oxygen Demand) removal, CO2 removal, and nitrogen recovery. By maintaining the organic load rate at 2.55 g COD/Ld and the anodic chamber polarization at +0.2 V vs. SHE (Standard Hydrogen Electrode), the increase of the nitrogen load rate promoted the ammonium migration and recovery, i.e., the percentage of current counterbalanced by the ammonium migration increased from 1% to 100% by increasing the nitrogen load rate by 30-fold. The CO2 removal slightly increased during the three periods, and permitted the removal of 65% of the influent CO2, which corresponded to an average removal of 2.2 g CO2/Ld. During the operation with the higher nitrogen load rate, the MEC energy consumption, which was simultaneously used for the different operations, was lower than the selected benchmark technologies, i.e., 0.47 kW/N·m3 for CO2 removal and 0.88 kW·h/kg COD for COD oxidation were consumed by the MEC while the ammonium nitrogen recovery consumed 2.3 kW·h/kg N.

Perspectives of electrochemical oxidation parameters in PRW treatment

Electrochemical oxidation as an efficient route of advanced electrochemical oxidation process AEOP had been successfully applied for the treatment of real petroleum refinery wastewater (PRW). The electrochemical oxidation was performed using batch electrochemical reactor with carbon felt anode to be compared with β-PbO2 anode. However, these anodic materials have higher oxygen evolution over potential and poor electrocatalysts for parasitic reactions with low cost. The experimental work considers a scope of operative and design parameters that influence the chemical oxygen demand (COD) removal of wastewater of a real national oil refinery effluent. Accordingly, a well-designed reactor accomplished to treat wastewater samples of 500-510 mg/L initial COD to study the effect of anode material, current density, and temperature on COD removal and oxidation kinetic. The results showed that the COD removal efficiency exhibits an exponential behaviour with the applied current density of more than 10 mA cm−2 indicating first-order reaction kinetics, and the reaction rate constant accurately estimated. Moreover, the impacts of pH and agitation speed on reaction rate constant were also studied.

The role of influent organic carbon-to-nitrogen (COD/N) ratio in removal rates and shaping microbial ecology in soil aquifer treatment (SAT)

Soil columns simulating soil aquifer treatment (SAT), fed with synthetic secondary effluent by intermittent infiltration of flooding/drying cycles, were characterized for nitrogen and organic carbon removal, and microbial ecology and biokinetics. The columns differed in the concentration ratio of chemical oxygen demand (COD) to the summed NH4+, NO2− and organic nitrogen—2 (C/N2) or 5 (C/N5). Chemical profiles along the column demonstrated a preference for COD oxidation over nitrification and coupled denitrification, with higher nitrogen loss (57% vs. 16%) in the C/N5 column. Unexpectedly, significant dominance of the genus Nitrospira over the genus Nitrobacter and ammonia-oxidizing bacteria (AOB) was strongly correlated at column depths where NH4+ removal occurred. Moreover, the Nitrospira profile had the strongest correlation to the profile of NH4+ (positive) and NO3− (negative), strongly indicating complete ammonia oxidation. 16S sequencing analysis of the topsoil in C/N2 vs. C/N5 columns revealed double the abundance of microbial aerobic potential (64% vs. 32%) vs. one-third the denitrification potential (13% vs. 31%). The concentrations and degradability levels of organic carbon were the most influential parameters shaping community structure. Niche differentiation within the biofilm attached to the soil is suggested to have an important role in the process's anoxic activity and nitrogen removal.

Fate of malathion and a phosphonic acid in activated sludge with varying solids retention times

This study examined the ability of activated sludge (AS) to sorb and biodegrade ethylmethylphosphonic acid (EMPA) and malathion, a degradation product and surrogate, respectively, for an organophosphate chemical warfare agent. Sorption equilibrium isotherm experiments indicate that sorption of EMPA and malathion to AS is negligible. EMPA at a concentration of 1 mg L−1 degraded by approximately 30% with apparent first-order kinetics, possibly via co-metabolism from nitrification. Heterotrophic bacteria and abiotic mechanisms, however, are largely responsible for malathion degradation also with apparent first-order kinetics. EMPA did not inhibit chemical oxygen demand (COD) oxidation or nitrification activity, although malathion did appear to induce a stress response resulting in inhibition of COD oxidation. The study also included a 30-day experiment in which malathion, at a concentration of 5 mg L−1, was repeatedly fed to AS in bench-scale sequencing batch reactors (SBRs) operating at different solids retention times (SRTs). Peak malathion concentrations occurred at day 4.5, with the longer SRTs yielding greater peak malathion concentrations. The AS reduced the malathion concentrations to nearly zero by day 10 for all SRTs, even when the malathion concentration in the influent increased to 20.8 mg L−1. The data suggest a biodegradation pathway for malathion involving an oxygenase. Phylogenetic analyses revealed that all samples had an abundance of Zoogloea, though there was greater bacterial diversity in the SBR with the SRT of 50 days. The SBR with an SRT of 9.5 days had an apparent reduction in the diversity of the bacterial community.

Using D-optimal experimental design to optimise remazol black B mineralisation by Fenton-like peroxidation

The mineralisation of remazol black B (RBB) was studied at concentrations ranging from 20-1000 mgL−1. The work was aimed at investigating the Fenton-like peroxidation of RBB at a concentration typically obtained in Batik cottage industries. Other response parameters were degradation and colour removal efficiencies. The parameters that were measured included total organic carbon (TOC), chemical oxygen demand (COD) as well as absorbance for mineralisation, degradation and colour. To optimise the process, the interaction effects of several controlling variables on the treatment process were examined using dispersion matrix-optimal design and response surface analysis. Four specific variables: initial dye concentration (Dye)o; the molar ratio of oxidant to dye organic strength (H2O2):(COD); the mass ratio of the oxidant to the catalyst (H2O2):(Fe3+) and reaction time (t r), were observed. Three reduced empirical models, one for each response, were developed for describing the treatment process. For 20, 510 and 1000 mgL−1, the optimum %TOC reduction and oxidation times were 44% for 95 min, 52% for 52.5 min and 68% for 10 min corresponding to 67, 81 and 75% COD reduction, respectively. The optimum COD reduction and oxidation times were 89% for 95 min, 91% for 10 min and 84% for 95 min for concentrations of 20, 510 and 1000 mg L−1, respectively. For all concentrations, total colour removal was achieved. A comparison of the results obtained in this study with literature values for traditional Fenton, photo-Fenton and photo-Fenton-like oxidation indicated that the TOC reduction obtained using the Fenton-like process was satisfactory.

Simultaneous removal of organic matter and nitrogen compounds by an aerobic/anoxic membrane biofilm reactor

The hydrogen-based membrane biofilm reactor (MBfR) has been well studied and applied for denitrification of nitrate-containing water and wastewater. Adding an oxygen-based MBfR allows total-nitrogen removal when the input nitrogen is ammonium. However, most wastewaters also contain a significant concentration or organic material, measured as chemical oxygen demand (COD). This study describes experiments to investigate the removal of organic and nitrogenous compounds in the combined Aerobic/Anoxic MBfR, in which an Aerobic MBfR (Aer MBfR) precedes an Anoxic MBfR (An MBfR). The experiments demonstrate that the Aer/An MBfR combination accomplished COD oxidation and nitrogen removal for a total oxygen demand flux (i.e., from COD and NH 4 oxidations) in the range of 1.2–7.2 g O 2/m 2-d for 4.5 psi (0.3 atm) oxygen pressure to the Aer MBfR, but was overloaded and did not accomplish nitrification for the total oxygen demand load higher than 14 g O 2/m 2-d. Total-nitrogen removal was controlled by nitrification in the Aer MBfR, because the An MBfR denitrified all NO 3 − provided to it by the Aer MBfR. The overload of total oxygen demand did not affect COD oxidation in the Aer MBfR, but caused a small increase of COD in the An MBfR due to net release of soluble microbial products (SMP).

Physical and oxidative removal of organics during Fenton treatment of mature municipal landfill leachate

Municipal landfill leachate, especially mature leachate, may disrupt the performance of moderately-sized municipal activated sludge wastewater treatment plants, and likewise tend to be recalcitrant to biological pretreatment. Recently, Fenton methods have been investigated for chemical treatment or pre-treatment of mature leachate. In this paper, the results of laboratory tests to determine the roles of oxidation and coagulation in reducing the organic content of mature leachate during Fenton treatment are presented. The efficiencies of chemical oxygen demand (COD) oxidation and coagulation were tested, and the ratio of COD removal by oxidation to that by coagulation was assessed, under various operating conditions. Low initial pH, appropriate relative and absolute Fenton reagent dosages, aeration, and stepwise addition of reagents increased COD removal by oxidation and the importance of oxidation relative to coagulation. Simultaneous aeration and stepwise reagent addition allowed comparable treatment without initial acidification pH, due to the generation of acidic organic intermediates and the continuous input of CO 2. On the other hand, high COD oxidation efficiency and low ferrous dosage inhibited COD removal by coagulation. At significantly high oxidation efficiency, overall COD reduction decrease slightly due to low coagulation efficiency. Under the most favorable conditions (initial pH 3, molar ratio [H 2O 2]/[Fe 2+] = 3, [H 2O 2] = 240 mM, and six dosing steps), 61% of the initial COD was removed, and the ratio of COD removal oxidation to coagulation was 0.75. Results highlighted the synergistic roles of oxidation and coagulation in Fenton treatment of mature leachate, and the role of oxidation in controlling the efficiency of removal of COD by coagulation.

Anodic oxidation with doped diamond electrodes: a new advanced oxidation process

Boron-doped diamond anodes allow to directly produce OH radicals from water electrolysis with very high current efficiencies. This has been explained by the very high overvoltage for oxygen production and many other anodic electrode processes on diamond anodes. Additionally, the boron-doped diamond electrodes exhibit a high mechanical and chemical stability. Anodic oxidation with diamond anodes is a new advanced oxidation process (AOP) with many advantages compared to other known chemical and photochemical AOPs. The present work reports on the use of diamond anodes for the chemical oxygen demand (COD) removal from several industrial wastewaters and from two synthetic wastewaters with malic acid and ethylenediaminetetraacetic (EDTA) acid. Current efficiencies for the COD removal between 85 and 100% have been found. The formation and subsequent removal of by-products of the COD oxidation has been investigated for the first time. Economical considerations of this new AOP are included.

Pre-oxidation of an extremely polluted industrial wastewater by the Fenton’s reagent

The pre-oxidation of an extremely polluted pharmaceutical wastewater (chemical oxygen demand (COD) value of 362,000 mg/l) using the Fenton’s reagent has been systematically studied using an experimental design technique. The parameters influencing the COD removal of the wastewater, namely temperature, ferrous ion and hydrogen peroxide concentrations have been optimized to achieve a COD global reduction of 56.4%. The total range of the proposed experimental design, however, could not be tested because under some conditions (hydrogen peroxide concentration over 5 M) the Fenton’s reaction became violent and could not be controlled, probably due to the high exothermic effect associated with COD oxidation. For the tested conditions, the optimal values of hydrogen peroxide and ferrous ion concentration were 3 and 0.3 M, respectively, whereas temperature only showed a mild positive effect on COD removal. In addition, during the first 10 min of Fenton’s reaction, more than 90% of the total COD removal can be achieved. Fenton’s reaction has proved to be a feasible technique for the pre-oxidation of the wastewater under study, and can be considered a suitable pre-treatment for this type of wastewaters.

Treatment of Photographic Effluents by Electrochemical Method

Fixing and bleach/fixing solutions from photographic process were treated in this investigation by an electrochemical reduction process for silver recovery and oxidation process to reduce chemical oxygen demand (COD) levels. The COD oxidation process was undertaken after the silver recovery process. According to these results, silver recovery rate from bleach/fixing solution depends heavily on pHs, whereas the nature of silver deposit from fixing solution is sensitive to cathode potential. The COD, NH4+-N, and total organic carbon (TOC) removal rates from both fixing and bleach/fixing solutions were also examined by electrochemical oxidation at a IrO2 + RuO2/Ti anode with and without the addition of NaCl. In the fixing solution, the oxidation rate of inorganic compounds is faster than that of organic compounds. Under the operating conditions, a current density of 10 A/dm2, and by adding 5% NaCl, about 90% of the COD and NH4+-N in the fixing solution was removed after electrolysis for 10 h. For a bleach/fixing solution, the COD removal rate was independent of the addition of NaCl; meanwhile, the NH4+-N removal rate increased with addition of NaCl. Under the operating conditions of 10 A/dm2 current density and the addition of 5% NaCl, over 95% of COD was removed after electrolysis for 10 h. At the same time, 42,000 mg/L NH4+-N was also completely removed. Key words: Electrochemical oxidation; silver recovery; photographic effluents