Palm oil is one of the most important agroindustries in Malaysia. Huge quantities of palm oil mill effluent (POME) pose a great threat to aqueous environment due to its very high COD. To make full use of discharged wastes, the integrated "zero discharge" pilot-scale industrial plant comprising "pretreatment-anaerobic and aerobic process-membrane separation" was continuously operated for 1 year. After pretreatment in the oil separator tank, 55.6% of waste oil in raw POME could be recovered and sold and anaerobically digested through 2 AnaEG reactors followed by a dissolved air flotation (DAF); average COD reduced to about 3587 mg/L, and biogas production was 27.65 times POME injection which was used to generate electricity. The aerobic effluent was settled for 3 h or/and treated in MBR which could remove BOD3 (30°C) to less than 20 mg/L as required by Department of Environment of Malaysia. After filtration by UF and RO membrane, all organic compounds and most of the salts were removed; RO permeate could be reused as the boiler feed water. RO concentrate combined with anaerobic surplus sludge could be used as biofertilizer.
The application of low-cost adsorbents obtained from plant wastes as a replacement for costly conventional methods of removing heavy metal ions from wastewater has been reviewed. It is well known that cellulosic waste materials can be obtained and employed as cheap adsorbents and their performance to remove heavy metal ions can be affected upon chemical treatment. In general, chemically modified plant wastes exhibit higher adsorption capacities than unmodified forms. Numerous chemicals have been used for modifications which include mineral and organic acids, bases, oxidizing agent, organic compounds, etc. In this review, an extensive list of plant wastes as adsorbents including rice husks, spent grain, sawdust, sugarcane bagasse, fruit wastes, weeds and others has been compiled. Some of the treated adsorbents show good adsorption capacities for Cd, Cu, Pb, Zn and Ni.
The adsorption of Cu(II) ions from aqueous solution by chitosan and chitosan/PVA beads was studied in a batch adsorption system. Chitosan solution was blended with poly(vinyl alcohol) (PVA) in order to obtain sorbents that are insoluble in aqueous acidic and basic solution. The adsorption capacities and rates of Cu(II) ions onto chitosan and chitosan/PVA beads were evaluated. The Langmuir, Freundlich and BET adsorption models were applied to describe the isotherms and isotherm constants. Adsorption isothermal data could be well interpreted by the Langmuir model. The kinetic experimental data properly correlated with the second-order kinetic model, which indicates that the chemical sorption is the rate-limiting step. The Cu(II) ions can be removed from the chitosan and chitosan/PVA beads rapidly by treatment with an aqueous EDTA solution. Results also showed that chitosan and chitosan/PVA beads are favourable adsorbers.
A new method of Standard Malaysian Rubber (SMR) process wastewater treatment was developed based on in situ hypochlorous acid generation. The hypochlorous acid was generated in an undivided electrolytic cell consisting of two sets of graphite as anode and stainless sheets as cathode. The generated hypochlorous acid served as an oxidizing agent to destroy the organic matter present in the SMR wastewater. For an influent COD concentration of 2960 mg/L at an initial pH 4.5+/-0.1, current density 74.5 mA/cm(2), sodium chloride content 3% and electrolysis period of 75 min, resulted in the following residual values pH 7.5, COD 87 mg/L, BOD(5) 60 mg/L, TOC 65 mg/L, total chlorine 146 mg/L, turbidity 7 NTU and temperature 48 degrees C, respectively. In the case of 2% sodium chloride as an electrolyte for the above said operating condition resulted in the following values namely: pH 7.2, COD 165 mg/L, BOD(5) 105 mg/L, TOC 120 mg/L, total chlorine 120 mg/L, turbidity 27 NTU and temperature 53 degrees C, respectively. The energy requirement were found to be 30 and 46 Wh/L, while treating 24 L of SMR wastewater at 2 and 3% sodium chloride concentration at a current density 74.5 mA/cm(2). The observed energy difference was due to the improved conductivity at high sodium chloride content.
In this study treatment of palm oil mill effluent (POME) was investigated using aerobic oxidation based on an activated sludge process. The effects of sludge volume index, scum index and mixed liquor suspended solids during the acclimatizing phase and biomass build-up phase were investigated in order to ascertain the reactor stability. The efficiency of the activated sludge process was evaluated by treating anaerobically digested and diluted raw POME obtained from Golden Hope Plantations, Malaysia. The treatment of POME was carried out at a fixed biomass concentration of 3900+/-200mg/L, whereas the corresponding sludge volume index was found to be around 105+/-5mL/g. The initial studies on the efficiency of the activated sludge reactor were carried out using diluted raw POME for varying the hydraulic retention time, viz: 18, 24, 30 and 36h and influent COD concentration, viz: 1000, 2000, 3000, 4000 and 5000mg/L, respectively. The results showed that at the end of 36h of hydraulic retention time for the above said influent COD, the COD removal efficiencies were found to be 83%, 72%, 64%, 54% and 42% whereas at 24h hydraulic retention time they were 57%, 45%, 38%, 30% and 27%, respectively. The effectiveness of aerobic oxidation was also compared between anaerobically digested and diluted raw POME having corresponding CODs of 3908 and 3925mg/L, for varying hydraulic retention time, viz: 18, 24, 30, 36, 42, 48, 54 and 60h. The dissolved oxygen concentration and pH in the activated sludge reactor were found to be 1.8-2.2mg/L and 7-8.5, respectively. The scum index was found to rise from 0.5% to 1.9% during the acclimatizing phase and biomass build-up phase.
Many industries discharge untreated wastewater into the environment. Heavy metals from many industrial processes end up as hazardous pollutants of wastewaters.Heavy metal pollution has increased in recent decades and there is a growing concern for the public health risk they may pose. To remove heavy metal ions from polluted waste streams, adsorption processes are among the most common and effective treatment methods. The adsorbents that are used to remove heavy metal ions from aqueous media have both advantages and disadvantages. Cost and effectiveness are two of the most prominent criteria for choosing adsorbents. Because cost is so important, great effort has been extended to study and find effective lower cost adsorbents.One class of adsorbents that is gaining considerable attention is agricultural wastes. Among many alternatives, palm oil biomasses have shown promise as effective adsorbents for removing heavy metals from wastewater. The palm oil industry has rapidly expanded in recent years, and a large amount of palm oil biomass is available. This biomass is a low-cost agricultural waste that exhibits, either in its raw form or after being processed, the potential for eliminating heavy metal ions from wastewater. In this article, we provide background information on oil palm biomass and describe studies that indicate its potential as an alternative adsorbent for removing heavy metal ions from wastewater. From having reviewed the cogent literature on this topic we are encouraged that low-cost oil-palm-related adsorbents have already demonstrated outstanding removal capabilities for various pollutants.Because cost is so important to those who choose to clean waste streams by using adsorbents, the use of cheap sources of unconventional adsorbents is increasingly being investigated. An adsorbent is considered to be inexpensive when it is readily available, is environmentally friendly, is cost-effective and be effectively used in economical processes. The advantages that oil palm biomass has includes the following:available and exists in abundance, appears to be effective technically, and can be integrated into existing processes. Despite these advantages, oil palm biomasses have disadvantages such as low adsorption capacity, increased COD, BOD and TOC. These disadvantages can be overcome by modifying the biomass either chemically or thermally. Such modification creates a charged surface and increases the heavy metal ion binding capacity of the adsorbent.
The adsorption behavior of chitosan (CS) beads modified with 3-aminopropyl triethoxysilane (APTES) for the removal of reactive blue 4 (RB4) in batch studies has been investigated. The effects of modification conditions, such as the APTES concentration, temperature and reaction time on RB4 removal, were studied. The adsorbent prepared at a concentration of 2 wt% APTES for 8h at 50 °C was the most effective one for RB4 adsorption. The adsorption capacity of modified CS beads (433.77 mg/g) was 1.37 times higher than that of unmodified CS beads (317.23 mg/g). The isotherm data are adequately described by a Freundlich model, and the kinetic study revealed that the pseudo-second-order rate model was in better agreement with the experimental data. The negative values of the thermodynamic parameters, including ΔG° (-2.28 and -4.70 kJ/mol at 30 ± 2 °C), ΔH° (-172.18 and -43.82 kJ/mol) and ΔS° (-560.71 and -129.08 J/mol K) for CS beads and APTES modified beads, respectively, suggest that RB4 adsorption is a spontaneous and exothermic process.
Advanced oxidation processes (AOPs) such as Fenton, electro-Fenton and photo-Fenton have been applied effectively to remove refractory organics from landfill leachate. The Fenton reaction is based on the addition of hydrogen peroxide to the wastewater or leachate in the presence of ferrous salt as a catalyst. The use of this technique has proved to be one of the best compromises for landfill leachate treatment because of its environmental and economical advantages. Fenton process has been used successfully to mineralize wide range of organic constituents present in landfill leachate particularly those recalcitrant to biological degradation. The present study reviews the use of Fenton and related processes in terms of their increased application to landfill leachate. The effects of various operating parameters and their optimum ranges for maximum COD and color removal are reviewed with the conclusion that the Fenton and related processes are effective and competitive with other technologies for degradation of both raw and pre-treated landfill leachate.
A pilot scale membrane plant was constructed and monitored in Shah Alam, Malaysia for municipal wastewater reclamation for industrial application purposes. The aim of this study was to verify its suitability under the local conditions and environmental constraints for secondary wastewater reclamation. Immersed-type crossflow microfiltration (IMF) was selected as the pretreatment step before reverse osmosis filtration. Secondary wastewater after chlorine contact tank was selected as feed water. The results indicated that the membrane system is capable of producing a filtrate meeting the requirements of both WHO drinking water standards and Malaysian Effluent Standard A. With the application of an automatic backwash process, IMF performed well in hydraulic performance with low fouling rate being achieved. The investigations showed also that chemical cleaning is still needed because of some irreversible fouling by microorganisms always remains. RO treatment with IMF pretreatment process was significantly applicable for wastewater reuse purposes and promised good hydraulic performance.
Municipal leachate was treated in an experimental unit of constructed wetlands of subsurface flow type. The parameters studied were organics (BOD and COD), solids and heavy metals (Zn, Ni, Cu, Cr and Pb). Using two types of emergent plants of Scirpus globulosus and Eriocaulon sexangulare, more than 80% removal was achieved for all the parameters. E. sexangulare removed organics and heavy metals better than Scirpus globulosus. A higher concentration of heavy metals in the influent did not change the removal efficiency.
This paper describes an investigation on the effect of microbial removal using IMF for high quality drinking water production. The comparison of IMF and IMF-PAC configuration was carried out in the study to highlight the importance of PAC in the system. The specific objective of this study was to study the effect of PAC adsorption in the IMF-PAC system particularly in removing microbial substances from contaminated raw water. A bench scale IMF-PAC configuration using a flat sheet microfiltration membrane was set up for experimental purposes. Experimentally, the result has shown high removal of microbial substances with the IMF-PAC system compared to IMF. The result of E. coli removal achieved was below the detectable level due to the microbial size, which is bigger than membrane pore size. The addition of PAC has shown a direct effect on total microbial removal. The adsorption of microbial onto PAC surfaces reduced the amount of smaller microbial present in permeate samples. As a conclusion, the configuration of IMF is a promising separation process in removing microbial substances, especially when the system is combined with PAC.
A laboratory-scale membrane bioreactor (MBR) was fed with synthetic wastewater to investigate the possibility of simultaneous removal of organic, nitrogen and phosphorus by intermittent aeration. The MBR consists of two compartments using a microfiltration membrane with 0.2 microm pore size and a surface area of 0.35 m2. Hydraulic retention time was set at 24 hours and solid retention time 25 days. MLSS concentration in the reactor was in the range of 2,500-3,800 mg/L. The MLSS internal recycling ratio was maintained at 100% influent flow rate. Intermittent aeration was applied in this study to provide an aerobic-anaerobic cycle. Three stages of operations were conducted to investigate the effect of aeration and non-aeration on simultaneous organic and nutrient removal. In Stage 1, time cycles of aeration and non-aeration were set at 90/150 min and 150/90 min in the first and second compartment, the removal efficiency was 97%, 94% and 70% for COD, nitrogen and phosphorus respectively. In Stage 2, time cycles of aeration and non-aeration were set at 60/120 min and 120/60 min in the first and second compartment, the removal efficiency was 97%, 96% and 71% for COD, nitrogen and phosphorus respectively. In Stage 3, time cycles of aeration and non-aeration were set at 120/120 min and 120/120 min in compartment 1 and 2, the removal efficiency was 98%, 96% and 78% for COD, nitrogen and phosphorus respectively. Results show that longer non-aeration time in the second compartment provided better performances of biological phosphorus removal.
As cobalt (Co) represents an effective transition metal for activating Oxone to degrade contaminants, tricobalt tetraoxide (Co3O4) is extensively employed as a heterogeneous phase of Co for Oxone activation. Since Co3O4 can be manipulated to exhibit various shapes, 2-dimensional plate-like morphology of Co3O4 can offer large contact surfaces. If the large plate-like surfaces can be even porous, forming porous nanoplate Co3O4 (PNC), such a PNC should be a promising catalyst for Oxone activation. Therefore, a facile but straightforward method is proposed to prepare such a PNC for activating Oxone to degrade pollutants. In particular, a cobaltic coordination polymer with a morphology of hexagonal nanoplate, which is synthesized through coordination between Co2+ and thiocyanuric acid (TCA), is adopted as a precursor. Through calcination, CoTCA could be transformed into hexagonal nanoplate-like Co3O4 with pores to become PNC. This PNC also shows different characteristics from the commercial Co3O4 nanoparticle (NP) in terms of surficial reactivity and textural properties. Thus, PNC exhibits a much higher catalytic activity than the commercial Co3O4 NP towards activation of Oxone to degrade a model contaminant, salicylic acid (SA). Specifically, SA was 100% degraded by PNC activating Oxone within 120 min, and the Ea of SA degradation by PNC-activated Oxone is 70.2 kJ/mol. PNC can also remain stable and effective for SA degradation even in the presence of other anions, and PNC could be reused over multiple cycles without significant loss of catalytic activity. These features validate that PNC is a promising and useful Co-based catalyst for Oxone activation.
Simulation of fluidized bed reactor (FBR) was accomplished for treating wastewater using Fenton reaction, which is an advanced oxidation process (AOP). The simulation was performed to determine characteristics of FBR performance, concentration profile of the contaminants, and various prominent hydrodynamic properties (e.g., Reynolds number, velocity, and pressure) in the reactor. Simulation was implemented for 2.8 L working volume using hydrodynamic correlations, continuous equation, and simplified kinetic information for phenols degradation as a model. The simulation shows that, by using Fe(3+) and Fe(2+) mixtures as catalyst, TOC degradation up to 45% was achieved for contaminant range of 40-90 mg/L within 60 min. The concentration profiles and hydrodynamic characteristics were also generated. A subsequent scale-up study was also conducted using similitude method. The analysis shows that up to 10 L working volume, the models developed are applicable. The study proves that, using appropriate modeling and simulation, data can be predicted for designing and operating FBR for wastewater treatment.
The structural and hydrodynamic features for granules were characterized using settling experiments, predefined mathematical simulations and ImageJ-particle analyses. This study describes the rheological characterization of these biologically immobilized aggregates under non-Newtonian flows. The second order dimensional analysis defined as D2=1.795 for native clusters and D2=1.099 for dewatered clusters and a characteristic three-dimensional fractal dimension of 2.46 depicts that these relatively porous and differentially permeable fractals had a structural configuration in close proximity with that described for a compact sphere formed via cluster-cluster aggregation. The three-dimensional fractal dimension calculated via settling-fractal correlation, U∝l(D) to characterize immobilized granules validates the quantitative measurements used for describing its structural integrity and aggregate complexity. These results suggest that scaling relationships based on fractal geometry are vital for quantifying the effects of different laminar conditions on the aggregates' morphology and characteristics such as density, porosity, and projected surface area.
Horizontal subsurface-flow (HSF) constructed wetland incorporating baffles was developed to facilitate upflow and downflow conditions so that the treatment of pollutants could be achieved under multiple aerobic, anoxic and anaerobic conditions sequentially in the same wetland bed. The performances of the baffled and conventional HSF constructed wetlands, planted and unplanted, in the removal of azo dye Acid Orange 7 (AO7) were compared at the hydraulic retention times (HRT) of 5, 3 and 2 days when treating domestic wastewater spiked with AO7 concentration of 300 mg/L. The planted baffled unit was found to achieve 100%, 83% and 69% AO7 removal against 73%, 46% and 30% for the conventional unit at HRT of 5, 3 and 2 days, respectively. Longer flow path provided by baffled wetland units allowed more contact of the wastewater with the rhizomes, microbes and micro-aerobic zones resulting in relatively higher oxidation reduction potential (ORP) and enhanced performance as kinetic studies revealed faster AO7 biodegradation rate under aerobic condition. In addition, complete mineralization of AO7 was achieved in planted baffled wetland unit due to the availability of a combination of aerobic, anoxic and anaerobic conditions.
The objectives of this study are to compare the performance of newly developed baffled and conventional horizontal subsurface-flow (HSF) constructed wetlands in the removal of nitrogen at the hydraulic retention times (HRT) of 2, 3 and 5 days and to evaluate the potential of rice husk as wetland media for wastewater treatment. The results show that the planted baffled unit achieved 74%, 84% and 99% ammonia nitrogen (NH(4)(+)-N) removal versus 55%, 70% and 96% for the conventional unit at HRT of 2, 3 and 5 days, respectively. The better performance of the baffled unit was explained by the longer pathway due to the up-flow and down-flow conditions sequentially thus allowing more contact of the wastewater with the rhizomes and micro-aerobic zones. Near complete total oxidized nitrogen was observed due to the use of rice husk as wetland media which provided the COD as the electron donor in the denitrification process.
This study aims to compare the performance of planted and unplanted constructed wetlands with gravel- and raw rice husk-based media for phenol and nitrogen removal. Four laboratory-scale horizontal subsurface-flow constructed wetland units, two of which planted with cattail (Typha latifolia) were operated outdoors. The units were operated at a nominal hydraulic retention time of 7 days and fed with domestic wastewater spiked with phenol concentration at 300 mg/L for 74 days and then at 500 mg/L for 198 days. The results show that planted wetland units performed better than the unplanted ones in the removal and mineralization of phenol. This was explained by the creation of more micro-aerobic zones in the root zone of the wetland plants which allow a faster rate of phenol biodegradation, and the phenol uptake by plants. The better performance of the rice husk-based planted wetland compared to that of the gravel-based planted wetland in phenol removal could be explained by the observation that more rhizomes were established in the rice husk-based wetland unit thus creating more micro-aerobic zones for phenol degradation. The role of rice husk as an adsorbent in phenol removal was considered not of importance.
This study investigated the removal of parabens, N,N-diethyl-m-toluamide (DEET), and phthalates by ozonation. The second-order rate constants for the reaction between selected compounds with ozone at pH 7 were of (2.2 +/-0.2) X 10(6) to (2.9 +/-0.3) X 10(6) M 1/s for parabens, (2.1+/- 0.3) to (3.9 +/-0.5) M-1/s for phthalates, and (5.2 +/-0.3) M-1/s for DEET. The rate constants for the reaction between selected compounds with hydroxyl radical ranged from (2.49 +/-0.06) x 10(9) to (8.5 +/-0.2) x 10(9) M-1/s. Ozonation of selected compounds in secondary wastewater and surface waters revealed that ozone dose of 1 and 3 mg/L yielded greater than 99% depletion of parabens and greater than 92% DEET and phthalates, respectively. In addition, parabens were found to transform almost exclusively through the reaction with ozone, while DEET and phthalates were transformed almost entirely by hydroxyl radicals (.OH).
This study investigated the reaction kinetics and degradation mechanism of parabens (methylparaben, ethylparaben, propylparaben and butylparaben) during ozonation. Experiments were performed at pH 2, 6 and 12 to determine the rate constants for the reaction of protonated, undissociated and dissociated paraben with ozone. The rate constants for the reaction of ozone with dissociated parabens (3.3 × 10(9)-4.2 × 10(9)M(-1)s(-1)) were found to be 10(4) times higher than the undissociated parabens (2.5 × 10(5)-4.4 × 10(5)M(-1)s(-1)) and 10(7) times higher than with the protonated parabens (1.02 × 10(2)-1.38 × 10(2)M(-1)s(-1)). The second-order rate constants for the reaction between parabens with hydroxyl radicals were found to vary from 6.8 × 10(9) to 9.2 × 10(9)M(-1)s(-1). Characterization of degradation by-products (DBPs) formed during the ozonation of each selected parabens has been carried out using GCMS after silylation. Twenty DBPs formed during ozonation of selected parabens have been identified. Hydroxylation has been found to be the major reaction for the formation of the identified DBPs. Through the hydroxylation reaction, a variety of hydroxylated parabens was formed.