The titrimetric method is used for on-site measurement of the concentration of volatile fatty acids (VFAs) in anaerobic treatment. In current practice, specific and interpolated pH-volume data points are used to obtain the concentration of VFA by solving simultaneous equations iteratively to convergence (denoted as SEq). Here, the least squares method (LSM) is introduced as an elegant alternative. Known concentrations of VFA (acetic acid and/or propionic acid) ranging from to 200 to 1,000 mg/L were determined using SEq and LSM. Using standard numbers of data points, SEq gave more accurate results compared with LSM. However, results favoured LSM when all data points in the range were included without any interpolation. For model refinement, unit monovalent activity coefficient (f(m) = 1) was found reasonable and arithmetic averages of dissociation constants and molecular weight of 80 mol% acetic acid were recommended in the model for VFA determination of mixtures. An accurate result was obtained with a mixture containing more VFA (butyric acid and valeric acid). In a typical VFA measurement of real anaerobic effluent, a satisfactory result with an error of 14% was achieved. LSM appears to be a promising mathematical model solver for determination of concentration of VFA in the titrimetric method. Validation of LSM in the presence of other electrolytes deserves further exploration.
In the present study, Electrochemical Oxidation was used to remove COD and color from semi-aerobic landfill leachate collected from Pulau Burung Landfill Site (PBLS), Penang, Malaysia. Experiments were conducted in a batch laboratory-scale system in the presence of NaCl as electrolyte and aluminum electrodes. Central composite design (CCD) under Response surface methodology (RSM) was applied to optimize the electrochemical oxidation process conditions using chemical oxygen demand (COD) and color removals as responses, and the electrolyte concentrations, current density and reaction time as control factors. Analysis of variance (ANOVA) showed good coefficient of determination (R(2)) values of >0.98, thus ensuring satisfactory fitting of the second-order regression model with the experimental data. In un-optimized condition, maximum removals for COD (48.77%) and color (58.21%) were achieved at current density 80 mA/cm(2), electrolyte concentration 3,000 mg/L and reaction time 240 min. While after optimization at current density 75 mA/cm(2), electrolyte concentration 2,000 mg/L and reaction time 218 min a maximum of 49.33 and 59.24% removals were observed for COD and color respectively.
A two-stage anoxic transformation process, involving growth of biomass utilizing two types of different electron acceptors, namely nitrate and nitrite, has been observed. The present water quality modules established for sewer processes cannot account for the two-stage process. This paper outlines the development of a model concept that enables the two-stage anoxic transformation process to be simulated. The proposed model is formulated in a matrix form that is similar to the Activated Sludge Models and Sewer Process Model matrices. The model was successfully applied to simulate changes in nitrate and nitrite concentrations during anoxic transformations in the bulkwater phase of municipal wastewater.
The objective of this study was to investigate the performance of employing H2O2 reagent in persulfate activation to treat stabilized landfill leachate. A central composite design (CCD) with response surface methodology (RSM) was applied to evaluate the relationships between operating variables, such as persulfate and H2O2 dosages, pH, and reaction time, to identify the optimum operating conditions. Quadratic models for the following two responses proved to be significant with very low probabilities (<0.0001): chemical oxygen demand (COD) and NH3-N removal. The obtained optimum conditions included a reaction time of 116 min, 4.97 g S2O8(2-), 7.29 g H2O2 dosage and pH 11. The experimental results were corresponding well with predicted models (COD and NH3-N removal rates of 81% and 83%, respectively). The results obtained in the stabilized leachate treatment were compared with those from other treatment processes, such as persulfate only and H2O2 only, to evaluate its effectiveness. The combined method (i.e., /S2O8(2-)/H2O2) achieved higher removal efficiencies for COD and NH3-N compared with other studied applications.
Boron is extensively used in the ceramic industry for enhancing mechanical strength of the tiles. The discharge of boron containing wastewater to the environment causes severe pollution problems. Boron is also dangerous for human consumption and causes organisms' reproductive impediments if the safe intake level is exceeded. Current methods to remove boron include ion-exchange, membrane filtration, precipitation-coagulation, biological and chemical treatment. These methods are costly to remove boron from the wastewater and hence infeasible for industrial wastewater treatment. In the present research, adsorption-flocculation mechanism is proposed for boron removal from ceramic wastewater by using Palm Oil Mill Boiler (POMB) bottom ash and long chain polymer or flocculant. Ceramic wastewater is turbid and milky in color which contains 15 mg/L of boron and 2000 mg/L of suspended solids. The optimum operating conditions for boron adsorption on POMB bottom ash and flocculation using polymer were investigated in the present research. Adsorption isotherm of boron on bottom ash was also investigated to evaluate the adsorption capacity. Adsorption isotherm modeling was conducted based on Langmuir and Freundlich isotherms. The results show that coarse POMB bottom ash with particle size larger than 2 mm is a suitable adsorbent where boron is removed up to 80% under the optimum conditions (pH=8.0, dosage=40 g bottom ash/300 ml wastewater, residence time=1h). The results also show that KP 1200 B cationic polymer is effective in flocculating the suspended solids while AP 120 C anionic polymer is effective in flocculating the bottom ash. The combined cationic and anionic polymers are able to clarify the ceramic wastewater under the optimum conditions (dosage of KP 1200 B cationic polymer=100 mg/L, dosage of AP 120 C anionic polymer=50 mg/L, mixing speed=200 rpm). Under the optimum operating conditions, the boron and suspended solids concentration of the treated wastewater were reduced to 3 mg/L and 5 mg/L respectively, satisfying the discharge requirement by Malaysia Department of Environment (DOE). The modeling study shows that the adsorption isotherm of boron onto POMB bottom ash conformed to the Freundlich Isotherm. The proposed method is suitable for boron removal in ceramic wastewater especially in regions where POMB bottom ash is abundant.
This work investigated the removal of boron from wastewater and its recovery by electrocoagulation and hydrothermal mineralization methods respectively. The experimental design was developed using Box-Behnken Model. An initial study was performed based on four preselected variables (pH, current density, concentration and time) using synthetic wastewater. Response surface methodology (RSM) was used to evaluate the effect of process variables and their interaction on boron removal. The optimum conditions were obtained as pH 6.3, current density 17.4 mA/cm(2), and time 89 min. At these applied optimum conditions, 99.7% boron removal from an initial concentration of 10.4 mg/L was achieved. The process was effectively optimized by RSM with a desirability value of 1.0. The results showed that boron removal efficiency enhanced with increase in current density and treatment time. Removal efficiency also increased when pH was increased from 4 to 7 and subsequently decreased at pH 10. Adsorption kinetics study revealed that the reaction followed pseudo second order kinetic model; evidenced by high correlation and goodness of fit. Thermodynamics study showed that mechanism of boron adsorption was chemisorption and the reaction was endothermic in nature. Furthermore, the adsorption process was spontaneous as indicated by negative values of the adsorption free energy. Treatment of real produced water using electrocoagulation resulted in 98% boron removal. The hydrothermal mineralization study showed that borate minerals (Inyoite, Takadaite and Nifontovite) can be recovered as recyclable precipitate from electrocoagulation flocs of produced water.
In this study, the removal of natural organic matter (NOM) using coconut fiber (CF) and palm oil fiber (POF) was investigated. Preliminary analysis was performed using a jar test for the selection of optimal medium before the fabricated column model experiment. The equilibrium studies on isotherms and kinetic models for NOM adsorption were analyzed using linearized correlation coefficient. Results showed that the equilibrium data were fitted to Langmuir isotherm model for both CF and POF. The most suitable adsorption model was the pseudo-first-order kinetic model for POF and pseudo-second-order kinetic model for CF. The adsorption capacities achieved by the CF and POF were 15.67 and 30.8 mg/g respectively. Based on this investigation, it can be concluded that the POF is the most suitable material for the removal of NOM in semi polluted river water.
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.
Four different lipases were compared for ultrasound-mediated synthesis of the biodegradable copolymer poly-4-hydroxybutyrate-co-6-hydroxyhexanoate. The copolymerization was carried out in chloroform. Of the enzymes tested, Novozym 435 exhibited the highest copolymerization rate, in fact the reaction rate was observed to increase with about 26-fold from 30 to 50°C (7.9×10(-3)Ms(-1)), sonic power intensity of 2.6×10(3)Wm(-2) and dissipated energy of 130.4Jml(-1). Copolymerization rates with the Candida antarctica lipase A, Candida rugosa lipase, and Lecitase Ultra™ were lower at 2.4×10(-4), 1.3×10(-4) and 3.5×10(-4)Ms(-1), respectively. The catalytic efficiency depended on the enzyme. The efficiency ranged from 4.15×10(-3)s(-1)M(-1) for Novozym 435-1.48×10(-3)s(-1)M(-1) for C. rugosa lipase. Depending on the enzyme and sonication intensity, the monomer conversion ranged from 8.2% to 48.5%. The sonication power, time and temperature were found to affect the rate of copolymerization. Increasing sonication power intensity from 1.9×10(3) to 4.5×10(3)Wm(-2) resulted in an increased in acoustic pressure (P(a)) from 3.7×10(8) to 5.7×10(8)Nm(-2) almost 2.4-3.7 times greater than the acoustic pressure (1.5×10(8)Nm(-2)) that is required to cause cavitation in water. A corresponding acoustic particle acceleration (a) of 9.6×10(3)-1.5×10(4)ms(-2) was calculated i.e. approximately 984-1500 times greater than under the action of gravity.
Biodiesel is a green (clean), renewable energy source and is an alternative for diesel fuel. Biodiesel can be produced from vegetable oil, animal fat and waste cooking oil or fat. Fats and oils react with alcohol to produce methyl ester, which is generally known as biodiesel. Because vegetable oil and animal fat wastes are cheaper, the tendency to produce biodiesel from these materials is increasing. In this research, the effect of some parameters such as the alcohol-to-oil molar ratio (4:1, 6:1, 8:1), the catalyst concentration (0.75%, 1% and 1.25% w/w) and the time for the transesterification reaction using ultrasonication on the rate of the fatty acids-to-methyl ester (biodiesel) conversion percentage have been studied (3, 6 and 9 min). In biodiesel production from chicken fat, when increasing the catalyst concentration up to 1%, the oil-to-biodiesel conversion percentage was first increased and then decreased. Upon increasing the molar ratio from 4:1 to 6:1 and then to 8:1, the oil-to-biodiesel conversion percentage increased by 21.9% and then 22.8%, respectively. The optimal point is determined by response surface methodology (RSM) and genetic algorithms (GAs). The biodiesel production from chicken fat by ultrasonic waves with a 1% w/w catalyst percentage, 7:1 alcohol-to-oil molar ratio and 9 min reaction time was equal to 94.8%. For biodiesel that was produced by ultrasonic waves under a similar conversion percentage condition compared to the conventional method, the reaction time was decreased by approximately 87.5%. The time reduction for the ultrasonic method compared to the conventional method makes the ultrasonic method superior.
This paper presents the successful application of ultrasound-assisted packed-bed (UAE-PB) method for the extraction of hypericin from the Hypericum perfuratum L. The Soxhlet system was utilized for the determination of suitable solvent from ethanol, methanol or from the mixture of different proportions of ethanol-methanol. The mixture of 50:50 v/v ethanol-methanol was obtained to be the most suitable solvent since it led to the highest extraction amount of hypericin. The extraction amount of hypericin increased by 13.6% and 21.4% when the solvent changed from pure methanol to the mixture of 50:50 v/v ethanol-methanol for the extraction time of 3 and 8 h, respectively. Subsequently, the extraction was conducted through the UAE-PB, and the effects of temperature, time, and the ratio of solvent to the dried plant were studied. The response surface method (RSM) was used to investigate the effect of parameters on the extraction in the UAE-PB system. At the temperature of 60 °C, extraction time of 105 min, and the solvent to plant ratio of 15.3, the maximum extraction yield of hypericin was achieved. In the optimal conditions, the amount of extraction was 0.112 mg hypericin/g dried plant, which was in accordance with the optimized predicted value (0.111 mg hypericin/g dried plant) from Design-Expert software.
Theoretically, Ultrasound method is an economical and environmentally friendly or "green" technology, which has been of interest for more than six decades for the purpose of enhancement of oil/heavy-oil production. However, in spite of many studies, questions about the effective mechanisms causing increase in oil recovery still existed. In addition, the majority of the mechanisms mentioned in the previous studies are theoretical or speculative. One of the changes that could be recognized in the fluid properties is viscosity reduction due to radiation of ultrasound waves. In this study, a technique was developed to investigate directly the effect of ultrasonic waves (different frequencies of 25, 40, 68 kHz and powers of 100, 250, 500 W) on viscosity changes of three types of oil (Paraffin oil, Synthetic oil, and Kerosene) and a Brine sample. The viscosity calculations in the smooth capillary tube were based on the mathematical models developed from the Poiseuille's equation. The experiments were carried out for uncontrolled and controlled temperature conditions. It was observed that the viscosity of all the liquids was decreased under ultrasound in all the experiments. This reduction was more significant for uncontrolled temperature condition cases. However, the reduction in viscosity under ultrasound was higher for lighter liquids compare to heavier ones. Pressure difference was diminished by decreasing in the fluid viscosity in all the cases which increases fluid flow ability, which in turn aids to higher oil recovery in enhanced oil recovery (EOR) operations. Higher ultrasound power showed higher liquid viscosity reduction in all the cases. Higher ultrasound frequency revealed higher and lower viscosity reduction for uncontrolled and controlled temperature condition experiments, respectively. In other words, the reduction in viscosity was inversely proportional to increasing the frequency in temperature controlled experiments. It was concluded that cavitation, heat generation, and viscosity reduction are three of the promising mechanisms causing increase in oil recovery under ultrasound.
The artificial neural network (ANN) modeling of m-cresol photodegradation was carried out for determination of the optimum and importance values of the effective variables to achieve the maximum efficiency. The photodegradation was carried out in the suspension of synthesized manganese doped ZnO nanoparticles under visible-light irradiation. The input considered effective variables of the photodegradation were irradiation time, pH, photocatalyst amount, and concentration of m-cresol while the efficiency was the only response as output. The performed experiments were designed into three data sets such as training, testing, and validation that were randomly splitted by the software's option. To obtain the optimum topologies, ANN was trained by quick propagation (QP), Incremental Back Propagation (IBP), Batch Back Propagation (BBP), and Levenberg-Marquardt (LM) algorithms for testing data set. The topologies were determined by the indicator of minimized root mean squared error (RMSE) for each algorithm. According to the indicator, the QP-4-8-1, IBP-4-15-1, BBP-4-6-1, and LM-4-10-1 were selected as the optimized topologies. Among the topologies, QP-4-8-1 has presented the minimum RMSE and absolute average deviation as well as maximum R-squared. Therefore, QP-4-8-1 was selected as final model for validation test and navigation of the process. The model was used for determination of the optimum values of the effective variables by a few three-dimensional plots. The optimum points of the variables were confirmed by further validated experiments. Moreover, the model predicted the relative importance of the variables which showed none of them was neglectable in this work.
Thermal characteristics of turbulent nanofluid flow in a rectangular pipe have been investigated numerically. The continuity, momentum, and energy equations were solved by means of a finite volume method (FVM). The symmetrical rectangular channel is heated at the top and bottom at a constant heat flux while the sides walls are insulated. Four different types of nanoparticles Al2O3, ZnO, CuO, and SiO2 at different volume fractions of nanofluids in the range of 1% to 5% are considered in the present investigation. In this paper, effect of different Reynolds numbers in the range of 5000 < Re < 25000 on heat transfer characteristics of nanofluids flowing through the channel is investigated. The numerical results indicate that SiO2-water has the highest Nusselt number compared to other nanofluids while it has the lowest heat transfer coefficient due to low thermal conductivity. The Nusselt number increases with the increase of the Reynolds number and the volume fraction of nanoparticles. The results of simulation show a good agreement with the existing experimental correlations.
In the present study, a comparison of central composite design (CCD) and Taguchi method was established for Fenton oxidation. [Dye]ini, Dye:Fe(+2), H2O2:Fe(+2), and pH were identified control variables while COD and decolorization efficiency were selected responses. L 9 orthogonal array and face-centered CCD were used for the experimental design. Maximum 99% decolorization and 80% COD removal efficiency were obtained under optimum conditions. R squared values of 0.97 and 0.95 for CCD and Taguchi method, respectively, indicate that both models are statistically significant and are in well agreement with each other. Furthermore, Prob > F less than 0.0500 and ANOVA results indicate the good fitting of selected model with experimental results. Nevertheless, possibility of ranking of input variables in terms of percent contribution to the response value has made Taguchi method a suitable approach for scrutinizing the operating parameters. For present case, pH with percent contribution of 87.62% and 66.2% was ranked as the most contributing and significant factor. This finding of Taguchi method was also verified by 3D contour plots of CCD. Therefore, from this comparative study, it is concluded that Taguchi method with 9 experimental runs and simple interaction plots is a suitable alternative to CCD for several chemical engineering applications.
This paper presents the modelled raindrop size parameters in Skudai region of the Johor Bahru, western Malaysia. Presently, there is no model to forecast the characteristics of DSD in Malaysia, and this has an underpinning implication on wet weather pollution predictions. The climate of Skudai exhibits local variability in regional scale. This study established five different parametric expressions describing the rain rate of Skudai; these models are idiosyncratic to the climate of the region. Sophisticated equipment that converts sound to a relevant raindrop diameter is often too expensive and its cost sometimes overrides its attractiveness. In this study, a physical low-cost method was used to record the DSD of the study area. The Kaplan-Meier method was used to test the aptness of the data to exponential and lognormal distributions, which were subsequently used to formulate the parameterisation of the distributions. This research abrogates the concept of exclusive occurrence of convective storm in tropical regions and presented a new insight into their concurrence appearance.
Water-in-diesel emulsion (WiDE) is an alternative fuel for CI engines that can be employed with the existing engine setup with no additional engine retrofitting. It has benefits of simultaneous reduction of both NO x and particulate matters in addition to its impact in the combustion efficiency improvement, although this needs further investigation. This review paper addresses the type of emulsion, the microexplosion phenomenon, emulsion stability and physiochemical improvement, and effect of water content on the combustion and emissions of WiDE fuel. The review also covers the recent experimental methodologies used in the investigation of WiDE for both transport and stationary engine applications. In this review, the fuel injection pump and spray nozzle arrangement has been found to be the most critical components as far as the secondary atomization is concerned and further investigation of the effect of these components in the microexplosion of the emulsion is suggested to be center of focus.
The mineralisation kinetics of petroleum refinery effluent (PRE) by Fenton oxidation were evaluated. Within the ambit of the experimental data generated, first-order kinetic model (FKM), generalised lumped kinetic model (GLKM), and generalized kinetic model (GKM) were tested. The obtained apparent kinetic rate constants for the initial oxidation step (k'2), their final oxidation step (k'1), and the direct conversion to endproducts step (k3') were 10.12, 3.78, and 0.24 min(-1) for GKM; 0.98, 0.98, and nil min(-1) for GLKM; and nil, nil, and >0.005 min(-1) for FKM. The findings showed that GKM is superior in estimating the mineralization kinetics.
Tungsten trioxide (WO₃) possesses a small band gap energy of 2.4-2.8 eV and is responsive to both ultraviolet and visible light irradiation including strong absorption of the solar spectrum and stable physicochemical properties. Thus, controlled growth of one-dimensional (1D) WO₃ nanotubular structures with desired length, diameter, and wall thickness has gained significant interest. In the present study, 1D WO₃ nanotubes were successfully synthesized via electrochemical anodization of tungsten (W) foil in an electrolyte composed of 1 M of sodium sulphate (Na₂SO₄) and ammonium fluoride (NH₄F). The influence of NH₄F content on the formation mechanism of anodic WO₃ nanotubular structure was investigated in detail. An optimization of fluoride ions played a critical role in controlling the chemical dissolution reaction in the interface of W/WO₃. Based on the results obtained, a minimum of 0.7 wt% of NH₄F content was required for completing transformation from W foil to WO₃ nanotubular structure with an average diameter of 85 nm and length of 250 nm within 15 min of anodization time. In this case, high aspect ratio of WO₃ nanotubular structure is preferred because larger active surface area will be provided for better photocatalytic and photoelectrochemical (PEC) reactions.
Grouped and single pile behavior differs owing to the impacts of the pile-to-pile interaction. Ultimate lateral resistance and lateral subgrade modulus within a pile group are known as the key parameters in the soil-pile interaction phenomenon. In this study, a series of experimental investigation was carried out on single and group pile subjected to monotonic lateral loadings. Experimental investigations were conducted on twelve model pile groups of configurations 1 × 2, 1 × 3, 2 × 2, 3 × 3, and 3 × 2 for embedded length-to-diameter ratio l/d = 32 into loose and dense sand, spacing from 3 to 6 pile diameter, in parallel and series arrangement. The tests were performed in dry sand from Johor Bahru, Malaysia. To reconstruct the sand samples, the new designed apparatus, Mobile Pluviator, was adopted. The ultimate lateral load is increased 53% in increasing of s/d from 3 to 6 owing to effects of sand relative density. An increasing of the number of piles in-group decreases the group efficiency owing to the increasing of overlapped stress zones and active wedges. A ratio of s/d more than 6d is large enough to eliminate the pile-to-pile interaction and the group effects. It may be more in the loose sand.