Palm shell activated carbon was modified via surface impregnation with polyethyleneimine (PEI) to enhance removal of Cu(2+) from aqueous solution in this study. The effect of PEI modification on batch adsorption of Cu(2+) as well as the equilibrium behavior of adsorption of metal ions on activated carbon were investigated. PEI modification clearly increased the Cu(2+) adsorption capacities by 68% and 75.86% for initial solution pH of 3 and 5 respectively. The adsorption data of Cu(2+) on both virgin and PEI-modified AC for both initial solution pH of 3 and 5 fitted the Langmuir and Redlich-Peterson isotherms considerably better than the Freundlich isotherm.
Atmospheric pollution and global warming issues are increasingly becoming major environmental concerns. Fire is one of the significant sources of pollutant gases released into the atmosphere; and tropical biomass fires, which are of particular interest in this study, contribute greatly to the global budget of CO and CO2. This pioneer research simulates the natural biomass burning strategy in Malaysia using an experimental burning facility. The investigation was conducted on the emissions (CO2, CO, and Benzene, Toluene, Ethylbenzene, Xylenes (BTEX)) from ten tropical biomass species. The selected species represent the major tropical forests that are frequently subjected to dry forest fire incidents. An experimental burning facility equipped with an on-line gas analyzer was employed to determine the burning emissions. The major emission factors were found to vary among the species, and the specific results were as follows. The moisture content of a particular biomass greatly influenced its emission pattern. The smoke analysis results revealed the existence of BTEX, which were sampled from a combustion chamber by enrichment traps aided with a universal gas sampler. The BTEX were determined by organic solvent extraction followed by GC/MS quantification, the results of which suggested that the biomass burning emission factor contributed significant amounts of benzene, toluene, and m,p-xylene. The modified combustion efficiency (MCE) changed in response to changes in the sample moisture content. Therefore, this study concluded that the emission of some pollutants mainly depends on the burning phase and sample moisture content of the biomass.
Glycerol is a by-product produced from biodiesel, fatty acid, soap and bioethanol industries. Today, the value of glycerol is decreasing in the global market due to glycerol surplus, which primarily resulted from the speedy expansion of biodiesel producers around the world. Numerous studies have proposed ways of managing and treating glycerol, as well as converting it into value-added compounds. The electrochemical conversion method is preferred for this transformation due to its simplicity and hence, it is discussed in detail. Additionally, the factors that could affect the process mechanisms and products distribution in the electrochemical process, including electrodes materials, pH of electrolyte, applied potential, current density, temperature and additives are also thoroughly explained. Value-added compounds that can be produced from the electrochemical conversion of glycerol include glyceraldehyde, dihydroxyacetone, glycolic acid, glyceric acid, lactic acid, 1,2-propanediol, 1,3-propanediol, tartronic acid and mesoxalic acid. These compounds are found to have broad applications in cosmetics, pharmaceutical, food and polymer industries are also described. This review will be devoted to a comprehensive overview of the current scenario in the glycerol electrochemical conversion, the factors affecting the mechanism pathways, reaction rates, product selectivity and yield. Possible outcomes obtained from the process and their benefits to the industries are discussed. The utilization of solid acid catalysts as additives for future studies is also suggested.
Removal of Cr(VI) ions from aqueous solution was investigated using modified palm shell activated carbon. Low Molecular Weight Polyethyleneimine (LMW PEI) was used for impregnation purpose. The maximum amount of LMW PEI adsorbed on activated carbon was determined to be approximately 228.2mg/g carbon. The adsorption experiments were carried out in a batch system using potassium dichromate K(2)Cr(2)O(7) as the source of Cr(VI) in the synthetic waste water and modified palm shell activated carbon as the adsorbent. The effects of pH, concentration of Cr(VI) and PEI loaded on activated carbon were studied. The adsorption data were found to fit well with the Freundlich isotherm model. This modified Palm shell activated carbon showed high adsorption capacity for chromium ions.
Redox mediators supply an effective way to promote electrons (and protons) transport between the electrode and substrate without being in direct physical contact with the electrode. Here, the carbon-based electrodes with Amberlyst-15 as the redox mediator were used in the electrocatalytic reduction to investigate their ability to indirectly convert glycerol into 1,2-propanediol. The process aims to study the influence of different activated carbon compositions (60%, 70%, 80%, and 90% of total weight) in the activated carbon composite (ACC) electrodes on the electrochemical properties, reaction mechanisms, and selectivity of the yielded products. Their electrochemical behavior and physicochemical properties were determined by cyclic voltammetry (CV) and chronoamperometry (CA), followed by FESEM-EDX for the selected ACC electrode. Electroactive surface area (EASA) plays a role in glycerol mass transport and electrons transfer. EASA of 60ACC, 70ACC, 80ACC, and 90ACC (geometrical surface area of 0.50 cm2) were 19.62, 24.50, 36.74 and 30.83 cm2, respectively. With the highest EASA, 80ACC enhanced the mass transport and electrons transfer process that eventually improved its electrocatalytic activity. It outperformed other ACC electrodes by generating Amberlyst-15 radicals (A-15•-) with high current density at low potential (-0.5 V vs. Ag/AgCl). A-15•- served as the electron-donor for the homogeneous redox reaction with glycerol in delivering highly reactive glycerol radical for further intermediates development and generated 1,2-propanediol at -2.5 V vs. Ag/AgCl (current density of -0.2018 A cm-2). High activated carbon content portrayed a dominant role in controlling EASA and favored consecutive acetol-1,2-propanediol production through the C-O bond breakage. From the galvanostatic electrolysis, 1,2-propanediol selectivity was higher on 80ACC (88.6%) compared to 60ACC (61.4%), 70ACC (70.4%) and 90ACC (72.5%). Diethylene glycol formation was found to be the side reaction but preferred low activated carbon percentage in 60ACC and 70ACC.
In this study, a twin-chamber upflow bio-electrochemical reactor packed with palm shell granular activated carbon as biocarrier and third electrode was used for sequential nitrification and denitrification of nitrogen-rich wastewater under different operating conditions. The experiments were performed at a constant pH value for the denitrification compartment. The effect of variables, namely, electric current (I) and hydraulic retention time (HRT), on the pH was considered in the nitrification chamber. The response surface methodology was used based on three levels to develop empirical models for the study on the effects of HRT and current values as independent operating variables on NH(4)(+)-N removal. The results showed that ammonium was reduced within the function of an extensive operational range of electric intensity (20-50 mA) and HRT (6-24h). The optimum condition for ammonium oxidation (90%) was determined with an I of 32 mA and HRT of 19.2h.
In this work a novel anode configuration consisting of an iron mesh double layer is proposed for the electrochemical treatment of wastewater. The removal of Reactive Black 5 dye (RB5) from synthetic contaminated water was used as a model system. At a constant anode surface area, identical process operating parameters and batch process mode, the iron mesh double layer electrode showed better performance compared to the conventional single layer iron mesh. The double layer electrode was characterized by RB5 and chemical oxygen demand (COD) removal efficiency of 98.2% and 97.7%, respectively, kinetic rate constant of 0.0385/min, diffusion coefficient of 4.9×10(-5)cm(2)/sec and electrical energy consumption of 20.53kWh/kgdye removed. In the continuous flow system, the optimum conditions suggested by Response Surface Methodology (RSM) are: initial solution pH of 6.29, current density of 1.6mA/cm(2), electrolyte dose of 0.15g/L and flow rate of 11.47mL/min which resulted in an RB5 removal efficiency of 81.62%.
In this work, a regression model obtained from response surface methodology (RSM) was proposed for the electrocoagulation (EC) treatment of textile wastewater. The Reactive Black 5 dye (RB5) was used as a model dye to evaluate the performance of the model design. The effect of initial solution pH, applied current and treatment time on RB5 removal was investigated. The total number of experiments designed by RSM amounted to 27 runs, including three repeated experimental runs at the central point. The accuracy of the model was evaluated by the F-test, coefficient of determination (R(2)), adjusted R(2) and standard deviation. The optimum conditions for RB5 removal were as follows: initial pH of 6.63, current of 0.075 A, electrolyte dose of 0.11 g/L and EC time of 50.3 min. The predicted RB5 removal was 83.3% and the percentage error between experimental and predicted results was only 3-5%. The obtained data confirm that the proposed model can be used for accurate prediction of RB5 removal. The value of the zeta potential increased with treatment time, and the X-ray diffraction pattern shows that iron complexes were found in the sludge.
Organic solvents are hazardous to human and environmental health. The emergence of interest in finding greener solvents to replace organic solvents has sparked a series of studies in the use of glycerol for extracting bioactive compounds from natural products. In this study, we will first identify the bioactive compounds of glycerol- and nonglycerol-based Thanaka (Hesperethusa crenulata) bark extracts using liquid chromatography-mass spectrometry profiles; then, we will determine their antioxidant capacity, free radical scavenging activity, and total phenolic and flavonoid contents. Thanaka bark powder was extracted using solvents, namely, ethanol (TKE), water (TKW), glycerol (TKG), glycerol/water (1:1, v/v) (TKGW), and glycerol/ethanol (1:1, v/v) (TKGE). Among the five extracts, the extract of TKG has the highest number of bioactive compounds, as well as the highest total flavonoid content. TKGE possessed the highest total phenolic content and highest antioxidant activity shown in azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) and ferric-reducing antioxidant power assays among the five extracts. Overall, glycerol has better efficiency in extracting bioactive compounds from Thanaka bark as compared to ethanol and water. Hence, from the phytochemical content and antioxidant properties of Thanaka extracts, we conclude that glycerol is a good green solvent alternative to replace organic solvents.
In recent years, the rapid swift increase in world biodiesel production has caused an oversupply of its by-product, glycerol. Therefore, extensive research is done worldwide to convert glycerol into numerous high added-value chemicals i.e., glyceric acid, 1,2-propanediol, acrolein, glycerol carbonate, dihydroxyacetone, etc. Hydroxyl acids, glycolic acid and lactic acid, which comprise of carboxyl and alcohol functional groups, are the focus of this study. They are chemicals that are commonly found in the cosmetic industry as an antioxidant or exfoliator and a chemical source of emulsifier in the food industry, respectively. The aim of this study is to selectively convert glycerol into these acids in a single compartment electrochemical cell. For the first time, electrochemical conversion was performed on the mixed carbon-black activated carbon composite (CBAC) with Amberlyst-15 as acid catalyst. To the best of our knowledge, conversion of glycerol to glycolic and lactic acids via electrochemical studies using this electrode has not been reported yet. Two operating parameters i.e., catalyst dosage (6.4-12.8% w/v) and reaction temperature [room temperature (300 K) to 353 K] were tested. At 353 K, the selectivity of glycolic acid can reach up to 72% (with a yield of 66%), using 9.6% w/v catalyst. Under the same temperature, lactic acid achieved its highest selectivity (20.7%) and yield (18.6%) at low catalyst dosage, 6.4% w/v.
Catalytic esterification of glycerol with oleic acid (OA) was optimized over hydrophobic mesoporous zirconia-silica heterogeneous acid catalyst (ZrO2-SiO2-Me&Et-PhSO3H) and benchmarked with commercial catalysts (Aquivion and Amberlyst 15) in order to examine the effect of catalyst acidity on conversion, yield and product selectivity. The process optimisation results showed an 80% conversion with a 59.4% glycerol mono-oleate (GMO) and 34.6% glycerol dioleate (GDO) selectivities corresponding to a combined GMO and GDO selectivity of 94.8% at equimolar OA-to-glycerol ratio, 160°C reaction temperature, 5 wt% catalyst concentration with respect to the OA weight and 4 h reaction time. This work reveals that the hydrophobic and mild acidic ZrO2-SiO2-Me&Et-PhSO3H catalyst outperformed Amberlyst 15 and Aquivion with a yield of 82% and GMO selectivity of 60%. It is found that catalyst acidity is a key parameter for catalytic activity and conversion rate. Nevertheless, high acidity/acid strength reduced the product yield in the glycerol esterification of OA.
The continuous adsorption of lead ions from aqueous solution on commercial, granular, unpretreated palm shell activated carbon (PSAC) was studied. Effect of pH, flow rates and presence of complexing agents (malonic and boric acids) were examined. The breakthrough period was longer at pH 5 indicating higher adsorption capacity of lead ions at higher pH. Increase of the flow rate, expectedly, resulted in the faster saturation of the carbon bed. Presence of complexing agents did not improve adsorption uptake of lead ions. However, presence of malonic acid resulted in smoother pH stabilization of solution compared to single lead and lead with boric acid systems. The results on continuous adsorption of lead were applied to the model proposed by Wang et al. [Y.-H. Wang, S.-H. Lin, R.-S. Juang, Removal of heavy metals ions from aqueous solutions using various low-cost adsorbents, J. Hazard. Mater. B 102 (2003) 291-302]. The agreement between experimental and modelled breakthrough curves was satisfactory at both pHs.
The performance of a commercially available palm shell based activated carbon to remove lead ions from aqueous solutions by adsorption was evaluated. The adsorption experiments were carried out at pH 3.0 and 5.0. The effect of malonic and boric acid presence on the adsorption of lead ions was also studied. Palm shell activated carbon showed high adsorption capacity for lead ions, especially at pH 5 with an ultimate uptake of 95.2mg/g. This high uptake showed palm shell activated carbon as amongst the best adsorbents for lead ions. Boric acid presence did not affect significantly lead uptake, whereas malonic acid decreased it. The diffuse layer surface complexation model was applied to predict the extent of adsorption. The model prediction was found to be in concordance with the experimental values.
Water pollution is one of the most concerning global environmental problems in this century with the severity and complexity of the issue increases every day. One of the major contributors to water pollution is the discharge of harmful heavy metal wastes into the rivers and water bodies. Without proper treatment, the release of these harmful inorganic waste would endanger the environment by contaminating the food chains of living organisms, hence, leading to potential health risks to humans. The adsorption method has become one of the cost-effective alternative treatments to eliminate heavy metal ions. Since the type of adsorbent material is the most vital factor that determines the effectiveness of the adsorption, continuous efforts have been made in search of cheap adsorbents derived from a variety of waste materials. Fruit waste can be transformed into valuable products, such as biochar, as they are composed of many functional groups, including carboxylic groups and lignin, which is effective in metal binding. The main objective of this study was to review the potential of various types of fruit wastes as an alternative adsorbent for Pb(II) removal. Following a brief overview of the properties and effects of Pb(II), this study discussed the equilibrium isotherms and adsorption kinetic by various adsorption models. The possible adsorption mechanisms and regeneration study for Pb(II) removal were also elaborated in detail to provide a clear understanding of biochar produced using the pyrolysis technique. The future prospects of fruit waste as an adsorbent for the removal of Pb(II) was also highlighted.
Nanostructured photoanodes were prepared via a novel combination of titanium dioxide (TiO2) nanoparticles and mesoporous carbon (C). Four different photoanodes were synthesized by sol-gel spin coating onto a glassy substrate of fluorine-doped tin oxide. The photocatalytic activities of TiO2, TiO2/C/TiO2, TiO2/C/C/TiO2, and TiO2/C/TiO2/C/TiO2 photoanodes were evaluated by exposing the synthesized photoanodes to UV-visible light. The photocurrent density observed in these photoanodes confirmed that an additional layer of mesoporous carbon could successfully increase the photocurrent density. The highest photocurrent density of ~1.022 mA cm(-2) at 1 V/saturated calomel electrode was achieved with TiO2/C/C/TiO2 under an illumination intensity of 100 mW cm(-2) from a solar simulator. The highest value of surface roughness was measured for a TiO2/C/C/TiO2 combination owing to the presence of two continuous layers of mesoporous carbon. The resulting films had a thickness ranging from 1.605 µm to 5.165 µm after the calcination process. The presence of double-layer mesoporous carbon resulted in a 20% increase in the photocurrent density compared with the TiO2/C/TiO2 combination when only a single mesoporous carbon layer was employed. The improved performance of these photoanodes can be attributed to the enhanced porosity and increased void space due to the presence of mesoporous carbon. For the first time, it has been demonstrated here that the photoelectrochemical performance of TiO2 can be improved by integrating several layers of mesoporous carbon. Comparison of the rate of removal of humic acid by the prepared photoanodes showed that the highest performance from TiO2/C/C/TiO2 was due to the highest photocurrent density generated. Therefore, this study showed that optimizing the sequence of mesoporous carbon layers can be a viable and inexpensive method for enhanced humic acid removal.
Climate engineering solutions with emphasis on CO2 removal remain a global open challenge to balancing atmospheric CO2 equilibrium levels. As a result, warnings of impending climate disasters are growing every day in urgency. Beyond ordinary CO2 removal through natural CO2 sinks such as oceans and forest vegetation, direct CO2 conversion into valuable intermediaries is necessary. Here, a direct electrosynthesis of the peroxydicarbonate anion (C2O62-) was investigated by the reaction of CO2 with the superoxide ion (O2·-), electrochemically generated from O2 reduction in bis(trifluoromethylsulfonyl)imide [TFSI-] anion derived ionic liquid (IL) media. This is the first time that the IL media were employed successfully for CO2 conversion into C2O62-. Moreover, the charge transfer coefficient for the O2·- generation process in the ILs was less than 0.5, indicating that the process was irreversible. Voltammetry experiments coupled with global electrophilicity index analysis revealed that, when CO2/O2 was contacted simultaneously in the IL medium, O2·- was generated in situ first at a potential of approximately -1.0 V. Also, CO2 was more susceptible to attack by O2·- before any possible interaction with the IL except for [PMIm+][TFSI-]. This was because CO2 has a higher global electrophilicity index (ωCO2 = 0.489 eV) than those for the [EDMPAmm+][TFSI-] and [MOEMMor+][TFSI-]. By further COSMO-RS modeling, CO2 absorption was proven feasible at the COSMO-surface of the [TFSI-] IL-anion where the charge densities were σ = -1.100 and 1.1097 e/nm2. Therefore, the susceptible competitiveness of either IL cations or CO2 to the nucleophilic effects of O2·- was a function of their positive character as estimated by their electrophilicity indices. As determined by experimental attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and DFT-FTIR computation, the reaction yielded C2O62- in the ILs. Consequently, the presence of O=O symmetric stretching FTIR vibrational mode at ∼844 cm-1 coupled with the disappearance of the oxidative cyclic voltammetry waves when sparging CO2 and O2 confirmed the presence of C2O62-. Moreover, based on DFT/B3LYP/6-31G, pure C2O62- has symmetric O=O stretching at ∼805 and ∼844 cm-1 when it is in association with the IL-cation. This was the first spectroscopic observation of C2O62- in ILs, and the O=O symmetric stretching vibration has peculiarity for identifying C2O62- in ILs. This will open new doors to utilize CO2 in industrial applications with the aid of reactive oxygen species.
Understanding the reaction mechanism that controls the one-electron electrochemical reduction of oxygen is essential for sustainable use of the superoxide ion (O2˙-) during CO2 conversion. Here, stable generation of O2˙- in butyltrimethylammonium bis(trifluoromethylsulfonyl)imide [BMAmm+][TFSI-] ionic liquid (IL) was first detected at -0.823 V vs. Ag/AgCl using cyclic voltammetry (CV). The charge transfer coefficient associated with the process was ∼0.503. It was determined that [BMAmm+][TFSI-] is a task-specific IL with a large negative isovalue surface density accrued from the [BMAmm+] cation with negatively charged C(sp2) and C(sp3). Consequently, [BMAmm+][TFSI-] is less susceptible to the nucleophilic effect of O2˙- because only 8.4% O2˙- decay was recorded from 3 h long-term stability analysis. The CV analysis also detected that O2˙- mediated CO2 conversion in [BMAmm+][TFSI-] at -0.806 V vs. Ag/AgCl as seen by the disappearance of the oxidative faradaic current of O2˙-. Electrochemical impedance spectroscopy (EIS) detected the mechanism of O2˙- generation and CO2 conversion in [BMAmm+][TFSI-] for the first time. The EIS parameters in O2 saturated [BMAmm+][TFSI-] were different from those detected in O2/CO2 saturated [BMAmm+][TFSI-] or CO2 saturated [BMAmm+][TFSI-]. This was rationalized to be due to the formation of a [BMAmm+][TFSI-] film on the GC electrode, creating a 2.031 × 10-9 μF cm-2 double-layer capacitance (CDL). Therefore, during the O2˙- generation and CO2 utilization in [BMAmm+][TFSI-], the CDL increased to 5.897 μF cm-2 and 7.763 μF cm-2, respectively. The CO2 in [BMAmm+][TFSI-] was found to be highly unlikely to be electrochemically converted due to the high charge transfer resistance of 6.86 × 1018 kΩ. Subsequently, O2˙- directly mediated the CO2 conversion through a nucleophilic addition reaction pathway. These results offer new and sustainable opportunities for utilizing CO2 by reactive oxygen species in ionic liquid media.
The extensive amount of available information on global warming suggests that this issue has become prevalent worldwide. Majority of countries have issued laws and policies in response to this concern by requiring their industrial sectors to reduce greenhouse gas emissions, such as CO2. Thus, introducing new and more effective treatment methods, such as biological techniques, is crucial to control the emission of greenhouse gases. Many studies have demonstrated CO2 fixation using photo-bioreactors and raceway ponds, but a comprehensive review is yet to be published on biological CO2 fixation. A comprehensive review of CO2 fixation through biological process is presented in this paper as biological processes are ideal to control both organic and inorganic pollutants. This process can also cover the classification of methods, functional mechanisms, designs, and their operational parameters, which are crucial for efficient CO2 fixation. This review also suggests the bio-trickling filter process as an appropriate approach in CO2 fixation to assist in creating a pollution-free environment. Finally, this paper introduces optimum designs, growth rate models, and CO2 fixation of microalgae, functions, and operations in biological CO2 fixation.
Accumulation of nitrite intermediate in autohydrogenotrophic denitrification process has been a challenging difficulty to tackle. This study showed that further growth of "true denitrifying" bacteria and adaptation to nitrite led to a faster reduction of nitrite than nitrate as a solution to circumvent nitrite accumulation. Moreover, two effective parameters namely pH and bicarbonate dose were optimized in order to achieve a better reduction rate. Sodium bicarbonate dose ranging from 20 to 2000 mg/L and pH in the range of 6.5-8.5 was selected to be examined employing 0.2 g MLVSS/L of reacclimatized denitrifying bacteria. Eleven runs of experiments were designed considering the interactive effect of these two operative parameters. A fairly close reduction time less than 4.5 h (>22.22 mg NO2(-)-N/g MLVSS/h) was gained for the pH range between 7 and 8. The highest specific nitrite reduction rate at 25 mg NO2(-)-N/g MLVSS/h was achieved applying 1000 mg NaHCO3/L at pH 7.5 and 8. The pH was found to be the leading parameter and bicarbonate as the less effective parameter on nitrite reduction removal. Central composite design (CCD) and response surface design (RSM) were employed to develop a model as well as define the optimum condition. Using the experimental data, the developed quadratic model predicted optimum condition at pH 7.8 and sodium bicarbonate dose 1070 mg/L upon which denitrifiers managed to accomplish reduction within 3.5 h and attained the specific degradation rate of 28.57 mg NO2(-)-N/g MLVSS/h.
In this study the kinetics of autohydrogenotrophic denitrification was studied under optimum solution pH and bicarbonate concentration. The optimal pH and bicarbonate concentration were firstly obtained using a design of experiment (DOE) methodology. For this purpose a total of 11 experiments were carried out. Sodium bicarbonate concentrations ranging of 20-2000 mg/L and pH values from 6.5 to 8.5 were used in the optimization runs. It was found that the pH has a more pronounced effect on the denitrification process as compared to the bicarbonate dose. The developed quadratic model predicted the optimum conditions at pH 8 and 1100 mg NaHCO(3)/L. Using these optimal conditions, the kinetics of denitrification for nitrate and nitrite degradation were investigated in separate experiments. Both processes were found to follow a zero order kinetic model. The ultimate specific degradation rates for nitrate and nitrite remediation were 29.60 mg NO(3)(-)-N/g MLVSS/L and 34.85 mg NO(3)(-)-N/g MLVSS/L respectively, when hydrogen was supplied every 0.5h.