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.
In this study, a potentiometric sensor composed of palm shell activated carbon modified with trioctylmethylammonium thiosalicylate (TOMATS) was used for the potentiometric determination of mercury ions in water samples. The proposed potentiometric sensor has good operating characteristics towards Hg (II), including a relatively high selectivity; a Nernstian response to Hg (II) ions in a concentration range of 1.0 × 10(-9) to 1.0 × 10(-2) M, with a detection limit of 1 × 10(-10) M and a slope of 44.08 ± 1.0 mV/decade; and a fast response time (~5 s). No significant changes in electrode potential were observed when the pH was varied over the range of 3-9. Additionally, the proposed electrode was characterized by good selectivity towards Hg (II) and no significant interferences from other cationic or anionic species.
In this study, a novel continuous reactor has been developed to produce high quality methyl esters (biodiesel) from palm oil. A microporous TiO2/Al2O3 membrane was packed with potassium hydroxide catalyst supported on palm shell activated carbon. The central composite design (CCD) of response surface methodology (RSM) was employed to investigate the effects of reaction temperature, catalyst amount and cross flow circulation velocity on the production of biodiesel in the packed bed membrane reactor. The highest conversion of palm oil to biodiesel in the reactor was obtained at 70 °C employing 157.04 g catalyst per unit volume of the reactor and 0.21 cm/s cross flow circulation velocity. The physical and chemical properties of the produced biodiesel were determined and compared with the standard specifications. High quality palm oil biodiesel was produced by combination of heterogeneous alkali transesterification and separation processes in the packed bed membrane reactor.
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.
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.
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.
Nitrates in different water and wastewater streams raised concerns due to severe impacts on human and animal health. Diverse methods are reported to remove nitrate from water streams which almost fail to entirely treat nitrate, except biological denitrification which is capable of reducing inorganic nitrate compounds to harmless nitrogen gas. Review of numerous studies in biological denitrification of nitrate containing water resources, aquaculture wastewaters and industrial wastewater confirmed the potential of this method and its flexibility towards the remediation of different concentrations of nitrate. The denitrifiers could be fed with organic and inorganic substrates which have different performances and subsequent advantages or disadvantages. Review of heterotrophic and autotrophic denitrifications with different food and energy sources concluded that autotrophic denitrifiers are more effective in denitrification. Autotrophs utilize carbon dioxide and hydrogen as the source of carbon substrate and electron donors, respectively. The application of this method in bio-electro reactors (BERs) has many advantages and is promising. However, this method is not so well established and documented. BERs provide proper environment for simultaneous hydrogen production on cathodes and appropriate consumption by immobilized autotrophs on these cathodes. This survey covers various designs and aspects of BERs and their performances.
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.
The inhalational anaesthetic agent - sevoflurane is widely employed for the induction and maintenance of surgical anaesthesia. Sevoflurane possesses a high global warming potential that imposes negative impact to the environment. The only way to resolve the issue is to remove sevoflurane from the medical waste gas before it reaches the atmosphere. A continuous adsorption study with a fixed-bed column was conducted using two commercial granular activated carbons (E-GAC and H-GAC), to selectively remove sevoflurane. The effect of bed depth (Z, 5-15 cm), gas flow rate (Q, 0.5-6.0 L/min) and inlet sevoflurane concentration (C0, ∼55-700 mg/L) was investigated. E-GAC demonstrated ∼60% higher adsorption capacity than H-GAC under the same operating conditions. Varying the levels of Z, Q and C0 showed significant differences in the adsorption capacities of E-GAC, whereas only changing the C0 level had significant differences for H-GAC. Three breakthrough models (Adams-Bohart, Thomas, and Yoon-Nelson) and Bed-depth/service time (BDST) analysis were applied to predict the breakthrough characteristics of the adsorption tests and determine the characteristic parameters of the column. The Yoon-Nelson and Thomas model-predicted breakthrough curves were in good agreement with the experimental values. In the case of the Adams-Bohart model, a low correlation was observed. The predicted breakthrough time (tb) based on kinetic constant (kBDST) in BDST analysis showed satisfactory agreement with the measured values. The results suggest the possibility of designing, scaling up and optimising an adsorption system for removing sevoflurane with the aid of the models and BDST analysis.
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.
Acclimation of autohydrogenotrophic denitrifying bacteria using inorganic carbon source (CO(2) and bicarbonate) and hydrogen gas as electron donor was performed in this study. In this regard, activated sludge was used as the seed source and sequencing batch reactor (SBR) technique was applied for accomplishing the acclimatization. Three distinct strategies in feeding of carbon sources were applied: (I) continuous sparging of CO(2), (II) bicarbonate plus continuous sparging of CO(2), and (III) only bicarbonate. The pH-reducing nature of CO(2) showed an unfavorable impact on denitrification rate; however bicarbonate resulted in a buffered environment in the mixed liquor and provided a suitable mean to maintain the pH in the desirable range of 7-8.2. As a result, bicarbonate as the only carbon source showed a faster adaptation, while carbon dioxide as the only carbon source as well as a complementary carbon source added to bicarbonate resulted in longer acclimation period. Adapted hydrogenotrophic denitrifying bacteria, using bicarbonate and hydrogen gas in the aforementioned pH range, caused denitrification at a rate of 13.33 mg NO(3)(-)-N/g MLVSS/h for degrading 20 and 30 mg NO(3)(-)-N/L and 9.09 mg NO(3)(-)-N/g MLVSS/h for degrading 50mg NO(3)(-)-N/L.
The effects of polyethyleneimine (PEI) impregnation on the Pb(2+) adsorption kinetics of palm shell-activated carbon and pH profile of bulk solution were investigated. Adsorption data were fitted to four established adsorption kinetics models, namely, pseudo-first-order, pseudo-second-order, Elovich equation and intraparticle diffusion. It was found that PEI impregnation at 16.68 and 29.82 wt% PEI/AC increased the Pb(2+) uptake rate while the opposite was observed for PEI impregnation at 4.76 and 8.41 wt% PEI/AC. The increased uptake rates were due to higher concentration of PEI molecules on the surface of clogged pores as well as varying pore volumes. The adsorption kinetics data fitted the pseudo-second-order model better than the pseudo-first-order model, implying chemisorption was the rate-controlling step. The bulk solution pH generally showed an increasing trend from the use of virgin to PEI-impregnated activated carbon.
Activated carbons have been reported to be useful for adsorptive removal of the volatile anaesthetic sevoflurane from a vapour stream. The surface functionalities on activated carbons could be modified through aqueous oxidation using oxidising solutions to enhance the sevoflurane adsorption. In this study, an attempt to oxidise the surface of a commercial activated carbon to improve its adsorption capacity for sevoflurane was conducted using 6 mol/L nitric acid, 2 mol/L ammonium persulfate, and 30 wt per cent (wt%) of hydrogen peroxide (H2O2). The adsorption tests at fixed conditions (bed depth: 10 cm, inlet concentration: 528 mg/L, and flow rate: 3 L/min) revealed that H2O2 oxidation gave desirable sevoflurane adsorption (0.510 ± 0.005 mg/m2). A parametric study was conducted with H2O2 to investigate the effect of oxidation conditions to the changes in surface oxygen functionalities by varying the concentration, oxidation duration, and temperature, and the Conductor-like Screening Model for Real Solvents (COSMO-RS) was applied to predict the interactions between oxygen functionalities and sevoflurane. The H2O2 oxidation incorporated varying degrees of both surface oxygen functionalities with hydrogen bond (HB) acceptor and HB donor characters under the studied conditions. Oxidised samples with enriched oxygen functionalities with HB acceptor character and fewer HB donor character exhibited better adsorption capacity for sevoflurane. The presence of a high amount of oxygen functional groups with HB donor character adversely affected the sevoflurane adsorption despite the enrichment of oxygen functional groups with HB acceptor character that have a higher tendency to adsorb sevoflurane.
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.
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.
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.
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.