The preparation of tamarind fruit seed granular activated carbon (TSAC) by microwave induced chemical activation for the adsorptive treatment of semi-aerobic landfill leachate has been attempted. The chemical and physical properties of TSAC were examined. A series of column tests were performed to determine the breakthrough characteristics, by varying the operational parameters, hydraulic loading rate (5-20 mL/min) and adsorbent bed height (15-21 cm). Ammonical nitrogen and chemical oxygen demand (COD), which provide a prerequisite insight into the prediction of leachate quality was quantified. Results illustrated an encouraging performance for the adsorptive removal of ammonical nitrogen and COD, with the highest bed capacity of 84.69 and 55.09 mg/g respectively, at the hydraulic loading rate of 5 mL/min and adsorbent bed height of 21 cm. The dynamic adsorption behavior was satisfactory described by the Thomas and Yoon-Nelson models. The findings demonstrated the applicability of TSAC for the adsorptive treatment of landfill leachate.
Phosphoric acid (H(3)PO(4)) and sodium hydroxide (NaOH) treated rice husks, followed by carbonization in a flowing nitrogen were used to study the adsorption of malachite green (MG) in aqueous solution. The effect of adsorption on contact time, concentration of MG and adsorbent dosage of the samples treated or carbonized at different temperatures were investigated. The results reveal that the optimum carbonization temperature is 500 degrees C in order to obtain adsorption capacity that is comparable to the commercial activated carbon for the husks treated by H(3)PO(4). It is interesting to note that MG adsorbed preferably on carbon-rich than on silica rich-sites. It is found that the behaviour of H(3)PO(4) treated absorbent followed both the Langmuir and Freundlich models while NaOH treated best fitted to only the Langmuir model.
This study examined the combustion profile and kinetics of hydrochar produced from hydrothermal carbonisation (HTC) of Karanj fruit hulls (KFH). The HTC-KFH hydrochar combustion kinetics was investigated at 5, 10, and 20°C/min by thermogravimetric analysis. The kinetics model, Kissinger-Akahira-Sunose revealed the combustion kinetics parameters for the extent of conversion from 0.1 to 0.8; the activation energy varies from 114 to 67 kJ/mol respectively. The hydrochar combustion followed multi-steps kinetics; the Coats-Redfern models predicted the activation energies and pre-exponential constants for the hydrochar combustion zones. The diffusion models are the effective mechanism in the second and third zone.
A series of experiments were conducted to compare the pore development in palm-shell and coconut-shell-based activated carbons produced under identical experimental conditions. Carbonization and activation processes were carried out at 850 degrees C using a fluidized bed reactor. Within the range of burn-off studied, at any burn-off, the micropore and mesopore volumes created in palm-shell-based activated carbon were always higher than those of coconut-shell-based activated carbon. On macropore volume, for palm-shell-based activated carbon, the volume increased with increase in burn-off up to 30% and then decreased. However, for coconut-shell-based activated carbon, the change in macropore volume with burn-off was almost negligible but the absolute macropore volume decreased with burn-off.
The bioregeneration efficiencies of powdered activated carbon (PAC) and pyrolyzed rice husk loaded with phenol and p-nitrophenol were quantified by oxygen uptake measurements using the respirometry technique in two approaches: (i) simultaneous adsorption and biodegradation and (ii) sequential adsorption and biodegradation. It was found that the applicability of the simultaneous adsorption and biodegradation approach was constrained by the requirement of adsorption preceding biodegradation in order to determine the initial adsorbent loading accurately. The sequential adsorption and biodegradation approach provides a good estimate of the upper limit of the bioregeneration efficiency for the loaded adsorbent in the simultaneous adsorption and biodegradation processes. The results showed that the mean bioregeneration efficiencies for PAC loaded with phenol and p-nitrophenol, respectively, obtained using the two approaches were in good agreement.
A kinetic model consisting of first-order desorption and biodegradation processes was developed to describe the bioregeneration of phenol- and p-nitrophenol-loaded powdered activated carbon (PAC) and pyrolyzed rice husk (PRH), respectively. Different dosages of PAC and PRH were loaded with phenol or p-nitrophenol by contacting with the respective phenolic compound at various concentrations. The kinetic model was used to fit the phenol or p-nitrophenol concentration data in the bulk solution during the bioregeneration process to determine the rate constants of desorption, k(d), and biodegradation, k. The results showed that the kinetic model fitted relatively well (R(2)>0.9) to the experimental data for the phenol- and p-nitrophenol-loaded PAC as well as p-nitrophenol-loaded PRH. Comparison of the values of k(d) and k shows that k is much greater than k(d). This indicates clearly that the desorption process is the rate-determining step in bioregeneration and k(d) can be used to characterize the rate of bioregeneration. The trend of the variation of the k(d) values with the dosages of PAC or PRH used suggests that higher rate of bioregeneration can be achieved under non-excess adsorbent dosage condition.
The role of bioregeneration process in renewing the adsorbent surface for further adsorption of organics during simultaneous adsorption and biodegradation processes has been well recognized. The extent of bioregeneration of powdered activated carbon (PAC) as an adsorbent loaded with phenol, p-methylphenol, p-ethylphenol and p-isopropylphenol, respectively, in the simultaneous adsorption and biodegradation processes were quantitatively determined using oxygen uptake as a measure of substrate consumption. Bioregeneration phenomenon was also evaluated in the simultaneous adsorption and biodegradation processes under sequencing batch reactor (SBR) operation to treat synthetic wastewater containing 1200 mg l(-1) phenol and p-methylphenol, respectively. The SBR systems were operated with FILL, REACT, SETTLE, DRAW and IDLE periods in the ratio of 4:6:1:0.75:0.25 for a cycle time of 12 h. The results show that the percentage of desorption from loaded PAC decreased in the order phenol>p-methylphenol>p-ethylphenol>p-isopropylphenol. For the treatment of phenol and p-methylphenol in the SBR reactors, respectively, the simultaneous adsorption and biodegradation processes were able to produce a consistent effluent quality of COD < or = 100 mg l(-1) when the applied PAC dosage was 0.115 and 0.143 g PAC per cycle, respectively. When no further PAC was added, the treatment performance deteriorated to that of the case without PAC addition after 68 and 48 cycles of SBR operation, respectively, for phenol and p-methylphenol. This observation is consistent with the greater extent of bioregeneration for phenol-loaded PAC as compared to p-methylphenol-loaded PAC.
In this study, chars from coconut pith (CP) were prepared aiming for superior adsorption towards elemental mercury (Hg(o)). The yield, proximate analysis, textural characteristics, surface functional groups and elemental composition analyses of the chars produced at pyrolysis temperature of 300 °C, 500 °C, 700 °C and 900 °C were compared. The surface area, pore volume, ash and carbon content of chars increased, while the yield and moisture content decreased with increasing pyrolysis temperatures. The changing of physical and chemical properties of the chars produced at variety pyrolysis temperature was much effect on the Hg(o) adsorption performance and definitely provides important information on the Hg(o) adsorption mechanism. The highest Hg(o) adsorption capacity was observed for CP900 (6067.49 μg/g), followed by CP700 (2395.98 μg/g), CP500 (289.76 μg/g), CP300 (1.68 μg/g), and CP (0.73 μg/g). The equilibrium data were well described by the Freundlich adsorption isotherm model. The pseudo-second order best described the kinetic data of the Hg(o) adsorption onto CP and CP300. For chars produced at higher pyrolysis temperature, however, the pseudo-zero order and pseudo-second order fitted well for the adsorption and breakthrough regions, respectively. The Hg(o) adsorption capacity of chars obtained from high pyrolysis temperature of CP significantly outperformed the commercial activated carbon (Darco KB-B) as well as superior to chars reported in the literature indicating the CP can be used as a precursor for preparation of chars as elemental mercury adsorbents.
In this study, palm shell activated carbon powder (PSAC) and magnesium silicate (MgSiO3) modified PSAC (MPSAC) were thoroughly investigated for fluoride (F-) adsorption. F- adsorption isotherms showed that PSAC and MPSAC over-performed some other reported F- adsorbents with adsorption capacities of 116 mg g-1 and 150 mg g-1, respectively. Interestingly, the MgSiO3 impregnated layer changed the adsorption behavior of F- from monolayer to heterogeneous multilayer based on the Langmuir and Freundlich isotherm models verified by chi-square test (X2). Thermodynamic parameters indicated that the F- adsorption on PSAC and MPSAC was spontaneous and exothermic. PSAC and MPSAC were characterized using FESEM-EDX, XRD, FTIR and XPS to investigate the F- adsorption mechanism. Based on the regeneration tests using NaOH (0.01 M), PSAC exhibited poor regeneration (<20%) while MPSAC had steady adsorption efficiencies (∼70%) even after 5 regeneration cycles. This is due to highly polarized C-F bond was found on PSAC while Mg-F bond was distinguished on MPSAC, evidently denoting that the F- adsorption is mainly resulted from the exchange of hydroxyl (-OH) group. It was concluded that PSAC would be a potential adsorbent for in-situ F- groundwater remediation due to its capability to retain F- without leaching out in a wide range pH. MPSAC would be an alternative adsorbent for ex-situ F- water remediation because it can easily regenerate with NaOH solution. With the excellent F- adsorption properties, both PSAC and MPSAC offer as promising adsorbents for F- remediation in the aqueous phase.
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.
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.
In this present study, silver (Ag) and titanium dioxide (TiO2) nanoparticles were successfully deposited on coconut shell-derived activated carbon (CSAC), to synthesize a novel nanocomposite (CSAC@AgNPs@TiO2NPs) for the adsorption of Methylene Blue (MB) dye from aqueous solution. The fabricated CSAC@AgNPs@TiO2NPs nanocomposite was analyzed by Scanning Electron Microscope (SEM), X-ray Diffraction (XRD), Fourier-Transform Infrared Spectroscopy (FTIR), Transmission Electron Microscope (TEM) equipped with Energy Dispersive X-ray spectroscopy (EDS) detector, X-ray Photoelectron Spectroscope (XPS), and Brunauer-Emmett-Teller (BET). The successful deposition of AgNPs and TiO2NPs on CSAC surface was revealed by the TEM/EDX, SEM, and XPS analysis. The mesopore structure of CSAC@AgNPs@TiO2NPs has a BET surface area of 301 m2/g. The batch adsorption studies were conducted and the influence of different parameters, i.e., adsorbent dose, adsorption time, initial dye concentration, pH and temperature were investigated. The nonlinear isotherm and kinetic modelling demonstrated that adsorption data were best fitted by Sips isotherm and pseudo-second-order models, respectively. The maximum adsorption capacity of MB onto CSAC@AgNPs@TiO2NPs by the Sips model was 184 mg/g. Thermodynamic results revealed that the adsorption was endothermic, spontaneous and physical in nature. CSAC@AgNPs@TiO2NPs revealed that MB absorption by CSAC@AgNPs@TiO2NPs was spontaneous and endothermic. The uptake capacity of MB was influenced significantly by the presence of competing ions including, NO3-, HCO3, Ca2+, and Na+. Repeated tests indicated that the CSAC@AgNPs@TiO2NPs can be regenerated and reused six times before being discarded. The primary separation mechanism between MB dye and CSAC@AgNPs@TiO2NPs was the electrostatic interaction. Thus, CSAC@AgNPs@TiO2NPs was an outstanding material, which displayed good applicability in real water with ≥ 97% removal of MB dye.
Due to increasing antibiotic pollution in the water environment, green and efficient adsorbents are urgently needed to solve this problem. Here we prepare magnetic bamboo-based activated carbon (MDBAC) through delignification and carbonization using ZnCl2 as activator, resulting in production of an activated carbon with large specific surface area (1388.83 m2 g-1). The influencing factors, such as solution pH, initial sulfadiazine (SD) concentration, temperature, and contact time, were assessed in batch adsorption experiments. The Langmuir isotherm model demonstrated that MDBAC adsorption capacity on SD was 645.08 mg g-1 at its maximum, being higher than majority of previously reported adsorbents. In SD adsorption, the kinetic adsorption process closely followed the pseudo-second kinetic model, and the thermodynamic adsorption process was discovered to be exothermic and spontaneous in nature. The MDBAC exhibited excellent physicochemical stability, facile magnetic recovery and acceptable recyclability properties. Moreover, the synergistic interactions between MDBAC and SD mainly involved electrostatic forces, hydrogen bonding, π-π stacking, and chelation. Within the benefits of low cost, ease of production and excellent adsorption performance, the MDBAC biosorbent shows promising utilization in removing antibiotic contaminants from wastewater.
Hydrothermal carbonization of biomass wastes presents a promising step in the production of cost-effective activated carbon. In the present work, mesoporous activated carbon (HAC) was prepared by the hydrothermal carbonization of rattan furniture wastes followed by NaOH activation. The textural and morphological characteristics, along with adsorption performance of prepared HAC toward methylene blue (MB) dye, were evaluated. The effects of common adsorption variables on performance resulted in a removal efficiency of 96% for the MB sample at initial concentration of 25mg/L, solution pH of 7, 30°C, and 8h. The Langmuir equation showed the best isotherm data correlation, with a maximum uptake of 359mg/g. The adsorbed amount versus time data was well fitted by a pseudo-second order kinetic model. The prepared HAC with a high surface area of 1135m(2)/g and an average pore size distribution of 35.5Å could be an efficient adsorbent for treatment of synthetic dyes in wastewaters.
In this work, palm shell waste powder activated carbon coated by magnesium silicate (PPAC-MS) were synthesized by the impregnation of magnesium silicate (MgSiO3) using economical material (silicon dioxide powder) via mild hydrothermal approach for the first time. As an effective adsorbent, PPAC-MS simultaneously removes BPA and Pb(II) in single and binary mode. Surprisingly, PPAC-MS exhibited a homogeneous thin plate mesh-like structure, as well as meso- and macropores with a high surface area of 772.1m2g-1. Due to its specific morphological characteristics, PPAC-MS had adsorption capacities of Pb(II) as high as 419.9mgg-1 and 408.8mgg-1 in single mode and binary mode based on Freudliuch isotherm model while those for BPA by PPAC-MS were 168.4mgg-1 and 254.7mgg-1 for single mode and binary modes corresponding to Langmuir isotherm model. Experiment results also indicated that the synergistic removal of BPA occurred because the precipitation process of Pb(II) leads to the co-precipitation of BPA with Pb(OH)2 compound. PPAC-MS showed a good reusability for 5 regeneration cycles using Mg(II) solution followed by thermal treatment. Overall, PPAC-MS has a high potential in the treatment process for wastewater containing both toxic heavy metals and emerging pollutants due to its high sorption capacities and reusability.
Box-Behnken model of response surface methodology was used to study the effect of adsorption process parameters for Rhodamine B (RhB) removal from aqueous solution through optimized large surface area date stone activated carbon. The set experiments with three input parameters such as time (10-600min), adsorbent dosage (0.5-10g/L) and temperature (25-50°C) were considered for statistical significance. The adequate relation was found between the input variables and response (removal percentage of RhB) and Fisher values (F- values) along with P-values suggesting the significance of various term coefficients. At an optimum adsorbent dose of 0.53g/L, time 593min and temperature 46.20°C, the adsorption capacity of 210mg/g was attained with maximum desirability. The negative values of Gibb(')s free energy (ΔG) predicted spontaneity and feasibility of adsorption; whereas, positive Enthalpy change (ΔH) confirmed endothermic adsorption of RhB onto optimized large surface area date stone activated carbons (OLSADS-AC). The adsorption data were found to be the best fit on the Langmuir model supporting monolayer type of adsorption of RhB with maximum monolayer layer adsorption capacity of 196.08mg/g.
In an effort to seek a new technical platform for disposal of drinking water treatment sludge (DWTS: alum sludge), pyrolysis of DWTS was mainly investigated in this study. To establish a more sustainable thermolytic platform for DWTS, this study particularly employed CO2 as reactive gas medium. Thus, this study laid great emphasis on elucidating the mechanistic roles of CO2 during the thermolysis of DWTS. A series of the TGA tests of DWTS in CO2 in reference to N2 revealed no occurrence of the heterogeneous reaction between CO2 and the sample surface of DWTS. As such, at the temperature regime before initiating the Boudouard reaction (i.e., ≥700 °C), the mass decay patterns of DWTS in N2 and CO2 were nearly identical. However, the gaseous effluents from lab-scale pyrolysis of DWTS in CO2 in reference to N2 were different. In sum, the homogeneous reactions between CO2 and volatile matters (VMs) evolved from the thermolysis of DWTS led to the enhanced generation of CO. Also, CO2 suppressed dehydrogenation of VMs. Such the genuine mechanistic roles of CO2 in the thermolysis of DWTS subsequently led to the compositional modifications of the chemical species in pyrolytic oil. Furthermore, the biochar composite was obtained as byproduct of pyrolysis of DWTS. Considering that the high content of Al2O3 and Fe-species in the biochar composite imparts a strong affinity for As(V), the practical use of the biochar composite as a sorptive material for arsenic (V) was evaluated at the fundamental levels. This work reported that adsorption of As(V) onto the biochar composite followed the pseudo-second order model and the Freundlich isotherm model.
This paper discusses heavy metal removal from wastewater by batch study and filtration technique through low-cost coarse media. Batch study has indicated that more than 90% copper (Cu) with concentration up to 50 mg/l could be removed from the solution with limestone quantity above 20 ml (equivalent to 56 g), which indicates the importance of limestone media in the removal process. This indicates that the removal of Cu is influenced by the media and not solely by the pH. Batch experiments using limestone and activated carbon indicate that both limestone and activated carbon had similar metal-removal efficiency (about 95%). Results of the laboratory-scale filtration technique using limestone particles indicated that above 90% removal of Cu was achieved at retention time of 2.31 h, surface-loading rate of 4.07 m3/m2 per day and Cu loading of 0.02 kg/m3 per day. Analyses of the limestone media after filtration indicated that adsorption and absorption processes were among the mechanisms involved in the removal processes. This study indicated that limestone can be used as an alternative to replace activated carbon.
In this research, two types of sequencing batch reactors (SBRs) with 8 h of cycle times, namely non-powdered activated carbon (NPAC-SBR) and powdered activated carbon (PAC-SBR), were used for the treatment of raw leachates at Kulim and Pulau Burung landfill sites. To test the performance of SBRs, phenols, total iron, zinc, ammonia, nitrite, nitrate, color, suspended solids, chemical oxygen demand, biochemical oxygen demand, and total dissolved salts removal efficiencies and sludge volume index (SVI) were studied at both sites. The rates of phenols removal, for instance in NPAC-SBRs and PAC-SBRs at Kulim, were 25% and 55%, respectively, whereas those at Pulau Buring were 94.81% and 97.75%, respectively. PAC as adsorbent in PAC-SBRs enhanced the removal efficiencies of the aforementioned pollutants from leachates at both sites. In addition, PAC as adsorbent decreased the SVI values at Kulim (59.7 mL/g) and Pulau Burung (91.4 mL/g) leachates and improved the nitrification and denitrification processes.
This study was conducted to determine the effects of rice husk ash (RHA) and Fe-coated rice husk ash (Fe-RHA) on the bioavailability and mobility of As, Cd, and Mn in mine tailings. The amendments were added to the tailings at 0, 5, 10, or 20% (w/w) and the mixtures were incubated for 0, 7, 15, 30, 45, and 60 days. The CaCl2 extractable As, Cd, and Mn in the amended tailings were determined at each interval of incubation period. In addition, the tailings mixture was leached with simulated rain water (SRW) every week from 0 day (D 0) until day 60 (D 60). The results showed that both RHA and Fe-RHA application significantly decreased the CaCl2-extractable Cd and Mn but increased that of As in the tailings throughout the incubation period. Consequently, addition of both RHA and Fe-RHA leached out higher amount of As from the tailings but decreased Cd and Mn concentration compared to the controls. The amount of As leached from the Fe-RHA-amended tailings was less than that from RHA-amended tailings. Application of both RHA and Fe-RHA could be an effective way in decreasing the availability of cationic heavy metals (Cd and Mn) in the tailings but these amendments could result in increasing the availability of anionic metalloid (As). Therefore, selection of organic amendments to remediate metal-contaminated tailings must be done with great care because the outcomes might be different among the elements.