In this work, mesoporous-activated carbon (CSAC) was prepared from chitosan flakes (CS) via single-step sodium hydroxide activation for the adsorption of methylene blue (MB). CSAC was prepared using different impregnation ratios of NaOH:CS (1:1, 2:1, 3:1, and 4:1) at 800°C for 90min. The adsorption performance of CSAC was evaluated for MB at different adsorption variables, such MB initial concentrations (25-400mg/L), solution pH (3-11), and temperature (30-50°C). The adsorption isotherm data of CSAC-MB were well fitted to Langmuir model with a maximum adsorption capacity 143.53mg/g at 50°C. Best representation of kinetic data was obtained by the pseudo-second order model. CSAC exhibited excellent adsorption uptake for MB and can potentially be used for other cationic dyes.
Canarium schweinfurthii fruit used in food and cosmetics produces waste nuts with a hard shell (hard-shell) and kernel. The hard-shell contained lignin and holocellulose, besides 51.99 wt% carbon, 6.0 wt% hydrogen, 41.68 wt% oxygen, and 70.97 wt% volatile matter. Therefore, this study commenced thermochemical investigations on the hard-shell through extensive intermediate pyrolysis and kinetic studies. During the active stage of thermogravimetric pyrolysis, the hard-shell lost a maximum of 56.45 wt%, and the activation energies obtained by the Kissinger-Akahira-Sunose, Flynn-Wall-Ozawa, and Starink methods were 223, 221 and 217 kJ/mol, respectively. The Flynn-Wall-Ozawa method depicted the degradation process accurately, where the Coat-Redfern method's contraction and diffusion mechanisms governed the pyrolysis reactions at activation energies of 16.62 kJ/mol and 38.83 kJ/mol, respectively. The pyrolysis process produced 25 wt% biochar and 25 wt% bio-oil under optimum conditions. The calorific values of the bio-oils with 6.81-7.11 wt% hydrogen and 68.01-71.12 wt% carbon was 26.32-27.83 MJ/kg, with phenolics and n-hexadecanoic and oleic acids as major compounds. Biochar, by contrast, has a high carbon content of 75.11-79.32 wt% and calorific values of 25.45-28.61 MJ/kg. These properties assert the biochar and bio-oils among viable bioenergy sources.
Nutrient leaching and volatilization cause environmental pollution, thus the pursuit of developing controlled-release fertilizer formulation is necessary. Biochar-based fertilizer exhibits slow-release characteristic, however the nutrient release mechanism needs to be improved. To overcome this limitation, the approach of applying encapsulation technology with biochar-based fertilizer has been implemented in this study. Black peppercorn waste was used to synthesize urea-impregnated biochar (UIB). Central composite design was used to investigate the effects of pyrolysis temperature, residence time and urea:biochar ratio on nitrogen content of UIB. The optimum condition to synthesize UIB was at 400 °C pyrolysis temperature, 120 min residence time and 0.6:1 urea:biochar ratio, which resulted in 16.07% nitrogen content. The tapioca starch/palm oil (PO) biofilm formulated using 8 g of tapioca starch and 0.12 µL of PO was coated on the UIB to produce encapsulated urea-impregnated biochar (EUIB). The UIB and EUIB pellets achieved complete release of nitrogen in water after 90 min and 330 min, respectively. The nutrient release mechanism of UIB and EUIB was best described by the Higuchi model and Korsmeyer-Peppas model, respectively. The improvement of water retention ratio of UIB and EUIB pellets was more significant in sandy-textural soil as compared to clayey-textural soil. The EUIB derived from peppercorn waste has the potential to be utilized as a sustainable controlled-release fertilizer for agriculture.
This work has focused on the co-pyrolysis of sugarcane waste (SW) with polyethylene terephthalate (PET) to gain insight on its thermal decomposition, product distribution, kinetics, and synergistic effect. SW and PET were blended at different ratios (100:0, 80:20, 60:40, 40:60, and 0:100), and the Coats-Redfern method was used to determine the kinetics parameters. To ascertain the synergistic effect between SW and PET, product yields and composition of chemicals were compared with the synergistic effect of the individual components of pyrolysis. The bio-oil yield was significant at 60% of PET, with a difference of 19.41 wt% compared to the theoretical value. The synergistic impact of SW:PET on ester formation and acid compound inhibition was the most dominant at the 60:40 ratio. The kinetics analysis revealed that the diffusion mechanism, power law, and order of reactions were the most probable reaction models that can explain the pyrolysis of SW, and PET, and their blends. The resultant co-pyrolysis oil contained slightly larger hydrogen and carbon contents with low oxygen, and sulphur, and nitrogen contents, which improved the quality of the bio-oil. The results of this work could be used as a guide in selecting proper reaction conditions with optimal synergy during the co-pyrolysis process.
In this work, the adsorption of malachite green (MG) on rattan sawdust (RSD) was studied at 30 degrees C. The results indicated that RSD can be used as a low-cost adsorbent for the removal of MG dye from aqueous solutions. Equilibrium data were analyzed by two isotherms, namely the Freundlich isotherm and the Langmuir isotherm. The best fit to the data was obtained with the Langmuir isotherm. The monolayer adsorption capacity of RSD was found to be 62.71 mg/g. The adsorption kinetics can be predicted by the pseudo-first-order model. The mechanism of adsorption was also studied. It was found that for a short time period the rate of adsorption is controlled by film diffusion. However, at longer adsorption times, pore-diffusion controls the rate of adsorption. The amount adsorbed on the outer surface was estimated from the time where film-diffusion stops controlling the adsorption rate.
In this work, the adsorption of malachite green (MG) was studied on activated carbon prepared from bamboo by chemical activation with K(2)CO(3) and physical activation with CO(2) (BAC). Adsorption studies were conducted in the range of 25-300 mg/L initial MG concentration and at temperature of 30 degrees C. The experimental data were analyzed by the Freundlich isotherm, the Langmuir isotherm, and the multilayer adsorption isotherm. Equilibrium data fitted well with the Langmuir model with maximum adsorption capacity of 263.58 mg/g. The rates of adsorption were found to confirm to pseudo-second-order kinetics with good correlation and the overall rate of dye uptake was found to be controlled by pore diffusion throughout the entire adsorption period. The results indicate that the BAC could be used to effectively adsorb MG from aqueous solutions.
In this work, pumpkin seed hull (PSH), an agricultural solid waste, is proposed as a novel material for the removal of methylene blue (MB) from aqueous solutions. The effects of the initial concentration, agitation time and solution pH were studied in batch experiments at 30 degrees C. The equilibrium process was described well by the multilayer adsorption isotherm. The adsorption kinetics can be predicted by the pseudo-first-order and the modified pseudo-first-order models. The mechanism of adsorption was also studied. It was found that for a short time period the rate of adsorption is controlled by film diffusion. However, at longer adsorption times, pore-diffusion controls the rate of adsorption. Pore diffusion takes place in two distinct regimes, corresponding to diffusion in macro- and mesopores. The results demonstrate that the PSH is very effective in the removal of MB from aqueous solutions.
In this paper, broad bean peels (BBP), an agricultural waste, was evaluated for its ability to remove cationic dye (methylene blue) from aqueous solutions. Batch mode experiments were conducted at 30 degrees C. Equilibrium sorption isotherms and kinetics were investigated. The kinetic data obtained at different concentrations have been analyzed using pseudo-first-order, pseudo-second-order and intraparticle diffusion equations. The experimental data fitted very well the pseudo-first-order kinetic model. Analysis of the temportal change of q indicates that at the beginning of the process the overall rate of adsorption is controlled by film-diffusion, then at later stage intraparticle-diffusion controls the rate. Diffusion coefficients and times of transition from film to pore-diffusion control were estimated by piecewise linear regression. The experimental data were analyzed by the Langmuir and Freundlich models. The sorption isotherm data fitted well to Langmuir isotherm and the monolayer adsorption capacity was found to be 192.7 mg/g and the equilibrium adsorption constant Ka is 0.07145 l/mg at 30 degrees C. The results revealed that BBP was a promising sorbent for the removal of methylene blue from aqueous solutions.
Oil palm trunk fibre (OPTF)--an agricultural solid waste--was used as low-cost adsorbent to remove malachite green (MG) from aqueous solutions. The operating variables studied were contact time, initial dye concentration, and solution pH. Equilibrium adsorption data were analyzed by three isotherms, namely the Freundlich isotherm, the Langmuir isotherm, and the multilayer adsorption isotherm. The best fit to the data was obtained with the multilayer adsorption. The monolayer adsorption capacity of OPTF was found to be 149.35 mg/g at 30 degrees C. Adsorption kinetic data were modeled using the Lagergren pseudo-first-order, Ho's pseudo-second-order and Elovich models. It was found that the Lagergren's model could be used for the prediction of the system's kinetics. The overall rate of dye uptake was found to be controlled by external mass transfer at the beginning of adsorption, then for initial MG concentrations of 25, 50, 100, 150, and 300 mg/L the rate-control changed to intraparticle diffusion at a later stage, but for initial MG concentrations 200 and 250 mg/L no evidence was found of intraparticle diffusion at any period of adsorption. It was found that with increasing the initial concentration of MG, the pore-diffusion coefficient increased while the film-diffusion coefficient decreased.
In this work, the potential feasibility of rice straw-derived char (RSC) for removal of C.I. Basic Green 4 (malachite green (MG)), a cationic dye from aqueous solution was investigated. The isotherm parameters were estimated by non-linear regression analysis. The equilibrium process was described well by the Langmuir isotherm model. The maximum RSC sorption capacity was found to be 148.74 mg/L at 30 degrees C. The kinetics of MG sorption on RSC followed the Lagergren's pseudo-first-order model and the overall rate of dye uptake was found to be controlled by external mass transfer at the beginning of adsorption, while intraparticle diffusion controlled the overall rate of adsorption at a later stage. The results indicated that RSC was an attractive adsorbent for removing basic dye from aqueous solutions.
The potentials of mesoporous TiO2-ZnO (3TiZn) were explored on photocatalytic degradation of doxycycline (DOX) antibiotic, likewise the influence of adsorption on the photocatalytic process. The 3TiZn was characterized for physical and chemical properties. Stability, reusability, kinetic and the ability of 3TiZn to degrade high concentration of pollutant under different operating conditions were investigated. Photocatalytic degradation of DOX was conducted at varied operating conditions, and the best was obtained at 1 g/L catalyst dosage, solution inherent pH (4.4) and 50 ppm of DOX. Complete degradation of 50 ppm and 100 ppm of DOX were attained within 30 and 100 min of the reaction time, respectively. The stability and reusability study of the photocatalyst proved that at the tenth (10th) cycle, the 3TiZn is as effective in the degradation of DOX as in the first cycle. This may be attributed to the fusion of the mixed oxides during calcination. The 3TiZn is mesoporous with a pore diameter of 17 nm, and this boosts it potential to degrade high concentration of DOX. It was observed that the adsorption capacity of 3TiZn enhance the photocatalytic process. It can be emphasized that 3TiZn portrayed a remarkable catalyst stability and good potentials for industrial application.
The adsorption of methylene blue (MB) from aqueous solution using a low-cost adsorbent, rejected tea (RT), has been studied by batch adsorption technique. The adsorption experiments were carried out under different conditions of initial concentration (50-500 mg/L), solution pH 3-12, RT dose (0.05-1g) and temperature (30-50 degrees C). The equilibrium data were fitted to Langmuir and Freundlich isotherms and the equilibrium adsorption was best described by the Langmuir isotherm model with maximum monolayer adsorption capacities found to be 147, 154 and 156 mg/g at 30, 40 and 50 degrees C, respectively. Three kinetic models, pseudo-first-order, pseudo-second-order and intraparticle diffusion were employed to describe the adsorption mechanism. The experimental results showed that the pseudo-second-order equation is the best model that describes the adsorption behavior with the coefficient of correlation R(2)>or=0.99. The results suggested that RT has high potential to be used as effective adsorbent for MB removal.
Palm ash, an agriculture waste residue from palm-oil industry in Malaysia, was investigated as a replacement for the current expensive methods of removing direct blue 71 dye from an aqueous solution. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption. Equilibrium data fitted well with Freundlich model in the range of 50-600mg/L. The equilibrium adsorption capacity of the palm ash was determined with the Langmuir equation and found to be 400.01mg dye per gram adsorbent at 30 degrees C. The rates of adsorption were found to conform to the pseudo-second-order kinetics with good correlation. The results indicate that the palm ash could be employed as a low-cost alternative to commercial activated carbon.
A substantive approach converting waste date pits to mercerized mesoporous date pit activated carbon (DPAC) and utilizing it in the removal of Cd(II), Cu(II), Pb(II), and Zn(II) was reported. In general, rapid heavy metals adsorption kinetics for Co range: 25-100 mg/L was observed, accomplishing 77-97% adsorption within 15 min, finally, attaining equilibrium in 360 min. Linear and non-linear isotherm studies revealed Langmuir model applicability for Cd(II) and Pb(II) adsorption, while Freundlich model was fitted to Zn(II) and Cu(II) adsorption. Maximum monolayer adsorption capacities (qm) for Cd(II), Pb(II), Cu(II), and Zn(II) obtained by non-linear isotherm model at 298 K were 212.1, 133.5, 194.4, and 111 mg/g, respectively. Kinetics modeling parameters showed the applicability of pseudo-second-order model. The activation energy (Ea) magnitude revealed physical nature of adsorption. Maximum elution of Cu(II) (81.6%), Zn(II) (70.1%), Pb(II) (96%), and Cd(II) (78.2%) were observed with 0.1 M HCl. Thermogravimetric analysis of DPAC showed a total weight loss (in two-stages) of 28.3%. Infra-red spectral analysis showed the presence of carboxyl and hydroxyl groups over DPAC surface. The peaks at 820, 825, 845 and 885 cm-1 attributed to Zn-O, Pb-O, Cd-O, and Cu-O appeared on heavy metals saturated DPAC, confirmed their binding on DPAC during the adsorption.
The purpose of this work is to obtain optimal preparation conditions for activated carbons prepared from rattan sawdust (RSAC) for removal of disperse dye from aqueous solution. The RSAC was prepared by chemical activation with phosphoric acid using response surface methodology (RSM). RSM based on a three-variable central composite design was used to determine the effect of activation temperature (400-600 degrees C), activation time (1-3h) and H(3)PO(4):precursor (wt%) impregnation ratio (3:1-6:1) on C.I. Disperse Orange 30 (DO30) percentage removal and activated carbon yield were investigated. Based on the central composite design, quadratic model was developed to correlate the preparation variables to the two responses. The most influential factor on each experimental design responses was identified from the analysis of variance (ANOVA). The optimum conditions for preparation of RSAC, which were based on response surface and contour plots, were found as follows: temperature of 470 degrees C, activation time of 2h and 14min and chemical impregnation ratio of 4.45.
The effects of three preparation variables: CO(2) activation temperature, CO(2) activation time and KOH:char impregnation ratio (IR) on the 2,4,6-trichlorophenol (2,4,6-TCP) uptake and carbon yield of the activated carbon prepared from oil palm empty fruit bunch (EFB) were investigated. Based on the central composite design, two quadratic models were developed to correlate the three preparation variables to the two responses. The activated carbon preparation conditions were optimized using response surface methodology by maximizing both the 2,4,6-TCP uptake and activated carbon yield within the ranges studied. The optimum conditions for preparing activated carbon from EFB for adsorption of 2,4,6-TCP were found as follows: CO(2) activation temperature of 814 degrees C, CO(2) activation time of 1.9h and IR of 2.8, which resulted in 168.89 mg/g of 2,4,6-TCP uptake and 17.96% of activated carbon yield. The experimental results obtained agreed satisfactorily with the model predictions. The activated carbon prepared under optimum conditions was mesoporous with BET surface area of 1141 m(2)/g, total pore volume of 0.6 cm(3)/g and average pore diameter of 2.5 nm. The surface morphology and functional groups of the activated carbon were respectively determined from the scanning electron microscopy and Fourier transform infrared analysis.
In this work, the adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) on activated carbon derived from date stones (DSAC) was studied with respect to pH and initial 2,4-D concentration. The experimental data were analyzed by the Freundlich isotherm, the Langmuir isotherm, and the Temkin isotherm. Equilibrium data fitted well with the Langmuir model with maximum adsorption capacity of 238.10 mg/g. Pseudo-first and pseudo-second-order kinetics models were tested with the experimental data, and pseudo-first-order kinetics was the best for the adsorption of 2,4-D by DSAC with coefficients of correlation R(2)>or=0.986 for all initial 2,4-D concentrations studied. The results indicated that the DSAC is very effective for the adsorption of 2,4-D from aqueous solutions.
The liquid-phase adsorption of phenol onto coconut shell-based activated carbon, CS850A was investigated for its equilibrium studies and kinetic modeling. Coconut shell was converted into high quality activated carbon through physiochemical activation at 850 degrees C under the influence of CO(2) flow. Beforehand, the coconut shell was carbonized at 700 degrees C and the resulted char was impregnated with KOH at 1:1 weight ratio. In order to evaluate the performance of CS850A, a series of batch adsorption experiments were conducted with initial phenol concentrations ranging from 100 to 500 mg l(-1), adsorbent loading of 0.2g and the adsorption process was maintained at 30+/-1 degrees C. The adsorption isotherms were in conformation to both Langmuir and Freundlich isotherm models. Chemical reaction was found to be a rate-controlling parameter to this phenol-CS850A batch adsorption system due to strong agreement with the pseudo-second-order kinetic model. Adsorption capacity for CS850A was found to be 205.8 mg g(-1).
Oil palm fibre was used to prepare activated carbon using physiochemical activation method which consisted of potassium hydroxide (KOH) treatment and carbon dioxide (CO(2)) gasification. The effects of three preparation variables: the activation temperature, activation time and chemical impregnation (KOH:char) ratio on methylene blue (MB) uptake from aqueous solutions and activated carbon yield were investigated. Based on the central composite design (CCD), a quadratic model and a two factor interaction (2FI) model were respectively developed to correlate the preparation variables to the MB uptake and carbon yield. From the analysis of variance (ANOVA), the significant factors on each experimental design response were identified. The optimum activated carbon prepared from oil palm fibre was obtained by using activation temperature of 862 degrees C, activation time of 1h and chemical impregnation ratio of 3.1. The optimum activated carbon showed MB uptake of 203.83 mg/g and activated carbon yield of 16.50%. The equilibrium data for adsorption of MB on the optimum activated carbon were well represented by the Langmuir isotherm, giving maximum monolayer adsorption capacity as high as 400mg/g at 30 degrees C.
The sorption of basic dye from aqueous solutions by banana stalk waste (BSW), an abundant agricultural waste in Malaysia, was studied in a batch system with respect to pH and initial dye concentration. Sorption isotherm of methylene blue (MB) onto the BSW was determined at 30 degrees C with the initial concentrations of MB in the range of 50-500 mg/L. At pH 2.0, the sorption of dye was not favorable, while the sorption at other pHs (4.0-12.0) was remarkable. Equilibrium data were fitted to the Langmuir, Freundlich and Temkin isotherm models. The equilibrium data were best represented by the Langmuir isotherm model, with maximum monolayer adsorption capacity of 243.90 mg/g. The sorption kinetic data were analyzed using pseudo-first-order, pseudo-second-order and intraparticle diffusion models. It was found that the pseudo-second-order kinetic model was the best applicable model to describe the sorption kinetics. The results showed that BSW sorbent was a promising for the removal of MB from aqueous solutions.