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.
Pharmaceutical pollutants substantially affect the environment; thus, their treatments have been the focus of many studies. In this article, the fixed-bed adsorption of pharmaceuticals on various adsorbents was reviewed. The experimental breakthrough curves of these pollutants under various flow rates, inlet concentrations, and bed heights were examined. Fixed-bed data in terms of saturation uptakes, breakthrough time, and the length of the mass transfer zone were included. The three most popular breakthrough models, namely, Adams-Bohart, Thomas, and Yoon-Nelson, were also reviewed for the correlation of breakthrough curve data along with the evaluation of model parameters. Compared with the Adams-Bohart model, the Thomas and Yoon-Nelson more effectively predicted the breakthrough data for the studied pollutants.
The presence of emerging contaminants (ECs) originating from pharmaceutical waste in water, wastewater, and marine ecosystems at various geographical locations has been clearly publicised. This review paper presents an overview of current monitoring data on the occurrences and distributions of ECs in coastal ecosystem, tap water, surface water, ground water, treated sewage effluents, and other sources. Technological advancements for EC removal are also presented, which include physical, chemical, biological, and hybrid treatments. Adsorption remains the most effective method to remove ECs from water bodies. Various types of adsorbents, such as activated carbons, biochars, nanoadsorbents (carbon nanotubes and graphene), ordered mesoporous carbons, molecular imprinting polymers, clays, zeolites, and metal-organic frameworks have been extensively used for removing ECs from water sources and wastewater. Extensive findings on adsorptive performances, process efficiency, reusability properties, and other related information are thoroughly discussed in this mini review.
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.
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.
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.
Chitosan-polyethyleneimine with calcium chloride as ionic cross-linker (CsPC) was synthesized as a new kind of adsorbent using a simple, green and cost-effective technique. The adsorption properties of the adsorbent for Acid Red 88 (AR88) dye, as a model analyte, were investigated in a batch system as the function of solution pH (pH 3-12), initial AR88 concentration (50-500 mg L-1), contact time (0-24 h), and temperature (30-50 °C). Results showed that the adsorption process obeyed the pseudo-first order kinetic model and the adsorption rate was governed by both intra-particle and liquid-film mechanism. Equilibrium data were well correlated with the Freundlich isotherm model, with the calculated maximum adsorption capacity (qm) of 1000 mg g-1 at 30 °C. The findings underlined CsPC to be an effective and efficient adsorbent, which can be easily synthesized via one-step process with promising prospects for the removal of AR88 or any other similar dyes from the aqueous solutions.
Cross-linked chitosan/sepiolite composite was prepared from sepiolite clay and chitosan, and was cross-linked using epichlorohydrin. Among the various weight ratio percentage of chitosan and sepiolite clay composites, CS50SP50 was selected as the best adsorbent for both methylene blue (MB) and reactive orange 16 (RO 16). At an optimum adsorbent dosage of 0.2g/100mL, the effects of initial dye concentration (25-400mg/L) and pH (3-11) on MB and RO 16 adsorption onto CS50SP50 composite were studied. Monolayer adsorption capacities of CS50SP50 composite for MB and RO 16 were 40.986mg/g and 190.965mg/g, respectively at 30°C. Freundlich, Langmuir and Temkin isotherms applied on the adsorption data for both the dyes reveal that data fitted best for Freundlich model. For both the dyes pseudo-second-order kinetics were found to describe the adsorption process better than pseudo-first-order kinetics. The adsorption capacity of CS50SP50 composite for both the dyes was found better compared to previous studies thus making it potentially low-cost adsorbent for removal of both cationic and reactive dyes.
Fabrication of an immobilized cross-linked chitosan-epichlorohydrine thin film (CLCETF) onto glass plate for adsorption of reactive orange 16 (RO16) dye was successfully studied using the direct casting technique. Adsorption experiments were performed as a function of contact time, initial dye concentration (25mg/L to 350mg/L), and pH (3-11). The adsorption isotherm followed the Langmuir model. The adsorption capacity of CLECTF for RO16 was 356.50mg/g at 27±2°C. The kinetics closely followed the pseudo-second-order model. Results supported the potential use of an immobilized CLECTF as effective adsorbent for the treatment of reactive dye without using filtration process.
Cross-linked beads of activated oil palm ash zeolite/chitosan (Z-AC/C) composite were prepared through the hydrothermal treatment of NaOH activated oil palm ash followed by beading with chitosan. The effects of initial dye concentration (50-400mg/L), temperature (30°C-50°C) and pH (3-13) on batch adsorption of methylene blue (MB) and acid blue 29 (AB29) were studied. Adsorption of both dyes was better described by Pseudo-second-order kinetics and Freundlich isotherm model. The maximum adsorption capacities of Z-AC/C were 151.51, 169.49, and 199.20mg/g for MB and 212.76, 238.09, and 270.27mg/g for AB29 at 30°C, 40°C, and 50°C, respectively.
In this study, a new magnetic Schiff's base-chitosan-glyoxal/fly ash/Fe3O4 biocomposite (Chi-Gly/FA/Fe3O4) was successfully synthesized by direct compositing of magnetic chitosan (Chi) with fly ash (FA) powder particles, and followed by Schiff's base formation via cross-linking reaction with glyoxal (Gly). Various techniques such as BET, XRD, FTIR, and SEM-EDX were utilized to characterize of Chi-Gly/FA/Fe3O4 biocomposite. The effectiveness of Chi-Gly/FA/Fe3O4 as an adsorbent was evaluated for the removal anionic azo dye such as reactive orange 16 (RO16) from aqueous environment. The effect of adsorption process parameters namely adsorbent dose (A: 0.02-0.1 g), solution pH (B: 4-10), temperature (C: 30-50 °C), and contact time (D: 5-20 min) were optimized via Box-Behnken design (BBD) in response surface methodology (RSM). The adsorption process followed the pseudo-second order (PSO) kinetic, and Freundlich isotherm models. The maximum adsorption capacity of Chi-Gly/FA/Fe3O4 biocomposite for RO16 dye was recorded to be 112.5 mg/g at 40 °C. The RO16 dye adsorption mechanism was attributed to various interactions such as electrostatic, n-π, H-bonding, and Yoshida H-bonding. Furthermore, the Chi-Gly/FA/Fe3O4 biocomposite exhibited a high ability to separate from the aqueous solution after adsorption process by external magnetic field.
In this work, chitosan (Chi) was cross-linked with glyoxal (Gly) and deposited onto glass plate to be a superior adsorbent film for two structurally different reactive orange 16 (RO-16) and methyl orange (MO) dyes by using non-conventional adsorption system without filtration process. The characterizations indicate that the cross-linked chitosan-glyoxal (Chi-Gly) film has a low swelling index, high adherence strength on glass plate, amine group (NH2) content was 32.52%, and pHpzc of ∼6.0 indicating a negative surface charge occurs above pHpzc. The adsorption isotherm data of RO-16 and MO by Chi-Gly film were in agreement with Langmuir isotherm, with maximum adsorption capacities of 1554.3 mg/g and 1451.9 mg/g, respectively. The pseudo-first-order kinetic model best described the kinetic data. The adsorption process was spontaneous and exothermic in nature at Chi-Gly film thickness of 8.55 μm, and pH ~3. The mechanism of adsorption included mainly electrostatic attractions, dipole-dipole hydrogen bonding interactions, n-π stacking attractions, and Yoshida H-bonding. This study reveals that immobilized Chi-Gly film as a good candidate for adsorption of reactive and acid dyes as it does not require any filtration process and adsorbent recovery during and post-adsorption process.
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.
Mesoporous silica nanoparticles (MSNs) were synthesized with variable microwave power in the range of 100-450 W, and the resulting enhancement of MSN crystal growth was evaluated for the adsorption and release of ibuprofen. X-ray diffraction (XRD) revealed that the MSN prepared under the highest microwave power (MSN450) produced the most crystallized and prominent mesoporous structure. Enhancement of the crystal growth improved the hexagonal order and range of silica, which led to greater surface area, pore width and pore volume. MSN450 exhibited higher ibuprofen adsorption (98.3 mg/g), followed by MSN300(81.3 mg/g) and MSN100(74.1 mg/g), confirming that more crystallized MSN demonstrated higher adsorptivity toward ibuprofen. Significantly, MSN450 also contained more hydroxyl groups that provided more adsorption sites. In addition, MSN450 exhibited comparable ibuprofen adsorption with conventionally synthesized MSN, indicating the potential of microwave treatment in the synthesis of related porous materials. In vitro drug release was also investigated with simulated biological fluids and the kinetics was studied under different pH conditions. MSN450 showed the slowest release rate of ibuprofen, followed by MSN300 and MSN100. This was due to the wide pore diameter and longer range of silica order of the MSN450. Ibuprofen release from MSN450 at pH 5 and 7 was found to obey a zero-order kinetic model, while release at pH 2 followed the Kosmeyer-Peppas model.
In this work, mesostructured silica nanoparticles (MSN(AP)) with high adsorptivity were prepared by a modification with 3-aminopropyl triethoxysilane (APTES) as a pore expander. The performance of the MSN(AP) was tested by the adsorption of MB in a batch system under varying pH (2-11), adsorbent dosage (0.1-0.5 g L(-1)), and initial MB concentration (5-60 mg L(-1)). The best conditions were achieved at pH 7 when using 0.1 g L(-1) MSN(AP) and 60 mg L(-1)MB to give a maximum monolayer adsorption capacity of 500.1 mg g(-1) at 303 K. The equilibrium data were evaluated using the Langmuir, Freundlich, Temkin, and Harkins-Jura isotherms and fit well to the Freundlich isotherm model. The adsorption kinetics was best described by the pseudo-second order model. The results indicate the potential for a new use of mesostructured materials as an effective adsorbent for MB.
Titanium dioxide (TiO(2)) with an enhanced photocatalytic activity was developed by doping it with calcium ions through a sol-gel method. The developed photocatalysts were characterized by Fourier transform infrared (FTIR) spectroscopy, N(2) physisorption, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction. Their surface morphologies were studied using surface scanning electron microscopy (SEM). The XPS analyses confirmed the presence of Ti, O, Ca, and C in the Ca-doped TiO(2) sample. The activities of the catalysts were evaluated by photocatalytic degradation of an azo dye, acid red 1 (AR1), using UV light irradiation. The results of the investigations revealed that the samples calcined at 300 °C for 3.6h in a cyclic (2 cycles) mode had the best performance. Lower percentage dopant, 0.3-1.0 wt.%, enhanced the photocatalytic activity of TiO(2), with the best at 0.5 wt.% Ca-TiO(2). The performance of 0.5 wt.% Ca-TiO(2) in the degradation of AR1 was far superior to that of a commercial anatase TiO(2) Sigma product CAS No. 1317-70-0. The effect of pH on the degradation of AR1 was studied, and the pH of the dye solution exerted a great influence on the degradation of the dye.
The removal of toxic herbicide from wastewater is challenging due to the availability of suitable adsorbents. The Langsat empty fruit bunch is an agricultural waste and was used in this study as a cheap precursor to produce activated carbon for the adsorption of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) at different initial concentrations ranging from 50 to 400 mg/L. The produced Langsat empty fruit bunch activated carbon (LEFBAC) was mesoporous and had high surface area of 1065.65 m(2)/g with different active functional groups. The effect of shaking time, temperature and pH on 2,4-D removal were investigated using the batch technique. The adsorption capacity of 2,4-D by LEFBAC was decreased with increase in pH of solution whereas adsorption capacity increased with temperature. The adsorption data was well described by Langmuir isotherm followed by removal capacity of 261.2 mg/g at 30 °C. The results from this work showed that LEFBAC can be used as outstanding material for anionic herbicide uptake from wastewater.
In this work, an activated electric arc furnace slag (A-EAFS) was investigated as an effective Fenton catalyst for the photodegradation of methylene blue (MB) and acid blue 29 (AB29). Fourier transform infrared spectroscopy and UV-visible absorption analyses indicated that A-EAFS offers additional Fe3O4 because of the changes in the iron oxide phase and the favorable response to visible light. It has been found that the highest degradation efficiency can reach up to 94% for MB under optimal conditions of 1 g L-1 of A-EAFS, 20 mM H2O2, and pH 3. The optimal conditions for AB29 were 0.1 g L-1 A-EAFS, 4 mM H2O2, and pH 3 to reach 98% degradation efficiency. Visible light enhanced the degradation of both dyes. In addition, A-EAFS, could be easily separated magnetically, exhibited good chemical stability after seven successive photodegradation cycles.
Mesoporous activated carbon was prepared using a hydrochar derived from coconut shell waste through hydrothermal carbonization and NaOH chemical activation process (COSHTC). Three sets of activated carbons were obtained with different hydrochar:NaOH impregnation ratios (1:1, 1:2, and 1:3). Among these ratios, 1:3 (COSHTC3) exhibited the optimum adsorption for methylene blue (MB). COSHTC3 adsorbed MB with an initial concentration of 25-250 mg/L at pH 3-11 and 30 °C. The adsorption isotherm of MB on COSHTC3 demonstrated that Langmuir isotherm could be better applied at a maximum monolayer adsorption capacity of 200.01 mg/g at 30 °C. The data was well fitted to the pseudo-second-order (PSO) kinetic model. These results show that the COSHTC3 prepared from low-cost agricultural waste (coconut shell) with average pore diameter 28.6 Å and surface area 876.14 m(2)/g acts as a better adsorbent for removal of cationic dyes and could pave the way for more low-cost adsorbents for dye removal.