Palm oil mill effluent contains carcinogenic coloured compounds that are difficult to separate due to their aromatic structure. Though colour treatment using adsorption processes at lower pH (<4) have been reported effectual, due to its acidity the remediated effluent poses an environmental hazard as a result. Thus, the current study focused on achieving decolourization at neutral pH by enhancing the morphology of the coconut shell activated carbon (CSAC) using N₂ as activating-agent with microwave irradiation heating. The microwave pretreated and non-pretreated CSAC were characterized using scanned electron microscopy (SEM), energy dispersive X-ray (EDX) and Brunauer-Emmett-Teller (BET) analysis. A significant modification in the porous structure with a 66.62% increase in the specific surface area was achieved after the pretreatment. The adsorption experimental matrix was developed using the central composite design to investigate the colour adsorption performance under varied pH (6⁻7), dosage (2⁻6 g) and contact time (10⁻100 min). At optimum conditions of neutral pH (7), 3.208 g dosage and contact time of 35 min, the percentage of colour removal was 96.29% with negligible differences compared with the predicted value, 95.855%. The adsorption equilibrium capacity of 1430.1 ADMI × mL/g was attained at the initial colour concentration of 2025 ADMI at 27 °C. The experimental data fitted better with the Freundlich isotherm model with R² 0.9851.
CO2 sequestration into coalbed seams is one of the practical routes for mitigating CO2 emissions. The adsorption mechanisms of CO2 onto Malaysian coals, however, are not yet investigated. In this research CO2 adsorption isotherms were first performed on dry and wet Mukah-Balingian coal samples at temperatures ranging from 300 to 348 K and pressures up to 6 MPa using volumetric technique. The dry S1 coal showed the highest CO2 adsorption capacity of 1.3 mmol g-1, at 300 K and 6 MPa among the other coal samples. The experimental results of CO2 adsorption were investigated using adsorption isotherms, thermodynamics, and kinetic models. Nonlinear analysis has been employed to investigate the data of CO2 adsorption onto coal samples via three parameter isotherm equilibrium models, namely Redlich Peterson, Koble Corrigan, Toth, Sips, and Hill, and four parameter equilibrium model, namely Jensen Seaton. The results of adsorption isotherm suggested that the Jensen Seaton model described the experimental data well. Gibb's free energy change values are negative, suggesting that CO2 adsorption onto the coal occurred randomly. Enthalpy change values in the negative range established that CO2 adsorption onto coal is an exothermic mechanism. Webber's pore-diffusion model, in particular, demonstrated that pore-diffusion was the main controlling stage in CO2 adsorption onto coal matrix. The activation energy of the coals was calculated to be below -13 kJ mol-1, indicating that adsorption of CO2 onto coals occurred through physisorption. The results demonstrate that CO2 adsorption onto coal matrix is favorable, spontaneous, and the adsorbed CO2 molecules accumulate more onto coal matrix. The observations of this investigation have significant implications for a more accurate measurement of CO2 injection into Malaysian coalbed seams.
Titania and ceria incorporated rice husk silica based catalyst was synthesized via sol-gel method using CTAB and glycerol as surface directing agents at room temperature and labeled as RHS-50Ti10Ce. The catalyst was used to study the adsorption and photodegradation of methylene blue (MB) under UV irradiation. The powder XRD pattern of RHS-50Ti10Ce was much broader (2θ=25-30°) than that of the parent RHS (2θ=22°). The catalyst exhibited type IV isotherm with H3 hysteresis loop, and the TEM images showed partially ordered pore arrangements. The TGA-DTG thermograms confirmed the complete removal of the templates after calcination at 500°C. RHS-50Ti10Ce exhibited excellent adsorption capability with more than 99% removal of MB from a 40 mg L(-1) solution in just 15 min. It also decolorized an 80 mg L(-1) MB solution under UV irradiation in 210 min, which was comparable with the commercialized pure anatase TiO2.
Silica supported iron catalyst was prepared from rice husk ash (RHA) via the sol-gel technique using an aqueous solution of iron(III) salt in 3.0 M HNO3. The sample was dried at 110 degrees C and labeled as RHA-Fe. A sample of RHA-Fe was calcined at 700 degrees C for 5 h and labeled as RHA-Fe700. X-ray diffraction spectrogram showed that both RHA-Fe and RHA-Fe700 were amorphous. The SEM/EDX results showed that the metal was present as agglomerates and the Fe ions were not homogeneously distributed in RHA-Fe but RHA-Fe700 was shown to be homogeneous. The specific surface areas for RHA-Fe and RHA-Fe700 were determined by BET nitrogen adsorption studies and found to be 87.4 and 55.8 m(2) g(-1), respectively. Both catalysts showed high activity in the reaction between toluene and benzyl chloride. The mono-substituted benzyltoluene was the major product and both catalysts yielded more than 92% of the product. The GC showed that both the ortho- and para-substituted monoisomers were present in about equal quantities. The minor products consisting of 16 di-substituted isomers were also observed in the GC-MS spectra of both catalytic products. The catalyst was found to be reusable without loss of activity and with no leaching of the metal.
Adsorption is one of the most efficient ways to remove heavy metal from wastewater. In this study, the adsorptive removal of hexavalent chromium, Cr (VI) from aqueous solution was investigated using natural zeolite, clinoptilolite, in the form of hollow fibre ceramic membrane (HFCM). The HFCM sample was prepared using phase inversion-based extrusion technique and followed by sintering process at different sintering temperatures in the range of 900-1050 °C. The fabricated HFCM was characterised using scanning electron microscopy (SEM), contact angle, water permeability, and mechanical strength for all HFCMs sintered at different temperatures. The adsorption and filtration test of Cr (VI) were performed using an in-house water permeation set up with a dead-end cross-flow permeation test. An asymmetric structure with sponge- and finger-like structures across the cross-section of HFCM was observed using SEM. Based on the characterisation data, 1050 °C was chosen to be the best sintering temperature as the water permeability and mechanical strength of this HFCM were 29.14 L/m2∙h and 50.92 MPa, respectively. The performance of the HFCM in adsorption/filtration was 44% of Cr (VI) removal at the Cr (VI) concentration of 40 mg/L and pH 4. In addition, the mathematical model was also performed in simulating the experimental data obtained from this study. All in all, the natural zeolite-based HFCM has a potential as a single-step Cr (VI) removal by membrane adsorption for the wastewater treatment.
The present work aimed to develop a novel composite material made up of activated cow bone powder (CBP) as a starting material for reducing chemical oxygen demand (COD) and ammonia-nitrogen (NH3N) from palm oil mill effluent (POME). The optimization of the reduction efficiency was investigated using response surface methodology (RSM). Six independent variables used in the optimization experiments include pH (4-10), speed (0.27-9.66 rcf), contact time (2-24 h), particle size (1-4.35 mm), dilution factor (100-500) and adsorbent dosage (65-125 g/L). The chemical functional groups were determined using Fourier transform irradiation (FTIR). The elemental composition were detected using SEM-EDX, while thermal decomposition was investigated using thermo gravimetric analysis (TGA) in order to determine the effects of carbonization temperature on the adsorbent. The results revealed that the optimal reduction of COD and NH3N from raw POME was observed at pH 10, 50 rpm, within 2 h and 3 mm of particle size as well as at dilution factor of 500 and 125 g L-1 of adsorbent dosage, the observed and predicted reduction were 89.60 vs. 85.01 and 75.61 vs. 74.04%, respectively for COD and NH3N. The main functional groups in the adsorbent were OH, NH, CO, CC, COC, COH, and CH. The SEM-EDX analysis revealed that the CBP-composite has a smooth surface with high contents of carbon. The activated CBP has very stable temperature profile with no significant weight loss (9.85%). In conclusion, the CBP-composite investigated here has characteristics high potential for the remediation of COD and NH3N from raw POME.
This study highlights the effectiveness of oyster shell biocomposite for the biosorption of Cd(II) and Pb(II) ions from an aqueous solution. The aim of this work was to modify a novel biocomposite derived from oyster shell for the adsorption of Cd(II) and Pb(II) ions from aqueous solution. The studied revealed the specific surface BET surface area was 9.1476 m2/g. The elemental dispersive x-ray analysis (EDS) indicated that C, O, Ag, Ca were the predominant elements on the surface of the biocomposite after which metals ions of Cd and Pb were noticed after adsorption. The Fourier transform Irradiation (FT-IR) revealed the presence of carboxyl and hydroxyl groups on the surface. The effect of process variables on the adsorption capacity of the modified biocomposite was examined using the central composite design (CCD) of the response surface methodology (RSM). The process variables which include pH, adsorbent dose, the initial concentration and temperature were the most effective parameters influencing the uptake capacity. The optimal process conditions of these parameters were found to be pH, 5.57, adsorbent dose, 2.53 g/L, initial concentration, 46.76 mg/L and temperature 28.48°C for the biosorption of Cd(II) and Pb(II) ions from aqueous solution at a desirability coefficient of 1. The analysis of variance (ANOVA) revealed a high coefficient of determination (R2 > 0.91) and low probability coefficients for the responses (P < 0.05) which indicated the validity and aptness of the model for the biosorption of the metal ions. Experimental isotherm data fitted better to the Langmuir model and the kinetic data fitted better to the pseudo-second-order model. Maximun Cd(II) and Pb(II) adsorption capacities of the oyster shell biocomposite were 97.54 and 78.99 mg/g respectively and was obtained at pH 5.56 and 28.48°C. This investigation has provided the possibility of the utilization of alternative biocomposite as a sustainable approach for the biosorption of heavy metal ions from the wastewater stream.
In this study, simultaneous adsorption of cationic dyes was investigated by using binary component solutions. Thiourea-modified poly(acrylonitrile-co-acrylic acid) (TMPAA) polymer was used as an adsorbent for uptake of cationic dyes (malachite green, MG and methylene blue, MB) from aqueous solution in a binary system. Adsorption tests revealed that TMPAA presented high adsorption of MG and MB at higher pH and higher dye concentrations. It suggested that there are strong electrostatic attractions between the surface functional groups of the adsorbent and cationic dyes. The equilibrium analyses explain that both extended Langmuir and extended models are suitable for the description of adsorption data in the binary system. An antagonistic effect was found, probably due to triangular (MG) and linear (MB) molecular structures that mutually hinder the adsorption of both dyes on TMPAA. Besides, the kinetic studies for sorption of MG and MB dyes onto adsorbent were better represented by a pseudo-second-order model, which demonstrates chemisorption between the polymeric TMPAA adsorbent and dye molecules. According to experimental findings, TMPAA is an attractive adsorbent for treatment of wastewater containing multiple cationic dyes.
Proper remediation of aquatic environments contaminated by toxic organic dyes has become a research focus globally for environmental and chemical engineers. This study evaluates the adsorption potential of a polymer-based adsorbent, thiourea-modified poly(acrylonitrile-co-acrylic acid) (T-PAA) adsorbent, for the simultaneous uptake of malachite green (MG) and methylene blue (MB) dye ions from binary system in a continuous flow adsorption column. The influence of inlet dye concentrations, pH, flow rate, and adsorbent bed depth on adsorption process were investigated, and the breakthrough curves obtained experimentally. Results revealed that the sorption capacity of the T-PAA for MG and MB increase at high pH, concentration and bed-depth. Thomas, Bohart-Adams, and Yoon-Nelson models constants were calculated to describe MG and MB adsorption. It was found that the three dynamic models perfectly simulate the adsorption rate and behavior of cationic dyes entrapment. Finally, T-PAA adsorbent demonstrated good cyclic stability. It can be regenerated seven times (or cycles) with no significant loss in adsorption potential. Overall, the excellent sorption capacity and multiple usage make T-PAA polymer an attractive adsorbent materials for treatment of multicomponent dye bearing effluent in a fixed-bed column system.
Palm shell was used to prepare activated carbon using potassium carbonate (K2CO3) as activating agent. The influence of carbonization temperatures (600-1000 degrees C) and impregnation ratios (0.5-2.0) of the prepared activated carbon on the pore development and yield were investigated. Results showed that in all cases, increasing the carbonization temperature and impregnation ratio, the yield decreased, while the adsorption of CO2 increased, progressively. Specific surface area of activated carbon was maximum about 1170 m2/g at 800 degrees C with activation duration of 2 h and at an impregnation ratio of 1.0.
For the synthesis of a highly active TiO2-chitosan nanocomposite, pH plays a crucial role towards controlling its morphology, size, crystallinity, thermal stability, and surface adsorption properties. The presence of chitosan (CS) biopolymer facilitates greater sustainability to the photoexcited electrons and holes on the catalysts' surface. The variation of synthesis pH from 2 to 5 resulted in different physico-chemical and photocatalytic properties, whereby a pH of 3 resulted in TiO2-chitosan nanocomposite with the highest photocatalytic degradation (above 99 %) of methylene orange (MO) dye. This was attributed to the efficient surface absorption properties, high crystallinity, and the presence of reactive surfaces of -NH2 and -OH groups, which enhances the adsorption-photodegradation effect. The larger surface oxygen vacancies coupled with reduced electron-hole recombination further enhanced the photocatalytic activity. It is undeniable that the pH during synthesis is critical towards the development of the properties of the TiO2-chitosan nanocomposite for the enhancement of photocatalytic activity.
Herein, a highly efficient and sustainable adsorbent of cross-linked chitosan-glyoxal/algae biocomposite (CHT-GLX/ALG) adsorbent was developed through an innovative hydrothermal cross-linking method. The CHT-GLX/ALG biocomposite was characterized using several complementary analytical methods that include CHN-O, XRD, FTIR, SEM-EDX, and pHpzc. This new adsorbent, named CHT-GLX/ALG, was utilized for the adsorption of a cationic dye (methyl violet 2B; MV 2B), from synthetic wastewater. The optimization of the dye adsorption process involved key parameters is listed: CHT-GLX/ALG dosage (from 0.02 to 0.1 g/100 mL), pH (from 4 to 10), and contact time (from 20 to 180 min) that was conducted using the Box-Behnken design (BBD). The optimal adsorption conditions for the highest decolorization efficiency of MV 2B (97.02 %) were estimated using the statistical model of the Box-Behnken design. These conditions include a fixed adsorbent dosage of 0.099 g/100 mL, pH 9.9, and a 179.9 min contact time. The empirical data of MV 2B adsorption by CHT-GLX/ALG exhibited favorable agreement with the Freundlich isotherm model. The kinetic adsorption profile of MV 2B by CHT-GLX/ALG revealed a good fit with the pseudo-second-order model. The maximum adsorption capacity (qmax) for MV 2B by CHT-GLX/ALG was estimated at 110.8 mg/g. The adsorption of MV 2B onto the adsorbent can be attributed to several factors, including electrostatic interactions between the negatively charged surface of CHT-GLX/ALG and the MV 2B cation, as well as n-π and H-bonding. These interactions play a crucial role in facilitating the effective adsorption of MV 2B onto the biocomposite adsorbent. Generally, this study highlights the potential of CHT-GLX/ALG as an efficient and sustainable adsorbent for the effective removal of organic dyes.
Herein, a natural material including chitosan (CTS) and algae (food-grade algae, FGA) was exploited to attain a bio-adsorbent (CTS/FGA) for enhanced methyl violet 2B dye removal. A study of the FGA loading into CTS matrix showed that the best mixing ratio between CTS and FGA to be used for the MV 2B removal was 50 %:50 % (CTS/FGA; 50:50 w/w). The present study employed the Box-Behnken design (RSM-BBD) to investigate the impact of three processing factors, namely CTS/FGA-(50:50) dose (0.02-0.1 g/100 mL), pH of solution (4-10), and contact time (5-15 min) on the decolorization rate of MV 2B dye. The results obtained from the equilibrium and kinetic experiments indicate that the adsorption of MV 2B dye on CTS/FGA-(50:50) follows the Langmuir and pseudo-second-order models, respectively. The CTS/FGA exhibits an adsorption capacity of 179.8 mg/g. The characterization of CTS/FGA-(50:50) involves the proposed mechanism of MV 2B adsorption, which primarily encompasses various interactions such as electrostatic forces, n-π stacking, and H-bonding. The present study demonstrates that CTS/FGA-(50:50) synthesized material exhibits a distinctive structure and excellent adsorption properties, thereby providing a viable option for the elimination of toxic cationic dyes from polluted water.
This work aims to apply the use of food-grade algae (FGA) composited with chitosan-benzaldehyde Schiff base biopolymer (CHA-BD) as a new adsorbent (CHA-BA/FGA) for methyl violet 2B (MV 2B) dye removal from aqueous solutions. The effect of three processing variables, including CHA-BA/FGA dosage (0.02-0.1 g/100 mL), pH solution (4-10), and contact duration (10-120 min) on the removal of MV 2B was investigated using the Box-Behnken design (BBD) model. Kinetic and equilibrium dye adsorption profiles reveal that the uptake of MV 2B dye by CHA-BA/FGA is described by the pseudo-second kinetics and the Langmuir models. The thermodynamics of the adsorption process (ΔG°, ΔH°, and ΔS°) reveal spontaneous and favorable adsorption parameters of MV 2B dye onto the CHA-BA/FGA biocomposite at ambient conditions. The CHA-BA/FGA exhibited the maximum ability to absorb MV 2B of 126.51 mg/g (operating conditions: CHA-BA/FGA dose = 0.09 g/100 mL, solution pH = 8.68, and temperature = 25 °C). Various interactions, including H-bonding, electrostatic forces, π-π stacking, and n-π stacking provide an account of the hypothesized mechanism of MV 2B adsorption onto the surface of CHA-BA/FGA. This research reveals that CHA-BA/FGA with its unique biocomposite structure and favorable adsorption properties can be used to remove harmful cationic dyes from wastewater.
The adsorption behavior of the amino acid, glycine (Gly), via the carboxyl, hydroxyl, and amino groups onto the surfaces of Al12N12 and Al16N16 fullerene-like cages were computationally evaluated by the combination of density functional theory (DFT) and molecular docking studies. It was found that Gly can chemically bond with the Al12N12 and Al16N16 fullerene-like cages as its amino group being more favorable to interact with the aluminum atoms of the adsorbents compared to carboxyl and hydroxyl groups. Oxygen and carbon doping were reported to reduce steric hindrance for Glycine interaction at Al site of Al12ON11/Gly and Al12CN11/Gly complexes. Interaction was further enhanced by oxygen doping due to its greater electron withdrawing effect. Herein, the Al12ON11/Gly complex where two carbonyl groups of Gly are bonded to the aluminum atoms of the Al12N12 fullerene-like cage is the most stable interaction configuration showing ∆adsH and ∆adsG values of -81.74 kcal/mol and -66.21 kcal/mol, respectively. Computational studies also revealed the frequency shifts that occurred due to the interaction process. Molecular docking analysis revealed that the Al12N12/Gly (-11.7 kcal/mol) and the Al12ON11/Gly (-9.2 kcal/mol) complexes have a good binding affinity with protein tumor necrosis factor alpha (TNF-α). TNF-α was implicated as a key cytokine in various diseases, and it has been a validated therapeutic target for the treatment of rheumatoid arthritis. These results suggest that the Al12N12/Gly complex in comparison with the Al16N16/Gly, Al12ON11/Gly, and the Al12CN11/Gly complexes could be efficient inhibitors of TNF-α.
Ultrafiltration has been proven to be very effective in the treatment of oil-in-water emulsions, since no chemical additives are required. However, ultrafiltration has its limitations, the main limits are concentration polarization resulting to permeate flux decline with time. Adsorption, accumulation of oil and particles on the membrane surface which causes fouling of the membrane. Studies have shown that the ultrasonic is effective in cleaning of fouled membrane and enhancing membrane filtration performance. But the effectiveness also, depends on the selection of appropriate membrane material, membrane geometry, ultrasonic module design, operational and processing condition. In this study, a hollow and flat-sheet polyurethane (PU) membranes synthesized with different additives and solvent were used and their performance evaluated with oil-in-water emulsion. The steady-state permeate flux and the rejection of oil in percentage (%) at two different modes were determined. A dry/wet spinning technique was used to fabricate the flat-sheet and hollow fibre membrane (HFMs) using Polyethersulfone (PES) polymer base, Polyvinylpyrrolidone (PVP) additive and N, N-Dimethylacetamide (DMAc) solvent. Ultrasonic assisted cross-flow ultrafiltration module was built to avoid loss of ultrasonic to the surrounding. The polyurethane (PU) was synthesized by polymerization and sulphonation to have an anionic group (-OH; -COOH; and -SO3H) on the membrane surface. Changes in morphological properties of the membrane had a significant effect on the permeate flow rate and oil removal. Generation of cavitation and Brownian motion by the ultrasonic were the dominant mechanisms responsible for ultrafiltration by cracking the cake layers and reducing concentration polarization at the membrane surface. The percentage of oil after ultrafiltration process with ultrasonic is about 90% compared to 49% without ultrasonic. Ultrasonic is effective in enhancing the membrane permeate flux and controlling membrane fouling.
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.
Meranti (Philippine mahogany) sawdust, an inexpensive material, showed strong scavenging behaviour through adsorption for the removal of methylene blue (MB) from aqueous solution. Batch studies were performed to evaluate and optimize the effects of various parameters such as contact time, pH, initial dye concentrations and adsorbent dosage. Langmuir, Freundlich and Temkin isotherms were used to analyze the equilibrium data at different temperatures. The experimental data fitted well with the Langmuir adsorption isotherm, indicating thereby the mono layer adsorption of the dye. The monolayer sorption capacity of meranti sawdust for MB was found to be 120.48, 117.64, 149.25 and 158.73 mg/g at 30, 40, 50 and 60 degrees C, respectively. Thermodynamic calculations showed that the MB adsorption process is endothermic and spontaneous in nature. Kinetic studies showed that the adsorption followed a pseudo-second-order kinetic model. The results indicated that the meranti sawdust could be an alternative material in place of more costly adsorbents used for dye removal.
The direct determination of toxic metal ions, in environmental samples, is difficult because of the latter's presence in trace concentration in association with complex matrices, thereby leading to insufficient sensitivity and selectivity of the methods used. The simultaneous removal of the matrix and preconcentration of the metal ions, through solid phase extraction, serves as the promising solution. The mechanism involved in solid phase extraction (SPE) depends on the nature of the sorbent and analyte. Thus, SPE is carried out by means of adsorption, ion exchange, chelation, ion pair formation, and so forth. As polymeric supports, the commercially available Amberlite resins have been found very promising for designing chelating matrices due to its good physical and chemical properties such as porosity, high surface area, durability and purity. This review presents an overview of the various works done on the modification of Amberlite XAD resins with the objective of making it an efficient sorbent. The methods of modifications which are generally based on simple impregnation, sorption as chelates and chemical bonding have been discussed. The reported results, including the preconcentration limit, the detection limit, sorption capacity, preconcentration factors etc., have been reproduced.
This study aims to develop a highly efficient adsorbent material. CNTs are prepared using a chemical vapor deposition method with acetylene and synthesized mesoporous Ni-MCM41 as the carbon source and catalyst, respectively, and are then functionalized using 3-aminopropyltriethoxysilane (APTES) through the co-condensation method and loaded with commercial TiO2. Results of X-ray powder diffraction (XRD), Raman spectra, and Fourier transform infrared spectroscopy (FTIR) confirm that the synthesized CNTs grown are multi-walled carbon nanotubes (MWNTs). Transmission electron microscopy shows good dispersion of TiO2 nanoparticles onto functionalized-CNTs loaded TiO2, with the diameter of a hair-like structure measuring between 3 and 8 nm. The functionalized-CNTs loaded TiO2 are tested as an adsorbent for removal of methyl orange (MO) in aqueous solution, and results show that 94% of MO is removed after 10 min of reaction, and 100% after 30 min. The adsorption kinetic model of functionalized-CNTs loaded TiO2 follows a pseudo-second order with a maximum adsorption capacity of 42.85 mg/g. This study shows that functionalized-CNTs loaded TiO2 has considerable potential as an adsorbent material due to the short adsorption time required to achieve equilibrium.