The chemical production of methyl oleate using chemically synthesized fatty acid alcohols and other toxic chemicals may lead to significant environmental hazards to mankind. Being a highly valuable fatty acid replacement raw material in oleochemical industry, the mass production of methyl oleate via environmentally favorable processes is of concern. In this context, an alternative technique utilizing Candida rugosa lipase (CRL) physically adsorbed on multi-walled carbon nanotubes (MWCNTs) has been suggested. In this study, the acid-functionalized MWCNTs prepared using a mixture of HNO3 and H2SO4 (1:3 v/v) was used as support for immobilizing CRL onto MWCNTs (CRL-MWCNTs) as biocatalysts. Enzymatic esterification was performed and the efficiency of CRL-MWCNTs was evaluated against the free CRL under varying conditions, viz. temperature, molar ratio of acid/alcohol, solvent log P, and enzyme loading. The CRL-MWCNTs resulted in 30-110 % improvement in the production of methyl oleate over the free CRL. The CRL-MWCNTs attained its highest yield (84.17 %) at 50 °C, molar ratio of acid/alcohol of 1:3, 3 mg/mL of enzyme loading, and iso-octane (log P 4.5) as solvent. Consequently, physical adsorption of CRL onto acid-functionalized MWCNTs has improved the activity and stability of CRL and hence provides an environmentally friendly means for the production of methyl oleate.
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.
Manganese has recently been a topic of interest among researchers, particularly when 1,752 million tonnes of manganese are expected to be produced by the steel industry in 2020. Manganese discharges from industrial effluents have increased manganese contamination in water sources. Its concentrations of more than 0.2 mg/L in the water sources could have negative impacts on human health and the aquatic ecosystem. Thereby, the available water treatment processes face challenges in effectively removing manganese at low cost. In response to these challenges, adsorption has emerged as one of the most practical water treatment processes for manganese removal. In particular, agricultural waste adsorbents received a lot of attention owing to their low cost and high efficiency (99%) in the removal of manganese. Therefore, this paper reviews the removal of manganese by adsorption process using agricultural waste adsorbents. The factors affecting the adsorption process, the mechanisms, and the performances of the adsorbents are elucidated in detail.
Various types of activated carbon nanofibers' (ACNFs) composites have been extensively studied and reported recently due to their extraordinary properties and applications. This study reports the fabrication and assessments of ACNFs incorporated with graphene-based materials, known as gACNFs, via simple electrospinning and subsequent physical activation process. TGA analysis proved graphene-derived rice husk ashes (GRHA)/ACNFs possess twice the carbon yield and thermally stable properties compared to other samples. Raman spectra, XRD, and FTIR analyses explained the chemical structures in all resultant gACNFs samples. The SEM and EDX results revealed the average fiber diameters of the gACNFs, ranging from 250 to 400 nm, and the successful incorporation of both GRHA and reduced graphene oxide (rGO) into the ACNFs' structures. The results revealed that ACNFs incorporated with GRHA possesses the highest specific surface area (SSA), of 384 m2/g, with high micropore volume, of 0.1580 cm3/g, which is up to 88% of the total pore volume. The GRHA/ACNF was found to be a better adsorbent for CH4 compared to pristine ACNFs and reduced graphene oxide (rGO/ACNF) as it showed sorption up to 66.40 mmol/g at 25 °C and 12 bar. The sorption capacity of the GRHA/ACNF was impressively higher than earlier reported studies on ACNFs and ACNF composites. Interestingly, the CH4 adsorption of all ACNF samples obeyed the pseudo-second-order kinetic model at low pressure (4 bar), indicating the chemisorption behaviors. However, it obeyed the pseudo-first order at higher pressures (8 and 12 bar), indicating the physisorption behaviors. These results correspond to the textural properties that describe that the high adsorption capacity of CH4 at high pressure is mainly dependent upon the specific surface area (SSA), pore size distribution, and the suitable range of pore size.
In this study, an optimized mesoporous sulfonated carbon (OMSC) catalyst derived from palm kernel shell biomass was developed using template carbonization and subsequent sulfonation under different temperatures and time conditions. The OMSC catalyst was characterized using acid-base titration, elemental analysis, XRD, Raman, FTIR, XPS, TPD-NH3, TGA-DTA, SEM, and N2 adsorption-desorption analysis to reveal its properties. Results proved that the OMSC catalyst is mesoporous and amorphous in structure with improved textural, acidic, and thermal properties. Both FTIR and XPS confirmed the presence of -SO3H, -OH, and -COOH functional groups on the surface of the catalyst. The OMSC catalyst was found to be efficient in catalyzing glycerol conversion to acetin via an acetylation reaction with acetic acid within a short period of 3 h. Response surface methodology (RSM), based on a two-level, three-factor, face-centered central composite design, was used to optimize the reaction conditions. The results showed that the optimized temperature, glycerol-to-acetic acid mole ratio, and catalyst load were 126 °C, 1:10.4, and 0.45 g, respectively. Under these optimum conditions, 97% glycerol conversion (GC) and selectivities of 4.9, 27.8, and 66.5% monoacetin (MA), diacetin (DA), and triacetin (TA), respectively, were achieved and found to be close to the predicted values. Statistical analysis showed that the regression model, as well as the model terms, were significant with the predicted R2 in reasonable agreement with the adjusted R2 (<0.2). The OMSC catalyst maintained excellent performance in GC for the five reaction cycles. The selectivity to TA, the most valuable product, was not stable until the fourth cycle, attributable to the leaching of the acid sites.
Industrial operations, domestic and agricultural activities worldwide have had major problems with various contaminants caused by environmental pollution. Heavy metal pollution in wastewater also a prominent issue; therefore, a well built and economical treatment technology is demanded for pollution-free wastewater. The present work emphasized pure cellulose extracted from jute fiber and further modification was performed by a free radical grafting reaction, which resulted in poly(methyl acrylate) (PMA)-grafted cellulose and poly(acrylonitrile)-grafted cellulose. Subsequently, poly(hydroxamic acid) and poly(amidoxime) ligands were prepared from the PMA-grafted cellulose and PAN-grafted cellulose, respectively. An adsorption study was performed using the desired ligands with heavy metals such as copper, cobalt, chromium and nickel ions. The binding capacity (qe) with copper ions for poly(hydroxamic acid) is 352 mg g-1 whereas qe for poly(amidoxime) ligand it was exhibited as 310 mg g-1. Other metal ions (chromium, cobalt and nickel) show significance binding properties at pH 6. The Langmuir and Freundlich isotherm study was also performed. The Freundlich isotherm model showed good correlation coefficients for all metal ions, indicating that multiple-layers adsorption was occurred by the polymer ligands. The reusability was evaluated and the adsorbents can be reused for 7 cycles without significant loss of removal performance. Both ligands showed outstanding metals removal capacity from the industrial wastewater as such 98% of copper can be removed from electroplating wastewater and other metals (cobalt, chromium, nickel and lead) can also be removed up to 90%.
The development of mixed matrix membranes (MMMs) for effective gas separation has been gaining popularity in recent years. The current study aimed at the fabrication of MMMs incorporated with various loadings (0-4 wt%) of functionalized KIT-6 (NH2KIT-6) [KIT: Korea Advanced Institute of Science and Technology] for enhanced gas permeation and separation performance. NH2KIT-6 was characterized by field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR), and N2 adsorption-desorption analysis. The fabricated membranes were subjected to FESEM and FTIR analyses. The effect of NH2KIT-6 loading on the CO2 permeability and ideal CO2/CH4 selectivity of the fabricated membranes were investigated in gas permeation and separation studies. The successfulness of (3-Aminopropyl) triethoxysilane (APTES) functionalization on KIT-6 was confirmed by FTIR analysis. As observed from FESEM images, MMMs with no voids in the matrix were successfully fabricated at a low NH2KIT-6 loading of 0 to 2 wt%. The CO2 permeability and ideal CO2/CH4 selectivity increased when NH2KIT-6 loading was increased from 0 to 2 wt%. However, a further increase in NH2KIT-6 loading beyond 2 wt% led to a drop in ideal CO2/CH4 selectivity. In the current study, a significant increase of about 47% in ideal CO2/CH4 selectivity was achieved by incorporating optimum 2 wt% NH2KIT-6 into the MMMs.
The recognition of cellulose nanofibrils (CNF) in the past years as a high prospect material has been prominent, but the impractical cellulose extraction method from biomass remained as a technological barrier for industrial practice. In this study, the telescopic approach on the fractionation of lignin and cellulose was performed by organosolv extraction and catalytic oxidation from oil palm empty fruit bunch fibers. The integration of these techniques managed to synthesize CNF in a short time. Aside from the size, the zeta potential of CNF was measured at -41.9 mV, which allow higher stability of the cellulose in water suspension. The stability of CNF facilitated a better dispersion of Fe(0) nanoparticles with the average diameter size of 52.3-73.24 nm through the formulation of CNF/Fe(0). The total uptake capacity of CNF towards 5-fluorouracil was calculated at 0.123 mg/g. While the synergistic reactions of adsorption-oxidation were significantly improved the removal efficacy three to four times greater even at a high concentration of 5-fluorouracil. Alternatively, the sludge generation after the oxidation reaction was completely managed by the encapsulation of Fe(0) nanoparticles in regenerated cellulose.
The contribution of palm oil fuel ash (POFA), an agricultural waste as a low cost adsorbent for the removal of arsenite (As(III)) and arsenate (As(V)) was explored. Investigation on the adsorbency characteristics of POFA suspension revealed that the surface area, particle size, composition, and crystallinity of the SiO2 rich mullite structure were the crucial factors in ensuring a high adsorption capacity of the ions. Maximum adsorption capacities of As(III) and As(V) at 91.2 and 99.4 mg g-1, respectively, were obtained when POFA of 30 μm particle size was employed at pH 3 with the highest calcination temperature at 1150 °C. An optimum dosage of 1.0 g of dried POFA powder successfully removed 48.7% and 50.2% of As(III) and As(V), respectively. Molecular modeling using the density functional theory consequently identified the energy for the proposed reaction routes between the SiO- and As+ species. The high stability of the POFA suspension in water in conjunction with good adsorption capacity of As(III) and As(V) seen in this study, thus envisages its feasibility as a potential alternative absorbent for the remediation of water polluted with heavy metals.
Heavy metal ions contamination has become more serious which is caused
by the releasing of toxic waterfrom industrial area and landfill that are very
harmful to all living organism especially human and can even cause death
if contaminated in small amount of heavy metal concentration. Currently,
peoples are using classic method namely electrochemical treatment,
chemical oxidation/reduction, chemical precipitation and reverse osmosis
to eliminate the metal ions from toxic water. Unfortunately, these methods
are costly and not environmentally friendly as compared to bioadsorption
method, where agricultural waste is used as biosorbent to remove heavy
metals. Two types of agricultural waste used in this research namely oil
palm mesocarp fiber (Elaesis guineensis sp.) (OPMF) and mangrove bark
(Rhizophora apiculate sp.) (MB) biomass. Through chemical treatment,
the removal efficiency was found to improve. The removal efficiency is
examined based on four specification namely dosage, of biosorbent to
adsorb fourtypes of metalsion explicitly nickel, lead, copper, and chromium.
The research has found that the removal efficiency of MB was lower than
OPMF; whereas, the multiple metals ions removal efficiency decreased in
the order of Pb2+ > Cu2+ > Ni2+ > Cr2+.
Newly discovered two-dimensional (2D) atomic crystals (nanosheet) of platinum diselenide (PtSe2) have progressively attracted attention due to their expected high performance in catalysis, sensing, electronics, and optoelectronics applications. Further extraordinary physicochemical properties are expected if these nanosheets of platinum diselenide can possess mesoporosity as this may enable a high range of molecular adsorption, enhancing their functionalities in catalysis, batteries, supercapacitors, and sensing. Here, we present for the first time a straightforward, aqueous-phase synthetic strategy for the preparation of scalable nanosheets of platinum diselenide with mesoporous structure via a surfactant-templated self-assembly followed by a thermal annealing phase-transformation process. We used hexamethylenetetramine as a hexagonal honeycomb (sp2-sp3 orbital) scaffold for assembling the Pt and Se organic complexes to form the nanosheet structure, which is stable, preserving the 2D structure and mesoporosity during a thermal annealing at 500 °C. Density functional theory analysis then indicated that the mesoporous nanosheets of platinum diselenide exhibit a high free-energy and large density of π electrons crossing the Fermi level, inferring a high-catalytic performance. This effortless strategy is currently being extended to the synthesis of other transition metal dichalcogenides, including the preparation of multi-metal atomic dichalcogenide nanosheets, for a wide variety of scientific and technological applications.
Chitosan-magnetic-graphene oxide (CMGO) nanocomposite was prepared for arsenic adsorption. The nanocomposite was characterized through BET, FTIR, FESEM, EDX, and VSM analyses. These characterizations confirmed the formation of CMGO nanocomposites with high specific surface area (152.38 m2/g) and excellent saturation magnetization (49.30 emu/g). Batch adsorption experiments were conducted to evaluate the performance of the nanocomposite in the adsorption of arsenic from aqueous solution. The effects of operational parameters, adsorption kinetic, equilibrium isotherm and thermodynamics were evaluated. The removal efficiency of arsenic increased with increasing adsorbent dosage and contact time. However, the effect of pH followed a different pattern, with the removal efficiency increasing from acidic to neutral pH, and then decreasing at alkaline conditions. The highest adsorption capacity (45 mg/g) and removal efficiency (61%) were obtained at pH 7.3. The adsorption kinetic followed a pseudo-second-order kinetic model. The analysis of adsorption isotherm shows that the adsorption data fitted well to Langmuir isotherm model, indicating a homogeneous process. Thermodynamic analysis shows that the adsorption of As(III) is exothermic and spontaneous. The superparamagnetic properties of the nanocomposite enabled the separation and recovery of the nanoparticles using an external magnetic field. Thus, the developed nanocomposite has a potential for arsenic remediation.
This present research aims to synthesize and investigate the adsorption potential of sugarcane bagasse (SCB) impregnated with iron oxide (Fe3O4) for dye removal. The surface morphology and functional groups of the newly developed adsorbent (ISCB) were studied using Scanning Electron Microscopy/Energy-dispersive X-ray spectroscopy (SEM/EDX), Fourier transforms infrared spectroscopy (FTIR), and X-ray powder diffraction (XRD) analysis. The effects of the operating parameters, including initial dye concentration, adsorbent dosage, contact time and initial pH of the dye solution on the adsorption efficiency were investigated to identify an optimal condition. The characterization of SEM-EDX and FTIR analyses shows that ISCB has a porous structure and carbon-containing functional groups. The adsorption result revealed that ISCB removed 93.7% of dye, 88.8% of color and had a dye adsorption capacity of 7.2 mg/g within 6 h of contact time using 0.7 g/L of ISCB at pH 8.4. The result obtained fitted well for Langmuir isotherms, and adsorption process followed the pseudo-second-order kinetic model. In conclusion, this study proved that ISCB has the potential to be used as an effective and low-cost adsorbent to remove dyes from wastewater.
A high-performance porous biochar adsorbent prepared by facile thermal pyrolysis of seaweed (Gelidiella acerosa) is reported. The textural characteristics of the prepared seaweed biochar (SWBC) and the performance in the adsorption of methylene blue (MB) dye were evaluated. The batch experiment for the adsorption of MB was conducted under different parameters, such as temperature, pH, and initial concentration of MB in the range of 25-400 mg/L. The developed SWBC exhibited a relatively high surface area, average pore size, and pore volume of 926.39 m2/g, 2.45 nm, and 0.57 cm3/g, respectively. The high surface area and pristine mineral constituents of the biochar promoted a high adsorption capacity of 512.67 mg/g of MB at 30 °C. The adsorption isotherm and kinetics data best fitted the Langmuir and pseudo-second-order equations. The results indicate that SWBC is efficient for MB adsorption and could be a potential adsorbent for wastewater treatment.
In this study, a binary mixture of petroleum coke and palm kernel shell had been investigated as potential starting materials for activated carbon production. Single-stage potassium carbonate (K2CO3) activation under nitrogen (N2) atmosphere was adopted in this research study. Effect of several operating parameters that included the impregnation ratio (1-3 wt./wt.), activation temperature (600-800 °C), and dwell time (1-2 hrs) were analyzed by using the Box-Behnken experimental design. Influence of these parameters towards activated carbon yield (Y1) and carbon dioxide (CO2) adsorption capacity at an atmospheric condition (Y2) were investigated. The optimum conditions for the activated carbon production were attained at impregnation ratio of 1.75:1, activation temperature of 680 °C, and dwell time of 1 h, with its corresponding Y1 and Y2 is 56.2 wt.% and 2.3991 mmol/g, respectively. Physicochemical properties of the pristine materials and synthesized activated carbon at the optimum conditions were analyzed in terms of their decomposition behavior, surface morphology, elemental composition, and textural characteristics. The study revealed that the blend of petroleum coke and palm kernel shell can be effectively used as the activated carbon precursors, and the experimental findings demonstrated comparable CO2 adsorption performance with commercial activated carbon as well as that in literatures.
In this study, glucose is used as a template to manufacture microporosity in silica. Based on this objective, five different molar ratios of glucose (0%, 10%, 20%, 30% and 50%) were used for this experiment to maximise its affinity to adsorb oil droplets. The sample has been characterized using
thermogravimetric analysis (TGA), Nitrogen Adsorption and UltravioletVisible (UV-Vis) pectroscopy. The adsorption of oil was tested in 1000 ppm oil-water emulsion in order to determine the performance of the templated silica. TGA analysis showed that 550 ̊C is a suitable temperature for material calcination for all the samples. N2 adsorption showed the glucose templated silica (50%) had limited porosity, with a low surface area of 2 m2 /g. This is much lower than non-templated silica which was mesoporous, with an average pore diameter of 2.6 nm and a surface area of 272 m2 /g. Interestingly, despite the low porosity of the templated silica, high oil-water
separations were achieved. This shows that glucose-templated silica is a promising material for oil-water separations.
This work studied the potential of using eggshell (ES) (200-300 μm) waste as adsorbent for sequential removal of heavy metals, soluble microbial products, and dye wastes. In this study, among soluble microbial products, chicken egg white (CEW) proteins were selected as simulated contaminants. ES was applied to capture heavy metal ions (e.g., Cu2+ and Zn2+) and the formed eggshell metal (ES-M) complex was use to absorb soluble microbial products (e.g., soluble proteins), followed by subsequent removal of dyes from aqueous solutions using ES-M-CEW adsorbent. The experimental conditions for the adsorption of CEW proteins by ES-M include shaking rate, adsorption pH, isothermal and kinetic studies. The maximum protein adsorption by ES-Zn and ES-Cu were 175.67 and 153.65 mg/g, respectively. Optimal removal efficiencies of the ES-M-CEW particles for Acid Orange (AO7) and Toluidine blue (TBO) dyes were at pH 2 and 12, respectively, achieving performance of 75.38 and 114.18 mg/g, respectively. The removal of TBO dye by ES-M-CEW adsorbent was equilibrated at 5 min. The results showed that low cost and simple preparation of the modified ES particles are feasible for treating various wastewaters.
This work incorporated technological values into Zn2Cr-layered double hydroxide (LDH), synthesized from unused resources, for removal of pyrophosphate (PP) in electroplating wastewater. To adopt a resource recovery for the remediation of the aquatic environment, the Zn2Cr-LDH was fabricated by co-precipitation from concentrated metals of plating waste that remained as industrial by-products from metal finishing processes. To examine its applicability for water treatment, batch experiments were conducted at optimum M2+/M3+, pH, reaction time, and temperature. To understand the adsorption mechanisms of the PP by the adsorbent, the Zn2Cr-LDH was characterized using Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analyses before and after adsorption treatment. An almost complete PP removal was attained by the Zn2Cr-LDH at optimized conditions: 50 mg/L of PP, 1 g/L of adsorbent, pH 6, and 6 h of reaction. Ion exchange controlled the PP removal by the adsorbent at acidic conditions. The PP removal well fitted a pseudo-second-order kinetics and/or the Langmuir isotherm model with 79 mg/g of PP adsorption capacity. The spent Zn2Cr-LDH was regenerated with NaOH with 86% of efficiency for the first cycle. The treated effluents could comply with the discharge limit of <1 mg/L. Overall, the use of the Zn2Cr-LDH as a low-cost adsorbent for wastewater treatment has contributed to national policy that promotes a zero-waste approach for a circular economy (CE) through a resource recovery paradigm.
There are many methods to separate or purify the rebaudioside A compound from Stevia rebaudiana extract. However, the ion-exchange chromatography using macroporous resin is still the most popular among those methods. The separation of rebaudioside A from stevia crude extract by macroporous resin AB-8 was optimised in this adsorption separation study. This approach was applied to evaluate the influence of four factors such as the adsorption temperature, desorption time, elution solution ratio, and adsorption volume on rebaudioside A yield of the purified stevia extract. The results showed that the low polarity resin AB-8 is able to separate rebaudioside A from stevia extract with 0.601 in yield compared to the high polarity resin HPD 600 with 0.204 in yield used in Anvari and Khayati study. The best conditions for rebaudioside A separation by macroporous resin AB-8 were at 35°C of adsorption temperature, 30 min of desorption time, elution solution ratio 2:1, and 50 mL of adsorption volume.