To realize sound disposal of hyperaccumulator harvested from phytoremediation, hydrothermal carbonization (HTC) has been employed to obtain superior hydrochar adsorbents for removal of phosphate and ammonium from water body. A series of hydrochars have been prepared under tuned HTC conditions to tailor hydrochar with desired properties. Generally, increased temperature and prolonged reaction time facilitated acidic oxygen functional groups on hydrochars, thereby improving adsorption capacity of hydrochar. In single solute system, a superior hydrochar, derived from HTC under 260 °C for 2 h, achieved a maximum phosphate and ammonium adsorption capacity of 52.46 mg/g and 27.56 mg/g at 45 °C, respectively. In binary system, synergistic adsorption was observed only in lower solute concentration, whereas competitive adsorption occurred under higher solute concentration. Characterization and adsorption kinetics suggested chemisorption may dominate the adsorption process, thus the adsorption capacity could be improved by tuning pHpzc of hydrochar. This study firstly demonstrates the sustainable utilization of hyperaccumulators into nutrients-enriched hydrochar as fertilizer for in-situ phytoremediation of contaminated sites with minimized environmental risks towards circular economy.
Three specific catalysts, namely ZIF-67 (zeolitic imidazolate framework-67), Co@NCF (Co@Nitrogen-Doped Carbon Framework), and 3D NCF (Three-Dimensional Nitrogen-Doped Carbon Framework), were prepared and studied for pulp and paper mill effluent degradation using heterogeneous activation of peroxymonosulfate (PMS). Numerous characterizations, including scanning electron microscopy (SEM), X-ray diffraction (XRD), and N2 adsorption, were used to characterize the properties of three different catalysts. 3D NCF is remarkably effective at heterogeneous activation of PMS to generate sulfate radicals to degrade pulp and paper mill effluent (PPME) compared to the other as-prepared catalysts. The catalytic activity reveals a sequence of 3D NCF > Co@NCF > ZIF-67.3D NCF could degrade organic pollutants in 30 min at an initial COD concentration of 1146 mg/L of PPME, 0.2 g/L catalysts, 2 g/L PMS, and 50 °C. Consequently, it was observed that the degradation of PPME using 3D NCF followed first-order kinetics, with an activation energy of 40.54 kJ mol-1. Overall, 3D NCF/PMS system reveals promising performance for PPME removal.
The paper presents the thermoluminescence (TL) response of strontium tetraborate glass subjected to electron irradiations at various Dy2O3 concentrations ranging from 0.00 to 1.00mol%. All glass samples exhibited single broad peak with maximum peak temperature positioned at 170-215°C. The optimum TL response was found at Dy2O3 concentration 0.75mol%. This glass showed good linearity and higher sensitivity for 7MeV compared to 6MeV electrons. Analysis of kinetic parameters showed that the glasses demonstrate second order kinetic.
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.
Each year, nearly 30 million tons of pineapple fruit are harvested for food and drinking industries, along with the release of a huge amount of pineapple wastes. Without the proper treatment, pineapple wastes can cause adverse impacts on the environment, calling for new technologies to convert them into valuable products. Here, we review the production and application of adsorbents derived from pineapple wastes. The thermal processing or chemical modification improved the surface chemistry and porosity of these adsorbents. The specific surface areas of the pineapple wastes-based adsorbents were in range from 4.2 to at 522.9 m2·g-1. Almost adsorption systems followed the pseudo second order kinetic model, and Langmuir isotherm model. The adsorption mechanism was found with the major role of electrostatic attraction, complexation, chelation, and ion exchange. The pineapple wastes based adsorbents could be easily regenerated. We suggest the potential of the pineapple wastes towards circular economy.
In this study, luminescent bio-adsorbent nitrogen-doped carbon dots (N-CDs) was produced and applied for the removal and detection of Hg (II) from aqueous media. N-CDs were synthesized from oil palm empty fruit bunch carboxymethylcellulose (CMC) and urea. According to several analytical techniques used, the obtained N-CDs display graphitic core with an average size of 4.2 nm, are enriched with active sites, stable over a wide range of pH and have great resistance to photobleaching. The N-CDs have bright blue emission with an improved quantum yield (QY) of up to 35.5%. The effect of the variables including pH, adsorbent mass, initial concentration and incubation time on the removal of Hg (II) was investigated using central composite design. The statistical results confirmed that the adsorption process could reach equilibrium within 30 min. The reduced cubic model (R2 = 0.9989) revealed a good correlation between the observed values and predicted data. The optimal variables were pH of 7, dose of 0.1 g, initial concentration of 100 mg/L and duration of 30 min. Under these conditions, adsorption efficiency of 84.6% was obtained. The adsorption kinetic data could be well expressed by pseudo-second-order kinetic and Langmuir isotherm models. The optimal adsorption capacity was 116.3 mg g-1. Furthermore, the adsorbent has a good selectivity towards Hg (II) with a detection limit of 0.01 μM due to the special interaction between Hg (II) and carboxyl/amino groups on the edge of N-CDs. This work provided an alternative direction for constructing low-cost adsorbents with effective sorption and sensing of Hg (II).
Water purification using adsorption is a crucial process for maintaining human life and preserving the environment. Batch and dynamic adsorption modes are two types of water purification processes that are commonly used in various countries due to their simplicity and feasibility on an industrial scale. However, it is important to understand the advantages and limitations of these two adsorption modes in industrial applications. Also, the possibility of using batch mode in industrial scale was scrutinized, along with the necessity of using dynamic mode in such applications. In addition, the reasons for the necessity of performing batch adsorption studies before starting the treatment on an industrial scale were mentioned and discussed. In fact, this review article attempts to throw light on these subjects by comparing the biosorption efficiency of some metals on utilized biosorbents, using both batch and fixed-bed (column) adsorption modes. The comparison is based on the effectiveness of the two processes and the mechanisms involved in the treatment. Parameters such as biosorption capacity, percentage removal, and isotherm models for both batch and column (fixed bed) studies are compared. The article also explains thermodynamic and kinetic models for batch adsorption and discusses breakthrough evaluations in adsorptive column systems. The review highlights the benefits of using convenient batch-wise biosorption in lab-scale studies and the key advantages of column biosorption in industrial applications.
Research into the speciation of sulfur and hydrogen molecules produced through the complex process of thermophilic dark fermentation has been conducted. Detailed surface studies of solid-gas systems using real biogas (biohydrogen) streams have unveiled the mechanisms and specific interactions between these gases and the physicochemical properties of a zeolite as an adsorbent. These findings highlight the potential of zeolites to effectively capture and interact with these molecules. In this study, the hydrogen sulphide removal analysis was conducted using 0.8 g of the adsorbent and at various reaction temperatures (25-125 °C), a flow rate of 100 mL min-1, and an initial concentration of approximately 5000 ppm hydrogen sulphide. The reaction temperature has been observed to be an essential parameter of Zeolite Socony Mobil - 5 adsorption capacity. The optimum adsorption capacity attains a maximum value of 0.00890 mg g-1 at an optimal temperature of 25 °C. The formation of sulphur species resulting from the hydrogen sulphide adsorption on the zeolite determines the kinetics, thermodynamics, and mass transfer behaviours of Zeolite Socony Mobil - 5 in hydrogen sulphide removal and Zeolite Socony Mobil - 5 is found to improve the quality of biohydrogen produced in thermophilic environments. Biohydrogen (raw gas) yield was enhanced from 2.48 mol H2 mol-1 hexose consumed before adsorption to 2.59 mol H2 mol-1 hexose consumed after adsorption at a temperature of 25 °C. The Avrami kinetic model was fitted for hydrogen sulphide removal on Zeolite Socony Mobil - 5. The process is explained well and fitted using the Temkin isotherm model and the investigation into thermodynamics reveals that the adsorption behaviour is exothermic and non-spontaneous. Furthermore, the gas molecule's freedom of movement becomes random. The adsorption phase is restricted by intra-particle diffusion followed by film diffusion during the transfer of hydrogen sulphide into the pores of Zeolite Socony Mobil - 5 prior to adsorption on its active sites. The utilisation of Zeolite Socony Mobil - 5 for hydrogen sulphide removal offers the benefit of reducing environmental contamination and exhibiting significant applications in industrial operations.
Driven by the need for solutions to address the global issue of waste accumulation from human activities and industries, this study investigates the thermal behaviors of empty fruit bunch (EFB), tyre waste (TW), and their blends during co-pyrolysis, exploring a potential method to convert waste into useable products. The kinetics mechanism and thermodynamics properties of EFB and TW co-pyrolysis were analysed through thermogravimetric analysis (TGA). The rate of mass loss for the blend of EFB:TW at a 1:3 mass ratio shows an increase of around 20% due to synergism. However, the blend's average activation energy is higher (298.64 kJ/mol) when compared with single feedstock pyrolysis (EFB = 257.29 kJ/mol and TW = 252.92 kJ/mol). The combination of EFB:TW at a 3:1 ratio does not result in synergistic effects on mass loss. However, a lower activation energy is reported, indicating the decomposition process can be initiated at a lower energy requirement. The reaction model that best describes the pyrolysis of EFB, TW and their blends can be categorised into the diffusion and power model categories. An equal mixture of EFB and TW was the preferred combination for co-management because of the synergistic effect, which significantly impacts the co-pyrolysis process. The mass loss rate experiences an inhibitive effect at an earlier stage (320 °C), followed by a promotional impact at the later stage (380 °C). The activation energy needed for a balanced mixture is the least compared to all tested feedstocks, even lower than the pyrolysis of a single feedstock. The study revealed the potential for increasing decomposition rates using lower energy input through the co-pyrolysis of both feedstocks. These findings evidenced that co-pyrolysis is a promising waste management and valorisation pathway to deal with overwhelming waste accumulation. Future works can be conducted at a larger scale to affirm the feasibility of EFB and TW co-management.
The natural blue colorant C-phycocyanin (C-PC) has many potential applications but its poor heat stability limits its commercial use. This study compares the production and thermal stability of C-PC from two cyanobacteria: the thermophilic Thermosynechococcus sp. TUBT-T01 and the mesophilic Synechococcus cedrorum TISTR8589. Thermosynechococcus sp. produced nearly 1.9-fold more C-PC than S. cedrorum. Batch adsorption using a chromatographic cationic ion exchange resin (Streamline Direct HST1) was used to effectively purify the C-PC. The equilibrium adsorption capacity (Qeq) of the resin for C-PC was the highest at pH 5. At this pH, the Qeq for the thermophilic C-PC was 5.5 ± 0.1 mg mL⁻¹ , whereas for the mesophilic C-PC it was 1.5 ± 0.2 mg mL⁻¹ . Purification increased the concentration of the thermophilic C-PC by 5.9-fold, and that of mesophilic C-PC by 4.2-fold. The purity ratios of the final products from the two cyanobacteria were similar at ∼2.2. At 60 °C and pH 7, the C-PC of Thermosynechococcus sp. had ∼12-times longer half-life than the mesophilic C-PC; however, the productivity of the thermophilic C-PC was comparatively low because of a low biomass productivity of Thermosynechococcus sp.
Frequent detection of terbutaline in wastewater highlights its potential risks to human health associated in the environment. Exposure to terbutaline through contaminated water sources or food chain have adverse effects to human health. This work emphasized on the removal of terbutaline from wastewater using adsorption technology. Mechanochemically synthesized [Cu(INA)2] metal-organic frameworks (MOFs) and its magnetic composite ([Cu(INA)2]-MOF@Fe3O4) are designed with higher specific surface areas and tailored features to accommodate the molecular size and structure of terbutaline. Thus, batch experiment has been conducted using the [Cu(INA)2]-MOF and [Cu(INA)2]-MOF@Fe3O4 for the terbutaline adsorption. The adsorption efficiency achieved by the MOFs was 91.8% and 99.3% for the Cu(INA)2]-MOF and [Cu(INA)2]-MOF@Fe3O4 respectively. The optimum for the adsorption study included terbutaline concentration of 40 mg/L, adsorbent dose of 5 mg/L, pH of 11, temperature of 25 °C and equilibrium time of 40 min. The kinetics and isotherms have been described by pseudo-second order and Langmuir models, while the thermodynamics revealed the exothermic and spontaneous nature of the process. The promising performance of the MOFs is manifested on the ease of regeneration and reusability, achieving adsorption efficiency of 85.0% and 94.7% by the Cu(INA)2]-MOF and [Cu(INA)2]-MOF@Fe3O4, respectively at five consecutive cycles. The higher performance of the MOFs demonstrates their excellent potentialities for the terbutaline adsorption from the aqueous solution.
In view of the simple and rapid conveniency of magnetic separation, magnetic nanocomposites had notably gained attention from researchers for environmental field applications. In this work, carboxylated magnetic multi-walled carbon nanotubes (c-MMWCNTs) and novel sulfonated MMWCNTs (s-MMWCNTs) were synthesized by a facile solvent-free direct doping method. Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscope, energy dispersive X-ray, vibrating sample magnetometer, and point of zero charge analyses confirmed the successful doping of the Fe3O4 nanoparticles into the functionalized MWCNTs to form MMWCNTs. Besides, the bonding stabilities of both c-MMWCNTs and s-MMWCNTs were compared, and results showed that s-MMWCNTs possessed more substantial bonding stability than that of c-MMWCNTs with significantly less leaching amount of Fe3O4. The adsorption capacity of s-MMWCNTs was higher than that of c-MMWCNTs owing to the stronger electronegativity sulfonic group in s-MMWCNTs. Moreover, the reusability experiments proved that the adsorbent remained consistently excellent MB removal efficiency (R > 94%) even reused for twelve cycles of batch adsorption. The finding of the present work highlights the simple fabrication of novel s-MMWCNTs and its potential to be served as a promising and sustainable adsorbent for water remediation owing to its enhanced bonding stability, high adsorption performance, magnetic separability, and supreme recyclability.
The current work aimed to investigate the degradation of the triclocarban (TCC) in aqueous solution using a modified zeolite/TiO2 composite (MZTC) synthesized by applying the electrochemical anodization (ECA). The synthesis process was conducted at different voltages (10, 40, and 60) V in 1 h and using electrophoresis deposition (EPD) in doping zeolite. The MZTC was covered with the array ordered, smooth and optimum elongated nanotubes with 5.1 μm of the length, 120.3 nm of the inner diameter 14.5 nm of the wall thickness with pure titanium and crystalline titania as determined by FESEM/EDS, and XRD. The kinetic study by following Langmuir-Hinshelwood(L-H) model and pseudo first order, the significant constant rate was obtained at pH 11 which was 0.079 ppm/min, 0.75 cm2 of MZTC catalyst loading size achieved 0.076 ppm/min and 5 ppm of TCC initial concentration reached 0.162 ppm/min. The high-performance liquid chromatography (HPLC) analysis for mechanism study of TCC photocatalytic degradation revealed eleven intermediate products after the whole process of photocatalysis. In regard of toxicology assessment by the bacteria which is Photobacterium phosphoreum, the obtained concentration of TCC at minute 60 was less satisfied with remained 0.36 ppm of TCC was detected indicates that the concentration was above allowable level. Where the allowable level of TCC in stream is 0.1 ppm.
Separation materials have received increasing attention given their broad applications in the management of environmental pollution. It is desired to balance the contradiction between high separation efficiency and selectivity of separation materials. The integration of ball-milled bone chars with electrospun membranes might achieve this balance. In this study, electrospun cellulose/chitosan/ball-milled bone char (CL/CS/MB) membranes were by well-dispersing ball-milled bone chars with nanoscale size (98.9-167.5 nm) and developed porosity (40.2-373.1 m2/g) in the electrospinning solvent. The synergistic integration of distributed MBs (5.4-31.5 wt.% of loading hydroxyapatite on the membrane matrix) allowed the efficient sorption of Pb(II) with fast kinetics (20.0 min), excellent capacity (219.9 mg/g at pH 5.0, T 298 K), and favorable selectivity coefficients (2.76-6.79). The formation of minerals was dominant for the selective sorption of Pb(II) by combining the spectral analysis and quantitative determination. The surface complexation with O-/reductive N-species, the cation exchange with inorganic Ca2+, the electrostatic attraction with deprotonated O-, and the cation-π coordination with the aromatic carbon via the π-electrons should be not ignored for the capture of Pb(II). This work demonstrated the feasibility of electrospun CL/CS/MB membranes as a promising candidate for the remediation of aquatic pollutants.
This study presents the kinetics and thermodynamics of biomass pyrolysis. The kinetics of the pyrolysis process was estimated using ten kinetic models from three different mechanisms, namely chemical reaction, diffusion, and nucleation and growth. Results showed that each pyrolysis subdivision was described by a different reaction model, signifying the complex nature of the pyrolysis process. The average values of activation energy determined from the kinetic models for empty fruit bunch, coconut shell, bamboo, and cardboard are 10.2-64.6 kJ/mol, 18.7-186.2 kJ/mol, 8.0-70.8 kJ/mol, and 13.1-277.3 kJ/mol, respectively. The biomass pyrolysis is endothermic and non-spontaneous and would require external energy to initiate the degradation process. The findings are helpful in characterizing the thermal degradation of biomass in exploring its potential as a source of alternative solid fuel.
This study reports the analysis of diclofenac removal from aqueous solution using a novel adsorbent coating with amphoteric surface. This adsorbent coating was improved using a new amphoteric ratio to increase its performance for the removal of pharmaceuticals such as diclofenac. The adsorbent coating was formulated using acrylic polymer emulsion, smectite-based clay powder and epichlorohydrin-dimethylamine to obtain a layer form via the implementation of a facile synthesis method. In a previous study, this adsorbent coating was successful to remove cationic and anionic dyes. Therefore, this research aimed to further investigate and test its application in the removal of other emerging water pollutants like pharmaceuticals. SEM, EDX, and FTIR analyses were carried out for the characterization of this novel adsorbent. The effects of adsorbent composition, diclofenac concentration, temperature, and solution pH were studied and modeled. The best conditions to improve the diclofenac adsorption was 303 K and pH 3 where the adsorption capacity was 25.59 mg/g. Adsorption isotherms and kinetics were quantified and modeled, and the corresponding adsorption mechanism was also analyzed. Diclofenac adsorption with this novel material was exothermic and spontaneous. This alternative adsorbent is promising for diclofenac removal from industrial wastewater systems.
Guided by efficient utilization of natural plant oil and sulfur as low-cost sorbents, it is desired to tailor the porosity and composition of polysulfides to achieve their optimal applications in the management of aquatic heavy metal pollution. In this study, polysulfides derived from soybean oil and sulfur (PSSs) with improved porosity (10.2-22.9 m2/g) and surface oxygen content (3.1-7.0 wt.%) were prepared with respect to reaction time of 60 min, reaction temperature of 170 °C, and mass ratios of sulfur/soybean oil/NaCl/sodium citrate of 1:1:3:2. The sorption behaviors of PSSs under various hydrochemical conditions such as contact time, pH, ionic strength, coexisting cations and anions, temperature were systematically investigated. PSSs presented a fast sorption kinetic (5.0 h) and obviously improved maximum sorption capacities for Pb(II) (180.5 mg/g), Cu(II) (49.4 mg/g), and Cr(III) (37.0 mg/g) at pH 5.0 and T 298 K, in comparison with polymers made without NaCl/sodium citrate. This study provided a valuable reference for the facile preparation of functional polysulfides as well as a meaningful option for the removal of aquatic heavy metals.
Partial hydrogenation is an effective approach for modulating the structural and functional properties of oils, however, the response behaviors of different glyceride molecular structures during hydrogenation remain insufficiently understood. In this study, hydrogenation models for triacylglycerol (TAG)-based and diacylglycerol (DAG)-based oils were systematically constructed under identical reaction conditions to directly compare their hydrogenation behaviors and resulting product differences. Kinetic analysis revealed that DAG-based oils exhibited higher overall hydrogenation rate constants than TAG-based oils, indicating superior hydrogenation efficiency attributed to the lower steric hindrance of DAG molecules. Compared with TAG-based oils, DAG-based oils achieved dramatically greater hardness and a broader solid fat content range under identical hydrogenation conditions, indicating superior plasticity regulation capability. Furthermore, DAG-based oils produced lower trans fatty acid levels and exhibited distinct polymorphic behavior, with coexistence of α, β', and β crystal forms. These findings demonstrate that glyceride molecular structure plays a significant role in determining hydrogenation behavior and quality formation, providing a theoretical basis for designing functional structured lipids and optimizing the quality of hydrogenated oil products through glyceride composition regulation.
Oleic acid is a mono-unsaturated fatty acid that can be found abundantly in various vegetable oils and potentially attractive to be used as raw material for epoxide chemical. In-situ epoxidation of oleic acid was conducted in batch reactor using peroxy-formic at 30-60°C. Pseudo-steady-state-hypothesis (PSSH) was applied to develop the kinetic model. Heterogeneous liquid-liquid system was chosen and four models which emphasized on the ring opening agent (ROA) and reversibility of the epoxidation reaction were proposed. It has been suggested that reversible model is well suited to represent the experimental data. Activation energy obtained from Arrhenius equation is in the range of 40-195 kJ/mol.
Recently, rubber seed oil (RSO) has been considered as a promising potential oil source for biodiesel production. However, RSO is a non-edible feedstock with a significant high free fatty acid (FFA) content which has an adverse impact on the process of biodiesel production. In this study, ultrasonic-assisted esterification process was conducted as a pre-treatment step to reduce the high FFA content of RSO from 40.14% to 0.75%. Response surface methodology (RSM) using central composite design (CCD) was applied to the design of experiments (DOE) and the optimization of esterification process. The result showed that methanol to oil molar ratio was the most influential factor for FFA reduction whereas the effect of amount of catalyst and the reaction were both insignificant. The kinetic study revealed that the activation energy and the frequency factor of the process are 52.577kJ/mol and 3.53×108min-1, respectively.