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.
In this study, activated carbon (AC) was prepared from agro-waste betel nut husks (BNH) through the chemical activation method. Different characterization techniques described the physicochemical nature of betel nut husks activated carbon (BNH-AC) through Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), and pH point of zero charge. Later, the produced AC was used for methylene blue (MB) adsorption via numerous batch experimental parameters: initial concentrations of MB dye (25-250 mg/L), contact time (0.5-24 hours) and initial pH (2-12). Dye adsorption isotherms were also assessed at three temperatures where the maximum adsorption capacity (381.6 mg/g) was found at 30 °C. The adsorption equilibrium data were best suited to the non-linear form of the Freundlich isotherm model. Additionally, non-linear pseudo-second-order kinetic model was better fitted with the experimental value as well. Steady motion of solute particles from the boundary layer to the BNH-AC's surface was the possible reaction dynamics concerning MB adsorption. Thermodynamic study revealed that the adsorption process was spontaneous and exothermic in nature. Saline water emerged as an efficient eluent for the desorption of adsorbed dye on AC. Therefore, the BNH-AC is a very promising and cost-effective adsorbent for MB dye treatment and has high adsorption capacity.
A novel nanocomposite of MGO-NGC, composed of magnetic Fe3O4 nanoparticles (M), graphene oxide (GO), and N-methyl-d-glucamine functionalized calix[4]arene (NGC), was synthesized and applied as an effective adsorbent for the removal of two selected pesticides, namely hexaconazole and chlorpyrifos from water samples. The adsorbent was characterized by FTIR, SEM, EDX, TEM, and XRD. The main parameters affecting the adsorption process such as adsorbent dosage, pH of sample solution, salt effect, pesticide concentration, and adsorption time were investigated. The data from kinetic studies fitted well to the pseudo-second order kinetic model with R2 > 0.99. Among the isotherm models of Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich, the Langmuir isotherm fitted well to the adsorption process and demonstrated the monolayer adsorption pattern of the pesticides. Moreover, high adsorption capacities of 78.74 and 93.46 mg g-1 were obtained for chlorpyrifos and hexaconazole, respectively. Thermodynamic and free energy data indicated the physisorption mechanism for the adsorption process. The new adsorbent can be employed as an efficient, environment friendly, and highly reusable alternative for the removal of chlorinated pesticides from aqueous media.
Polyelectrolyte composite nanospheres are relatively new adsorbents which have attracted much attention for their efficient pollutant removal and reuse performance. A novel polyelectrolyte nanosphere with magnetic function (SA@AM) was synthesized via the electrostatic reaction between the polyanionic sodium alginate (SA) and the surface of a prepared terminal amino-based magnetic nanoparticles (AMs). SA@AM showed a size of 15-22 nm with 6.85 emu·g-1 of magnetization value, exhibiting a high adsorption capacity on Pb(II) ions representing a common heavy metal pollutant, with a maximum adsorption capacity of 105.8 mg g-1. The Langmuir isotherm adsorption fits the adsorption curve, indicating uniform adsorption of Pb(II) on the SA@AM surfaces. Repeated adsorption desorption experiments showed that the removal ratio of Pb(II) by SA@AM was more than 76%, illustrating improved regeneration performance. These results provide useful information for the production of bio-based green magnetic nano scale adsorption materials for environmental remediation applications.
Medium-chain diacylglycerol (MCD), medium-long-chain diacylglycerol (MLCD), and long-chain diacylglycerol (LCD) were prepared through enzymatic esterification using different conditions at temperatures of 55-70 °C and reaction times of 1.5-5 h and in the presence of 5-6% Novozym 435. Subsequently, purification was performed using three different techniques, namely, molecular distillation (MD), deodorization (DO), and silica gel column chromatography (SGCC). Variations in terms of the physicochemical and thermodynamic properties, crystallization properties, and kinetics of the diacylglycerols (DAGs) before and after purification were determined. Irrespective of the DAG chain lengths, SGCC was able to produce samples with high DAG purity (96-99 wt %), followed by MD (58-79 wt %) and DO (39-59 wt %). A higher 1,3-DAG/1,2-DAG ratio was recorded for all samples, with the highest ratio recorded for SGCC purified samples. Regardless of the purification techniques used, the solid fat content (SFC) profiles of crude samples with steep curves were altered post-purification, showing a gradual increment in SFC along with increasing temperature. Modification of the Avrami constant and coefficient suggested the modification of the crystal growth mechanism post-purification. Crystallization and melting temperatures of products with a higher DAG purity were shifted to a higher temperature region. Variations were also reflected in terms of the crystal polymorphism, whereby the α and β' crystals transitioned into the more stable β form in purified samples accompanied by modification in the microstructures and crystal sizes. However, there was insignificant change in the morphology of MLCD crystal after purification, except for the decrease in crystal sizes. In conclusion, synthesis of MCD, MLCD, and LCD comprising different DAG purities had distinctive SFC profiles, thermodynamic properties, crystallization kinetics, and crystal morphologies, which can be further incorporated into the preparation of a variety of fat products to obtain end products with desired characteristics.
In this study, a mineral-based coated urea was fabricated in a rotary pan coater using a mixture of gypsum/sulfur/zeolite (G25S25Z50) as an effective and low-cost coating material. The effects of different coating compositions on the dissolution rate of urea and the crushing strength and morphology of the coated urea were investigated. A 25:25:50 (wt %) mixture of gypsum/sulfur/zeolite (G25S25Z50) increased the coating effectiveness to 34.1% with the highest crushing strength (31.06 N). The effectiveness of coated urea was further improved to 46.6% with the addition of a microcrystalline wax (3%) as a sealant. Furthermore, the release mechanisms of various urea fertilizers were determined by fitting the release profiles with six mathematical models, namely, the zeroth-order, first-order, second-order, Higuchi, Ritger & Peppas, and Kopcha models. The results showed that the release mechanism of the uncoated urea and all other coated urea followed the Ritger & Peppas model, suggesting the diffusional release from nonswellable delivery systems. In addition, due to the increased mass-transfer resistance, the kinetic constant was decreased from 0.2233 for uncoated urea to 0.1338 for G25S25Z50-coated urea and was further decreased to 0.0985 when 3% Witcovar 146 sealant was applied.
We test the feasibility of TiO2(B)@carbon composites as adsorbents, derived from wheat straws, for tetracycline (TC) adsorption from aqueous solutions. Hydrochar (HC), biochar (BC), and hydrochar-derived pyrolysis char (HDPC) are synthesized hydrothermally from the waste and then functionalized with TiO2(B), named as 'Composite-1', 'Composite-2', and 'Composite-3', respectively. A higher loading of TiO2(B) into the HC was also synthesized for comparison, named as 'Composite-4'. To compare their physico-chemical changes before and after surface modification, the composites are characterized using FESEM-EDS, XRD, BET, FRTEM, and FTIR. The effects of H2O2 addition on TC removal are investigated. Adsorption kinetics and isotherms of TC removal are studied, while TC adsorption mechanisms are elaborated. We found that the Composite-4 has the highest TC removal (93%) at pH 7, 1 g/L of dose, and 4 h of reaction time at 50 mg/L of TC after adding H2O2 (10 mM). The TC adsorption capacities of the Composite-1 and Composite-4 are 40.65 and 49.26 mg/g, respectively. The TC removal by the Composite-1 follows the pseudo-second order. Overall, this suggests that converting the wheat straw into HC and then functionalizing its surface with TiO2(B) as a composite has added values to the waste as an adsorbent for wastewater treatment.
Neodymium-doped polyaniline supported Zn-Al layered double hydroxide (PANI@Nd-LDH) nanocomposite has been prepared via an ex-situ oxidative polymerization process. The as-prepared nanocomposite shows selective fluorescence detection and adsorption of hexavalent chromium Cr(VI) within a short period. The fluorescence intensity of PANI@Nd-LDH decreases linearly with Cr(VI) concentrations ranging from 200 ppb to 1000 ppb with a limit of detection (LOD) of 1.5 nM and a limit of quantification (LOQ) of 96 nM. The sensing mechanism can be ascribed by the inner filter effect of Cr(VI), the intercalation of Cr(VI) within the intergallery region of LDH, and the synergistic affinity of metal ions along with the polymer chain for Cr(VI). The adsorption performance of PANI@Nd-LDH nanocomposite is evaluated for Cr(VI) from wastewaters, which displayed high removal capacity towards Cr(VI) (219 mg/g) as compared on bare Nd-LDH (123 mg/g) and LDH (88 mg/g) respectively. The adsorption of Cr(VI) on PANI@Nd-LDH depends on the pH of the aqueous solution. The adsorption isotherm and kinetics are supported by the Langmuir model and pseudo-second-order model, respectively. Owing to the highly sensitive detection and adsorption of Cr(VI) from aqueous water samples demonstrated the potential application of PANI@Nd-LDH as an excellent environmental probe can be exploited.
In this paper, the adsorptive performance of synthesized thiourea (TU) modified poly(acrylonitrile-co-acrylic acid) (TU-P(AN-co-AA)) polymeric adsorbent for capturing p-nitrophenol (PNP) from aqueous solution was investigated. TU-P(AN-co-AA) was synthesized via the redox polymerization method with acrylonitrile (AN) and acrylic acid (AA) as the monomers, then modified chemically with thiourea (TU). Characterization analysis with Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), elemental microanalysis for CHNS, zeta potential measurement, Brunauer-Emmett-Teller (BET) surface analysis and thermal analyses were carried out to determine the morphology and physico-chemical properties of the synthesized polymer. The characterization results indicated successful surface modification of polymer with TU. The performance of TU-P(AN-co-AA) for the removal of PNP was investigated under various experimental parameters (adsorbent dosage, initial adsorbate concentration, contact time and temperature). The results demonstrated that the Freundlich isotherm model and pseudo-second-order kinetic model best described the equilibrium and kinetic data, respectively. Thermodynamic studies showed that the uptake of PNP by TU-P(AN-co-AA) was spontaneous and exothermic in nature. The results of the regeneration studies suggested that the TU-P(AN-co-AA) polymer is a reusable adsorbent with great potential for removing PNP from wastewater.
Synthetic dyes used in the textile and paper industries pose a major threat to the environment. In the present research work, the adsorption efficiency of the natural adsorbent Strychnos potatorum Linn (Fam: Loganiaceae) seeds were examined against the reactive orange-M2R dye from aqueous solution by varying the process conditions such as contact time, pH, adsorbent dosage, and initial dye concentration on adsorption of anionic azo dye. This study compares different types of artificial neural networks which are feedforward artificial neural network (FANN) and nonlinear autoregressive exogenous (NARX) model to predict the efficiency of a cost-effective natural adsorbent Strychnos potatorum Linn seeds on removing reactive orange-M2R dye from aqueous solution. Twelve training algorithms of neural network were compared, and the prediction on the adsorption performance of anionic azo dye from aqueous solution using Strychnos potatonum Linn seeds was evaluated by using the root mean squared error (RMSE), mean absolute error (MAE), coefficient of determination (R2), and accuracy. For FANN model, Levenberg-Marquardt (LM) backpropagation with 19 hidden neurons was selected as the optimum FANN model, with R2 of 0.994 and accuracy of 87.20%, 98.21%, and 66.60% for training, testing, and validation datasets, respectively. For NARX model, LM with 8 hidden neurons was selected as the most suitable training algorithm, with R2 value of more than 0.99 and accuracy of 88.00%, 90.91%, and 75.00% for training, testing, and validation datasets, respectively. NARX model accurately predicted the adsorption of anionic azo dye from aqueous solution using Strychnos potatonum Linn seeds with better performance than FANN model.
The present study aimed to investigate the removal efficiency of cephalexin (CFX) by a novel Cu-Zn bionanocomposite biosynthesized in the secondary metabolic products of Aspergillus arenarioides EAN603 with pumpkin peels medium (CZ-BNC-APP). The optimization study was performed based on CFX concentrations (1, 10.5 and 20 ppm); CZ-BNC-APP dosage (10, 55 and 100 mg/L); time (10, 55 and 100 min), temperature (20, 32.5 and 45 °C). The artificial neural network (ANN) model was used to understand the CFX behavior for the factors affecting removal process. The CZ-BNC-APP showed an irregular shape with porous structure and size between 20 and 80 nm. The FTIR detected CC, C-O and OH groups. ANN model revealed that CZ-BNC-APP dosage exhibited the vital role in the removal process, while the removal process having a thermodynamic nature. The CFX removal was optimized with 12.41 ppm CFX, 60.60 mg/L of CZ-BNC-APP, after 97.55 min and at 35 °C, the real maximum removal was 95.53% with 100.52 mg g-1 of the maximum adsorption capacity and 99.5% of the coefficient. The adsorption of CFX on CZ-BNC-APP was fitted with pseudo-second-order model and both Langmuir and Freundlich isotherms models. These findings revealed that CZ-BNC-APP exhibited high potential to remove CFX.
The physico-chemical properties of spray-dried pitaya peel powders kept at accelerated (45 ± 2°C) and room temperature (28 ± 2°C) for 14 weeks and 6 months, respectively were evaluated. Changes in physico-chemical properties of the peel powder were used as indicators of stability, while changes of the betacyanin pigment retention was used to calculate the shelf-life of the powder. Storage temperatures significantly (p < 0.05) affected all the studied parameters and Hunter a value had the most significant change. The pigment retention of peel powder was approximately 87% at 45°C and 89% at room temperature storage. Degradation of betacyanin pigment in the powder followed the first order reaction kinetics with the half-life (t1/2) of approximately 76 weeks at 45°C and 38 months at 28°C. The spray-dried pitaya peel powder had a solubility of 87 to 92% and low in powder hygroscopicity. The final Aw of the powder did not exceed 0.6 for both storage temperatures.
Dried kiwis are highly needed in food industries such as cereals, ice-cream, beverages and supplemental products. In this paper, drying characteristics and product quality of hot air dried kiwi slices were studied. Hot air drying of kiwi slices was investigated at drying temperature ranged from 40°C to 60°C and slice thickness of 0.3 cm and 0.6 cm. Results showed that drying of kiwi slices at higher drying temperature stimulates the drying rate, which leads to shorter total drying time required. The drying kinetics of kiwi slices was best fitted by approximation diffusion model. Increased in drying temperatures and slice thickness of kiwi enhanced the effective moisture diffusivity (Deff). The highest Deff of the kiwi slices was recorded as 1.5681 x 10-8 m2 /min at slice thickness of 0.6 cm. In terms of quality analysis, kiwi slices dried at temperature of 60°C with fastest drying rate retained most of the Total Phenolic Content (TPC) in the dried sample. However, drying of kiwi slices at high drying temperature deteriorated the vitamin C content of kiwi slices due to thermal degradation. Thinner kiwi slices could preserve higher amount of TPC and vitamin C during the drying process, yet the best hot air drying temperature for drying of kiwi slices could be relied on the consumers’ preference based on the dried product quality as reported in the current work.
This research investigated the potential of palm kernel shell (PKS), empty fruit bunch (EFB) and palm oil sludge (POS), abundantly available agricultural wastes, as feedstock for biochar production by slow pyrolysis (50mLmin(-1) N2 at 500°C). Various characterization tests were performed to establish the thermochemical properties of the feedstocks and obtained biochars. PKS and EFB had higher lignin, volatiles, carbon and HHV, and lower ash than POS. The thermochemical conversion had enhanced the biofuel quality of PKS-char and EFB-char exhibiting increased HHV (26.18-27.50MJkg(-1)) and fixed carbon (53.78-59.92%), and decreased moisture (1.03-2.26%). The kinetics of pyrolysis were evaluated by thermogravimetry at different heating rates (10-40°C). The activation energies determined by Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa models were similar, and comparable with literature data. The findings implied that PKS and EFB are very promising sources for biochars synthesis, and the obtained chars possessed significant biofuel potential.
The biomass of Urochloa mutica was subjected to thermal degradation analyses to understand its pyrolytic behavior for bioenergy production. Thermal degradation experiments were performed at three different heating rates, 10, 30 and 50°Cmin-1 using simultaneous thermogravimetric-differential scanning calorimetric analyzer, under an inert environment. The kinetic analyses were performed using isoconversional models of Kissenger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO). The high heating value was calculated as 15.04MJmol-1. The activation energy (E) values were shown to be ranging from 103 through 233 kJmol-1. Pre-exponential factors (A) indicated the reaction to follow first order kinetics. Gibbs free energy (ΔG) was measured to be ranging from 169 to 173kJmol-1 and 168 to 172kJmol-1, calculated by KAS and FWO methods, respectively. We have shown that Para grass biomass has considerable bioenergy potential comparable to established bioenergy crops such as switchgrass and miscanthus.
The presence of heavy metals in aquatic systems has become a serious problem. Heavy metals can haveadverse effects on the environment as well as on human health. As a result, much attention has beengiven to new technologies for removal of heavy metal ions from contaminated waters. In this study,Microwave Incinerated Rice Husk Ash (MIRHA), a locally available agricultural waste, was used for theremoval of Cd (as a representative heavy metal) from synthetic wastewater by batch adsorption process.The effects of pH, initial metal concentration, and contact time on Cd removal efficiency were studied.pH 4 was found to be the optimum. The removal efficiency was found to be correlated with the initialmetal concentration and contact time between adsorbent and adsorbate. Cd adsorption kinetics followedthe pseudo-second-order model and implied chemisorption. The adsorption equilibrium of Cd can bewell described by the Freundlich isotherm model.
This study aims to evaluate the effect of heat and the simultaneous application of heat (80-95°C) and ultrasonic waves (thermosonication) on the inactivation kinetic of peroxidase and vitamin C degradation in seedless guava. Ultrasonic wave’s amplitudes except 25 and 100% had significant (P 0.98). In the heat blanching process, the peroxidase inactivation rate constant increased from 1.1×10-2 to 4.6×10-2 s-1. However, the inactivation rate of peroxidase was increased by 1.5–3 times in the temperature range 80–95ºC, with the 50 and 75% ultrasonic wave amplitudes, respectively. Decreases in vitamin C contents due to blanching treatments were found. Blanching processes at high temperature and short time resulted in higher vitamin C retention. It was found that thermosonication treatment inactivates seedless guava peroxidase at less severe blanching conditions and consequently retains vitamin C content at higher levels. The present findings will help to design the blanching conditions in order to reduce the severity of conventional thermal treatments and, therefore, improving the quality of the thermally treated product.
Mixed microbial culture used in this study was developed from sludge that was taken from local textile wastewater treatment tank. Acclimatization process was performed before starting the biodegradation experiment to obtain a microbial culture with high degradation properties. Kinetic studies by the mixed microbial culture were determined quantitatively for the model pollutant, Reactive Black 5 (RB 5). By using Michaelis-Menten model, the constants were found to be 11.15 mg l-1 h -1 and 29.18 mg l-1 for Vm and Km respectively. The values of kinetic constants for Monod model were found to be 33.11 mg l-1 cell h-1 for the maximum specific microbial growth rate, µm and 86.62 mg l-1 for Monod constant, Ks. The effects of process parameters such as pH, inoculum size and initial dye concentration on the biodegradation of azo dye, RB 5 were systematically investigated. Maximum removal efficiencies observed in this study were 75% for pH 6, 100% for 15% inoculum concentration and 75% for 20 ppm of initial dye concentration.
Lead-free solder paste printing processes account for the majority of assembly defects in the electronic manufacturing industry. In the stencil printing process, the solder paste must be able to withstand low and high shear rates which result in continuous structural breakdown and build-up. This study investigated the effect of the addition of nickel and platinum powders to the thixotropic behaviour of lead-free Sn/Ag/Cu solder pastes using the structural kinetic model. A hysteresis loop test and constant shear test were utilized to investigate the thixotropic behaviour of the pastes using parallel plate rheometry at 25ºC. In this study, the shear rates were increased from 0.01 s–1 to 10 s–1 and the second curve was a result of decreasing the shear rate from 10 s–1 to 0.01 s–1. For the constant shear test, the samples were subjected to five different shear rates of 0.01s–1, 0.1s–1, 1s–1, 10s–1 and 100s–1. The constant shear rate test was designed to study the structural breakdown and build-up of the paste materials. From this investigation, the hysteresis loop test was shown to be an effective test method to differentiate the extent of structural recovery in the solder pastes. All the pastes showed a high degree of shear thinning behaviour with time. This might be due to the agglomeration of particles in the flux that prohibited paste flow under low shear rate. The action of high shear rate would break the agglomerates into smaller pieces which facilitated the flow of pastes, thus viscosity was reduced at high shear rate.
Low methoxyl (LM) pectin was extracted from pomelo peels using subcritical water in a dynamic mode. The effects of pressure and temperature were analyzed through a face-centred central composite design. Extraction yield and the rate of extraction were found to be predominantly influenced by temperature. Optimization of the subcritical water extraction (SWE) yielded an optimized operating condition of 120°C and 30bar with a predicted pectin yield of 18.8%. The corresponding experimental yield was 19.6%, which is in close agreement with the predicted data. The pectin obtained from the optimized condition was further analyzed for its physicochemical properties. The kinetics of the SWE was also evaluated whereby the one-site kinetic desorption model was found to be in good agreement with experimental data (R2>0.94).