Bis (2-ethylhexyl)phosphoric acid (HDEHP) is a renowned extractant, favored for its affinity to selectively remove uranium via its P=O groups. We previously synthesized HDEHP-functionalized mesoporous silica microspheres for solid-phase uranium adsorption. Herein, we investigated the kinetic and isothermal behavior of uranyl ion adsorption in mesoporous silica microspheres functionalized with phosphate groups. Adsorption experiments were conducted by equilibrating 20 mg of silica samples with 50 mL of uranium solutions, with concentrations ranging from 10 to 100 mgU L−1 for isotherms and 100 mgU L−1 for kinetics. Three distinct samples were prepared with varying HDEHP to TEOS molar ratios (x = 0.16 and 0.24) and underwent hydrothermal treatment at different temperatures, resulting in distinct textural properties. Contact times spanned from 1 to 120 hours. For x = 0.16 samples, it took around 50 and 11 hours to reach equilibrium for the hydrothermally treated samples at 343 K and 373 K, respectively. Adsorbed quantities were similar (99 and 101 mg g-1, respectively), indicating consistent functional group content. This suggests that the key factor influencing uranium adsorption kinetics is pore size of the silica. The sample treated at 373 K, with a larger pore size (22.7 nm) compared to 343 K (11.5 nm), experienced less steric hindrance, allowing uranium species to diffuse more easily through the mesopores. The data confirmed the excellent fit of pseudo-second-order kinetic model (R2 > 0.999) and closely matched the experimental value, suggesting that chemisorption governs the rate-controlling step. To gain further insights into uranium adsorption behavior, we conducted an adsorption isotherm analysis at various initial concentrations under a constant pH of 4. Both the Langmuir and Freundlich isotherm models were applied, with the Langmuir model providing a superior fit. The relatively high R2 value indicated its effectiveness in describing the adsorption process, suggesting homogenous sorbate adsorption on an energetically uniform adsorbent surface via a monolayer adsorption and constant adsorption site density, without any interaction between adsorbates on adjacent sites. Remarkably, differences in surface area did not significantly impact uranium removal efficiency. This observation strongly suggests that the adsorption capacity is primarily governed by the loading amount of HDEHP and the inner-sphere complexation with the phosphoryl group (O=P). Our silica composite exhibited an impressive adsorption capacity of 133 mg g-1, surpassing the results reported in the majority of other silica literature.
This study presents the synthesis, characterization, and utilization of marine macroalgae-derived bio-carbon catalysts (BC and KOH-AC) for the efficient conversion of waste cooking oil (WCO) into biodiesel. The biochar (BC) was produced through slow pyrolysis of macroalgal biomass, which was subsequently activated with potassium hydroxide (KOH) to produce a KOH-modified activated carbon (KOH-AC) catalyst. Advanced characterization techniques, including SEM, EDX, XRD, FTIR, and TGA, were used to examine the physicochemical characteristics of the catalysts. The synthesized catalysts were utilized to produce biodiesel from WCO, and the results revealed that the highest biodiesel yields, 98.96%, and 47.54%, were obtained using KOH-AC and BC catalysts, respectively, under optimal reaction conditions of 66 °C temperature, 12.3 M/O molar ratio, 130 min time, and 3.08 wt.% catalyst loading via RSM optimization. The kinetic and thermodynamic parameters, such as k, Ea, ΔH, ΔS, and ΔG, were determined to be 0.0346 min− 1, 43.31 kJ mol− 1, 38.98 kJ mol− 1, − 158.38 J K− 1 mol− 1, and 92.58 kJ mol− 1, respectively. The KOH-AC catalyst was recycled up to five times, with a significant biodiesel yield of 80.37%. The fuel properties of the biodiesel met ASTM (D6751) specifications, ensuring that it has excellent fuel characteristics and can be used as an alternative fuel.
This study examined the influence of operating parameters on the electrosorptive recovery system of lithium ions from aqueous solutions using a spinel-type lithium manganese oxide adsorbent electrode and investigated the electrosorption kinetics and isotherms. The results revealed that the electrosorption data of lithium ions from the lithium containing aqueous solution were well-fitted to the Langmuir isotherm at electrical potentials lower than –0.4 V and to the Freundlich isotherm at electrical potentials higher than –0.4 V. This result may due to the formation of a thicker electrical double layer on the surface of the electrode at higher electrical potentials. The results showed that the electrosorption reached equilibrium within 200 min under an electrical potential of –1.0 V, and the pseudo-second-order kinetic model was correlated with the experimental data. Moreover, the adsorption of lithium ions was dependent on pH and temperature, and the results indicate that higher pH values and lower temperatures are more suitable for the electrosorptive adsorption of lithium ions from aqueous solutions. Thermodynamic results showed that the calculated activation energy of 22.61 kJ mol–1 during the electrosorption of lithium ions onto the adsorbent electrode was primarily controlled by a physical adsorption process. The recovery of adsorbed lithium ions from the adsorbent electrode reached the desorption equilibrium within 200 min under reverse electrical potential of 3.5 V.
Recently EC-MBR (Elctrocoagulation - Membrane Bio Reactor) has been suggested as one of alternative processes to overcome membrane fouling problems. Most important operational parameters in the EC-MBR are known to current density and contact time. Their effect on membrane filtration performances has been reported well, however, quantitative interrelationship between both parameters not been investigated yet. The purpose of this study is to give a kinetic model suggesting the current density and the contact time required to reduce the membrane fouling. The 4 different set of current densities (2.5, 6, 12 and 24 A/m2) and contact times (0, 2, 6 and 12 hr) were selected as operational parameters. After each electro-coagulation under the 16 different conditions, a series of membrane filtration was carried out. The membrane fouling decreased as the current density and contact time increased, Total fouling resistances under different conditions, Rt(=Rc+Rf) were calculated and compared to those of the controls (R0), which were calculated from the data of experiments without electro-coagulation. A kinetic approach for the fouling reduction rate (Rt / R0) was carried out and the equation ρi0.46t=7.0 was obtained, which means that the product of current density and the contact time needed to reduce the fouling in certain amounts (in this study, 10% of fouling reduction) is always constant.
Carboxylated multi-wall carbon nanotubes (MWCNTs-COOH) have been used as efficient adsorbents for the removal of picric acid from aqueous solutions under stirring and ultrasound conditions. Batch experiments were conducted to study the influence of the different parameters such as pH, amount of adsorbents, contact time and concentration of picric acid on the adsorption process. The kinetic data were fitted with pseudo-first order, pseudo-secondorder, Elovich and intra-particle diffusion models. The kinetic studies were well described by the pseudo-second-order kinetic model for both methods. In addition, the adsorption isotherms of picric acid from aqueous solutions on the MWCNTs were investigated using six two-parameter models (Langmuir, Freundlich, Tempkin, Halsey, Harkins-Jura, Fowler- Guggenheim), four three-parameter models (Redlich-Peterson, Khan, Radke-Prausnitz, and Toth), two four-parameter equations (Fritz-Schlunder and Baudu) and one five-parameter equation (Fritz-Schlunder). Three error analysis methods, correlation coefficient, chi-square test and average relative errors, were applied to determine the best fit isotherm. The error analysis showed that the models with more than two parameters better described the picric acid sorption data compared to the two-parameter models. In particular, the Baudu equation provided the best model for the picric acid sorption data for both methods.
주스의 품질악화를 초래하는 효소를 불활성화시키기 위해서 감귤 주스와 사과 주스 추출물에 초고압 처리와 열처리를 하여 각 시료의 PPO와 POD의 불활성화 정도를 확인하고 동역학 모델에 적용하여 이들의 불활성화 특성을 연구하였다. 감귤 주스와 사과 주스에서 모두 PPO가 POD보다 열과 압력에 대해서 상대적으로 내성을 갖는 것을 알 수 있었으며, 초고압 처리 과정을 거쳤을 때 보다는 열처리 과정을 거쳤을 때 PPO와 POD가 효과적으로 불활성화되는 것을 확인할 수 있었다. 초고압 기술은 처리 후에도 제품의 영양분과 색의 변화에 영향을 미치지 않기에, 최상의 상태와 품질로 제품을 제공 할 수 있는 장점을 가지고 있지만, 효소를 불활성시키기에는 부족하다는 단점을 가지고 있다. 이를 보완하여 산업적으로 이용되어지기 위해서는 영양분이 파괴되지 않는 열 처리 조건을 잡고, 효소를 효과적으로 불활성시킬 수 있는 초고압 처리 조건과 결합하여 최상의 결과를 얻을 수 있는 조건을 찾는 연구가 필요하다고 판단된다.
Bagasse fly ash (BFA) is one of the important wastes generated in the sugar industry; it has been studied as a prospective low-cost adsorbent in the removal of congo red (CR) from aqueous solutions. Chemical treatment with H2O2 was applied in order to modify the adsorbability of the raw BFA. Batch studies were performed to evaluate the influence of various experimental parameters such as dye solution pH, contact time, adsorbent dose, and temperature. Both the adsorbents were characterized by Fourier-transform infrared spectrometer, energy-dispersive X-ray spectrophotometer and nitrogen adsorption at 77 K. Equilibrium isotherms for the adsorption of CR were analyzed by Langmuir, Freundlich and Temkin models using non-linear regression technique. Intraparticle diffusion seems to control the CR removal process. The obtained experimental data can be well described by Langmuir and also followed second order kinetic models. The calculated thermodynamic parameters indicate the feasibility of the adsorption process for the studied adsorbents. The results indicate that BFA can be efficiently used for the treatment of waste water containing dyes.
Kinetic studies on the ligand substitution reactions of cyanocomplexes were performed in several micellar solutions. It showed the observed rate constants was found to be independent of the entering ligand concentration at high concentration of cyanopyridine and pyrazinecarboxylate. We could see also that in nonionic and anionic micellar solutions no influence of changes in the surfactant concentration on the observed rate constants was found. Taking into account the hydrophilic nature of the cobalt complex, the cobalt complex molecule was expected to be located in the aqueous phase of the micellar systems, where the reaction would take place. In cationic micellar solutions, a small increase in the observed rate constant was found when the cationic surfactant concentration increased. After reaching a maximum, the rate constant decreased on increasing surfactant concentration and subsequently it reached a plateau, where the observed rate constant was independent of changes in the surfactant concentration.
The adsorption of phenolic compound resorcinol on activated carbons prepared from Moringa oleifera (Drumstick bark) has been investigated. Activated carbon was prepared by impregnating Moringa oleifera with 50% phosphoric acid in the ratio of 1:1 and 1:2(w/w), designated as MOAC1 and MOAC2. Equilibrium and isotherm studies were carried out. The influences of variables such as contact time, initial concentration of resorcinol, carbon dosage in the solution on percentage adsorption and adsorption capacity of the bark have been analysed. The equilibration time was found to be 4 h. Kinetics of resorcinol onto activated carbons was checked for pseudo first order and pseudo second order model. It was found that the adsorption of resorcinol follows pseudo second order kinetics for both MOAC1 and MOAC2. The isotherm data were correlated with isotherm models, namely Langmuir and Freundlich. Adsorption isotherms were satisfactorily fitted by both the Langmuir and Freundlich model for MOAC1 and MOAC2.
Granular Activated Carbon (GAC) has been proven to be an excellent material for many industrial applications. A systematic study has been carried out of the kinetics of physical as well as chemical activation of phenolic resin chars. Physical activation was carried out using CO2 and chemical activation using KOH as activating agent. There are number of factors which influence the rate of activation. The activation temperature and residence time at HTT varied in the range 550~1000℃ and ½~8 hrs respectively. Kinetic studies show that the rate of chemical activation is 10 times faster than physical activation even at much lower temperature. Above study show that the chemical activation process is suitable to prepare granular activated carbon with very high surface area i.e. 2895 m2/g in short duration of time i.e. 1 to 2 hrs at lower temperature i.e. 750℃ from phenolic resins.
Biomass as a renewable energy source has several limitations in terms of the potential for steady supply and its thermal characteristics. This study conducted a thermal weight change analysis and determined its kinetics to address this problem. Sawdust was chosen as the biomass, and PE and PP were the plastics used. Based on the result of thermogravimetric analysis (TGA), the kinetic characteristics were analyzed using Kissinger, Ozawa, and Friedman methods, which are the most common methods used to obtain reaction coefficients and activation energy. The methods used to determine the thermal degradation kinetics were considered feasible for evaluating the pyrolytic behavior of the materials tested. The experimental results of this study provided insights into mixed biomass/plastics pyrolysis kinetics and their optimal operation conditions.