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Comparison Between Sorption and Sono-Sorption Efficiencies, Equilibriums and Kinetics in the Uptake of Direct Red 23 from the Aqueous Solutions
2016
Oguz, Ensar | Bire, Murat | Nuhoglu, Yasar
Using ZnO nanoparticles, comparisons between sorption and sono-sorption efficiencies, equilibrium and kinetics in Direct Red 23 have been researched under the various experimental conditions. Pseudo-second-order model was practiced for the experimental data. The mechanism of the dye uptake was clarified based on the analyses of X-ray diffraction (XRD) and scanning electron microscopy (SEM). Brunauer-Emmett-Teller (BET) surface area and total pore volume of the nanoparticles were obtained. The highest Direct Red 23 (DR23) removal efficiencies by sorption and sono-sorption processes were determined as 78.6 and 96.8 %, respectively. Experimental data have been evaluated according to Langmuir, Freundlich and Dubinin-Radushkevich. The mean energies of sorption and sono-sorption processes were calculated to be 16.22 and 25.41 kJ/mol, respectively. Arrhenius equation was used to calculate the activation energies. ΔH° and ΔG° values indicated that sorption and sono-sorption processes were endothermic processes. But, negative free energy values of ΔG° indicated that sorption and sono-sorption processes were favoured at high temperatures.
Mostrar más [+] Menos [-]Energetic and Entropic Features of Cu(II) Sorption Equilibria on Fibrous Clay Minerals
2016
Khosravi, Parisa | Shirvani, Mehran | Bakhtiary, Somayeh | Shariatmadari, Hossein
Sorption equilibria of copper(II) ions onto palygorskite and sepiolite clay minerals were studied as a function of temperature. The experimental data were fitted to the Langmuir, Freundlich, Temkin, and R-D models to obtain the isothermal constants. van’t Hoff, Gibbs, Clausius–Clapeyron, and modified Arrhenius equations were also employed to evaluate the thermodynamic parameters involved in Cu sorption. The results showed that fibrous clay minerals exhibit enhanced Cu(II) sorption capacities at higher temperatures. Enthalpy changes (ΔH°) were found to be positive, confirming that the process of Cu(II) sorption on both palygorskite and sepiolite was endothermic. Positive values were also obtained for the entropy changes (ΔS°), which suggests increased randomness at the solid-solution interface during the sorption of Cu(II) ions on both fibrous clay minerals investigated. The free energy changes (ΔG°) were negative for all the different temperatures and initial Cu(II) concentrations tested, indicating that sorption on the minerals is spontaneous and favorable. It was, therefore, concluded that sorption of Cu(II) ions on fibrous clay minerals is entropically driven. The values of isosteric heat of sorption (∆H ₓ) decreased with increasing sorption density, which shows that the clay surface is heterogeneous in terms of the active sites available for Cu(II) retention. The values of activation energy (E ₐ) and sticking probability (S *) generally lied within the ranges associated with physisorption for palygorskite and chemisorptions for sepiolite. In conclusion, the thermodynamic parameters investigated revealed the higher tendency and capacity of sepiolite, compared to palygorskite, for the feasible, spontaneous, and endothermic retention of Cu(II). However, the intensity of Cu(II) interactions with the fibrous clay minerals was found to depend to a large extent on the temperature and the initial Cu loading of the systems.
Mostrar más [+] Menos [-]Projection Pursuit-Based Microcystis Bloom Warning in a Riverside Lake
2016
Wang, Hua | Zhizhang, Zhang | Zhao, Yijun | Dongfang, Liang
A high-dimensional driving function for Microcystis bloom warning was developed, in which both the inhibition and promotion impacts on Microcystis growth activation energy are integrally considered. Five factors, including flow disturbance, temperature, light intensity, nutrient concentration, and biological inhibition, are embedded in the equation, which results in a high-dimensional problem. The projection pursuit principle was applied for dimension reduction to resolve the numerical problem, and an integrated hydro-environmental model was established. Jinshan Lake, a typical riverside lake, was selected as the research area, and six bloom grades were determined for warning analysis. Based on the established model, the processes of Microcystis growth under varied hydrodynamic conditions were simulated. It was found that the established warning model could well reveal the Microcystis bloom processes in Jinshan Lake. The low-water year was characterized by the largest number of days on which Microcystis bloom might occur for its poor water exchange frequency; The areas where Microcystis bloom might occur in the flood seasons of high-water year, common-water year, and low-water year varied with the uneven-distributed dynamic conditions, which were respectively 0.15, 0.91, and 1.26 km².
Mostrar más [+] Menos [-]A soil-column gas chromatography (SCGC) approach to explore the thermal desorption behavior of hydrocarbons from soils
2016
Yu, Ying | Liu, Liang | Shao, Ziying | Ju, Tianyu | Sun, Bing | Benadda, Belkacem
A soil-column gas chromatography approach was developed to simulate the mass transfer process of hydrocarbons between gas and soil during thermally enhanced soil vapor extraction (T-SVE). Four kinds of hydrocarbons—methylbenzene, n-hexane, n-decane, and n-tetradecane—were flowed by nitrogen gas. The retention factor k’ and the tailing factor T f were calculated to reflect the desorption velocities of fast and slow desorption fractions, respectively. The results clearly indicated two different mechanisms on the thermal desorption behaviors of fast and slow desorption fractions. The desorption velocity of fast desorption fraction was an exponential function of the reciprocal of soil absolute temperature and inversely correlated with hydrocarbon’s boiling point, whereas the desorption velocity of slow desorption fraction was an inverse proportional function of soil absolute temperature, and inversely proportional to the log K OW value of the hydrocarbons. The higher activation energy of adsorption was found on loamy soil with higher organic content. The increase of carrier gas flow rate led to a reduction in the apparent activation energy of adsorption of slow desorption fraction, and thus desorption efficiency was significantly enhanced. The obtained results are of practical interest for the design of high-efficiency T-SVE system and may be used to predict the remediation time.
Mostrar más [+] Menos [-]Kinetic modeling and determination role of sono/photo nanocatalyst-generated radical species on degradation of hydroquinone in aqueous solution
2016
Rahimi, Sajad | Ayati, Bita | Rezaee, Abbas
Experimental findings of sonophotocatalytic process were used in degradation of hydroquinone to assess kinetic modeling and determine the effect of various active radical species. First, the effects of three photocatalytic, sonocatalytic, and sonophotocatalytic processes were studied for hydroquinone removal to determine kinetic constants and calculate the activation energy of reactions, and then the selected process was evaluated to determine active radical species. The reactor was composed of two parts, one included ultrasonic probe (sonocatalytic part) with powers 22, 80, and 176 W and the second part was the location of UV lamp (photocatalytic part) with tubular flow and power 15 W. After three systems were examined and the efficient system was selected, the role of different active species such as hydroxyl radical (OH·), superoxide radical (O₂ ·⁻), hole (h⁺), electrons (e ⁻), and single oxygen molecule (¹O₂) and contribution of each of them were determined in hydroquinone degradation. According to tests, the results of this study showed that sonophotocatalytic integrated method as selected system among three systems studied followed the first-order equation for hydroquinone degradation and active hydroxyl species with 45 % and electron and hole with 15 and 10 %, respectively, had the highest and lowest contributions to conversion of hydroquinone. The findings showed that dissolved oxygen increases the capability of active radical formation so that 28.2 % of hydroquinone removal was increased under aeration compared to without aeration. Also, removal efficiency decreased 62 % with N₂ injection due to the withdrawal of oxygen from the sample. By adding 25 Mm of sodium azide (NaN₃) to stock solution, 46.5 % reduction was developed because single oxygen (¹O₂) played the role of an active species. The advantages of integrated sonocatalytic and photocatalytic method are the generation of active radical species with more variety and ultimately the formation of higher amounts of powerful hydroxyl radical that increases degradation rates of refractory compounds and low-risk internal and final products. It has an appropriate performance in the degradation of refractory compounds by optimizing effective operational factors.
Mostrar más [+] Menos [-]Activated carbon fiber for heterogeneous activation of persulfate: implication for the decolorization of azo dye
2016
Chen, Jiabin | Hong, Wei | Huang, Tianyin | Zhang, Liming | Li, Wenwei | Wang, Ying
Activated carbon fiber (ACF) was used as a green catalyst to activate persulfate (PS) for oxidative decolorization of azo dye. ACF demonstrated a higher activity than activated carbon (AC) to activate PS to decolorize Orange G (OG). The decolorization efficiency of OG increased as ACF loading, PS dosage, and temperature increased. OG decolorization followed a pseudo first-order kinetics, and the activation energy was 40.902 kJ/mol. pH had no apparent effect on OG decolorization. Radical quenching experiments with various radical scavengers (e.g., alcohols, phenol) showed that radical-induced decolorization of OG took place on the surface of ACF, and both SO₄ ·⁻ and HO· were responsible for OG decolorization. The impact of inorganic salts was also evaluated because they are important compositions of dye wastewater. Cl⁻ and SO₄ ²⁻ exhibited a promoting effect on OG decolorization, and the accelerating rate increased with elevating dosage of ions. Addition of Cl⁻ and SO₄ ²⁻ could increase the adsorption of OG on ACF surface, thus favorable for OG decolorization caused by the surface-bound SO₄ ·⁻ and HO·. Conversely, HCO₃ ⁻ and humic acid (HA) slightly inhibited OG decolorization. The azo band and naphthalene ring on OG were remarkably destructed to other intermediates and finally mineralized to CO₂ and H₂O.
Mostrar más [+] Menos [-]Thermodynamic analysis of fatty acid harvesting by novel carbon-based adsorbent
2016
Do, Quoc Cuong | Kang, Seoktae
In this study, separation and concentration of fatty acids (FA) from the synthetic food processing wastewater containing low concentration of FA (250 mg/L) were investigated using expanded graphite (EG) as a novel adsorbent at different temperatures (298~318 K). The adsorption results were further analyzed to verify adsorption mechanisms and thermodynamics of FA onto EG. Results show that the adsorption of FA onto EG was explained well by the Langmuir model with the maximum adsorption capacity up to 8.01 g FA/g EG at 298 K, and considerably affected by temperature. The adsorption kinetics fitted with pseudo-second-order kinetic model and the adsorption mechanism analysis showed that the intraparticle diffusion was not the rate-limiting step, but the coalescence of FA droplets played the significant role for novel adsorption of FA onto EG. The calculated activation energy and thermodynamic parameters such as Gibbs free energy change (ΔG⁰), enthalpy change (ΔH⁰), and entropy change (ΔS⁰) indicated that the adsorption of FA onto EG was very feasible, was highly spontaneous, occurred physically, was exothermic in nature, and was stable in aquatic environmental changes. Overall, FA can be effectively harvested and concentrated from the food processing wastewater by EG even at low concentration.
Mostrar más [+] Menos [-]USPIO assisting degradation of MXC by host/guest-type immobilized laccase in AOT reverse micelle system
2016
Yang, Yu-Xiang | Bi, Na | Zhang, Jian-Bo | Huang, Yan | Yao, Ping-Ping | Xi, Yan-Jie | Yuan, Hong-Ming
The laccase and ultrasmall superparamagnetic iron oxide nanoparticles (USPIO) have been assembled inside the tubular mesoporous silica via co-adsorption technology to prepare host/guest-type immobilized laccase, which is applied to degrade methoxychlor (MXC) in aqueous and reverse micelle environments. The effects of various parameters on degradation of MXC were studied. Under the optimum conditions, the degradation rate could reach maximum value of 45.6 % and remain at 20.8 % after seven cycles. Moreover, the addition of small molecular compound 2, 2′-azinobis-(3-ethylbenzthiazoline-6-sulphonate) to the system could greatly improve the degradation efficiency. The MXC degradation process is a first-order reaction, and the activation energy of MXC degradation catalyzed by immobilized laccase (41.46 kJ mol⁻¹) is relatively lower than that catalyzed by free laccase (44.91 kJ mol⁻¹). Based on the degradation products measured by gas chromatograph-mass spectrometer (GC-MS) and nuclear magnetic resonance (NMR), the degradation mechanism of MXC has also been proposed.
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