Journal of Korean Society of Environmental Engineers
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v.35
no.10
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pp.710-716
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2013
New and renewable energy sources have drawn attention because of climate change. Many studies have been carried out in waste-to-energy field. Fast pyrolysis of waste lignocelluosic biomass is one of the waste-to-energy technologies. Bubbling fluidized bed (BFB) reactor is widely used for fast pyrolysis of the biomass. In BFB pyrolyzer, bubble behavior influences on the chemical reaction. Accordingly, in the present study, hydrodynamic characteristics and fast pyrolysis reaction of waste lignocellulosic biomass occurring in a BFB pyrolyzer are scrutinized. The computational fluid dynamics (CFD) simulation of the fast pyrolysis reactor is carried out by using Eulerian-Granular approach. And two-stage semi-global kinetics is applied for modeling the fast pyrolysis reaction of waste lignocellulosic biomass. To summarize, generation and ascendant motion of bubbles in the bed affect particle behavior. Thus biomass particles are well mixed with hot sand and consequent rapid heat transfer occurs from sand to biomass particles. As a result, primary reaction is observed throughout the bed. And reaction rate of tar formation is the highest. Consequently, tar accounts for 66wt.% of the product gas. However, secondary reaction occurs mostly in the freeboard. Therefore, it is considered that bubble behavior and particle motions hardly influences on the secondary reaction.
Background: The continuing growth of the ethanol industry has generated large amounts of various distillers grains co-products. These are characterized by a wide variation in chemical composition and ruminal degradability. Therefore, their precise formulation in the ruminant diet requires the systematic evaluation of their degradation profiles in the rumen. Methods: Three distillers grains plus soluble co-products (DDGS) namely, corn DDGS, high-protein corn DDGS (HP-DDGS), and wheat DDGS, were subjected to an in situ trial to determine the degradation kinetics of the dry matter (DM) and crude protein (CP). Soybean meal (SBM), a feed with highly degradable protein in the rumen, was included as the fourth feed. The four feeds were incubated in duplicate at each time point in the rumen of three ruminally cannulated Hanwoo cattle for 1, 2, 4, 6, 8, 12, 24, and 48 h. Results: Wheat DDGS had the highest filterable and soluble A fraction of its DM (37.2 %), but the lowest degradable B (49.5 %; P < 0.001) and an undegradable C fraction (13.3 %; P < 0.001). The filterable and soluble A fraction of CP was greatest with wheat DDGS, intermediate with corn DDGS, and lowest with HP-DDGS and SBM; however, the undegradable C fraction of CP was the greatest with HP-DDGS (41.2 %), intermediate with corn DDGS (2.7 %), and lowest with wheat DDGS and SMB (average 4.3 %). The degradation rate of degradable B fraction ($%\;h^{-1}$) was ranked from highest to lowest as follows for 1) DM: SBM (13.3), wheat DDGS (9.1), and corn DDGS and HP-DDGS (average 5.2); 2) CP: SBM (17.6), wheat DDGS (11.6), and corn DDGS and HP-DDGS (average 4.4). The in situ effective degradability of CP, assuming a passage rate of $0.06h^{-1}$, was the highest (P < 0.001) for SBM (73.9 %) and wheat DDGS (71.2 %), intermediate for corn DDGS (42.5 %), and the lowest for HP-DDGS (28.6 %), which suggests that corn DDGS and HP-DDGS are a good source of undegraded intake protein for ruminants. Conclusions: This study provided a comparative estimate of ruminal DM and CP degradation characteristics for three DDGS co-products and SBM, which might be useful for their inclusion in the diet according to the ruminally undegraded to degraded intake protein ratio.
Adsorption characteristics of reactive red 120 (RR 120) dye by a coal-based granular activated carbon (CGAC) from an aqueous solution were investigated using the amount of activated carbon, pH, initial concentration, contact time and temperature as adsorption variables. Isotherm equilibrium relationship showed that Langmuir's equation fits better than that of Freundlich's equation. The adsorption mechanism was considered to be superior to the adsorption of monolayer with uniform energy distribution. From the evaluated Langmuir separation coefficients (RL = 0.181~0.644), it was found that this adsorption process belongs to an effective treatment area (RL = 0~1). The adsorption energy determined by Temkin's equation and Dubinin-Radushkevich's equation was E = 15.31~7.12 J/mol and B = 0.223~0.365 kJ/mol, respectively. The adsorption process showed the physical adsorption (E < 20 J/mol and B < 8 kJ/mol). The adsorption kinetics followed the pseudo first order model. The adsorption reaction of RR 120 dye on CGAC was found to increase spontaneously with increasing the temperature because the free energy change decreased with increasing the temperature. The enthalpy change (12.747 kJ/mol) indicated an endothermic reaction. The isosteric heat of adsorption (△Hx = 9.78~24.21 kJ/mol) for the adsorption reaction of RR 120 by CGAC was revealed to be the physical adsorption (△Hx < 80 kJ/mol).
Kim, Byung-Su;Park, Jin-Tae;Kim, Dong-Sik;Yoo, Jae-Min;Lee, Jae-Chun
Resources Recycling
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v.15
no.4
s.72
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pp.44-51
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2006
Most electric arc furnace dust (EAFD) treatment processes to recover zinc from EAFD employ carbon as a reducing agent for the zinc oxide in the EAFD. In the present work, the reduction reaction of zinc oxide with carbon in the present of iron oxide was kinetically studied. The experiments were carried out at temperatures between 1173 K and 1373 K under nitrogen atmosphere using a weight-loss technique. From the experimental results, it was concluded that adding the proper amount of iron oxide to the reactant accelerates the reaction rate of zinc oxide with carbon. This is because iron oxide in the reduction reaction of zinc oxide with carbon promotes the carbon gasification reaction. The spherical shrinking core model for a surface chemical reaction control was found to be useful in describing kinetics of the reaction over the entire temperature range. The reaction has an activation energy of 53 kcal/mol (224 kJ/mol) for ZnO-C reaction system, an activation energy of 42 kcal/mol (175 kJ/mol) for $ZnO-Fe_{2}O_{3}-C$ reaction system, and an activation energy of 44 kcal/mol (184 kJ/mol) for ZnO-mill scale-C reaction system.
Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
/
v.17
no.2
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pp.127-137
/
2019
Zr electrorefining is demonstrated herein using Zirlo tubes in a chloride-fluoride mixed molten salt in the presence of $AlF_3$. Cyclic voltammetry reveals a monotonic shift in the onset of metal reduction kinetics towards positive potential and an increase in intensity of the additional peaks associated with Zr-Al alloy formation with increasing $AlF_3$ concentration. Unlike the galvanostatic deposition mode, a radial plate-type Zr growth is evident at the top surface of the salt during Zr electrorefining at a constant potential of -1.2 V. The diameter of the plate-type Zr deposit gradually increases with increasing $AlF_3$ concentration. Scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDX) and X-ray photoelectron spectroscopy (XPS) analyses for the plate-type Zr deposit show that trace amount of Al is incorporated as Zr-Al alloys with different chemical compositions between the top and bottom surface of the deposit. Addition of $AlF_3$ is effective in lowering the residual salt content in the deposit and in improving the current efficiency for Zr recovery.
The adsorption of disperse yellow 3 (DY 3) on granular activated carbon (GAC) was investigated for isothermal adsorption and kinetic and thermodynamic parameters by experimenting with initial concentration, contact time, temperature, and pH of the dye as adsorption parameters. In the pH change experiment, the adsorption percent of DY 3 on activated carbon was highest in the acidic region, pH 3 due to electrostatic attraction between the surface of the activated carbon with positive charge and the anion (OH-) of DY 3. The adsorption equilibrium data of DY 3 fit the Langmuir isothermal adsorption equation best, and it was found that activated carbon can effectively remove DY 3 from the calculated separation factor (RL). The heat of adsorption-related constant (B) from the Temkin equation did not exceed 20 J mol-1, indicating that it is a physical adsorption process. The pseudo second order kinetic model fits well within 10.72% of the error percent in the kinetic experiments. The plots for Weber and Morris intraparticle diffusion model were divided into two straight lines. The intraparticle diffusion rate was slow because the slope of the stage 2 (intraparticle diffusion) was smaller than that of stage 1 (boundary layer diffusion). Therefore, it was confirmed that the intraparticle diffusion was rate controlling step. The free energy change of the DY 3 adsorption by activated carbon showed negative values at 298 ~ 318 K. As the temperature increased, the spontaneity increased. The enthalpy change of the adsorption reaction of DY 3 by activated carbon was 0.65 kJ mol-1, which was an endothermic reaction, and the entropy change was 2.14 J mol-1 K-1.
Adsorption characteristics of carbol fuchsin (CF) dye by coal-based activated carbon (CAC) were investigated using pH, initial concentration, temperature and contact time as adsorption variables. CF dissociates in water to have a cation, NH2+, which is bonded to the negatively charged surface of the activated carbon in the basic region by electrostatic attraction. Under the optimum condition of pH 11, 96.6% of the initial concentration was adsorbed. Isothermal adsorption behavior was analyzed using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models. Langmuir's equation was the best fit for the experimental results. Therefore, the adsorption mechanism was expected to be adsorbed as a monolayer on the surface of activated carbon with a uniform energy distribution. From the evaluated Langmuir's dimensionless separation coefficients (RL = 0.503~0.672), it was found that CF can be effectively treated by activated carbon. The adsorption energies determined by Temkin and Dubinin-Radushkevich models were E = 15.31~7.12 J/mol and B = 0.223~0.365 kJ/mol, respectively. Therefore, the adsorption process was physical (E < 20 J/mol, B < 8 kJ/mol). The experimental result of adsorption kinetics fit better the pseudo second order model. In the adsorption reaction of CF dye to CAC, the negative free energy change increased as the temperature increased. It was found that the spontaneity also increased with increasing temperature. The positive enthalpy change (40.09 kJ/mol) indicated an endothermic reaction.
In this paper, parameter characteristics such as pH effect, isotherm, kinetic and thermodynamic parameters and competitive adsorption of dyes including malachite green (MG), direct red 81 (DR 81) and thioflavin S (TS), which have different functional groups, being adsorbed onto activated carbon were investigated. Langmuir, Freundlich and Temkin isotherm models were employed to find the adsorption mechanism. Effectiveness of adsorption treatment of three dyes by activated carbon were confirmed by the Langmuir dimensionless separation factor. The mechanism was found to be a physical adsorption which can be verified through the adsorption heat calculated by Temkin equation. The adsorption kinetics followed the pseudo second order and the rate limiting step was intra-particle diffusion. The positive enthalpy and entropy changes showed an endothermic reaction and increased disorder via adsorption at the S-L interface, respectively. For each dye molecule, negative Gibbs free energy increased with the temperature, which means that the process is spontaneous. In the binary component system, it was found that the same functional groups of the dye could interfere with the mutual adsorption, and different functional groups did not significantly affect the adsorption. In the ternary component system, the adsorption for MG lowered a bit, likely to be disturbed by the other dyes meanwhile DR 81 and TS were to be positively affected by the presence of MG, thus resulting in much higher adsorption.
Reductive reactivity of zero-valent iron nanoparticles was investigated for removal of nitrate-nitrogen which is considered one of the major water pollutants. To elucidate the difference in reactivity between preparation methods, iron nanoparticles were synthesized respectively from microemulsion and aqueous solution of ferric ions. Iron nanoparticles prepared from microemulsion were deposited on aluminum by electrophoretic method, and their reaction kinetics was compared to that of the same nanoparticles suspended in aqueous batch reaction. With an approximation of pseudo-first-order reaction, rate constants for suspended nanoparticles prepared from microemulsion and dilute aqueous solution were $3.49{\times}10^{-2}min^{-1}$ and $1.40{\times}10^{-2}min^{-1}$, respectively. Iron nanoparticles supported on aluminum showed ca. 30% less reaction rate in comparison with the identical nanoparticles in suspended state. However, supported nanoparticles showed the superior effectiveness in terms of nitrate-nitrogen removal per zero-valent iron input especially when excess amounts of nitrates were present. Iron nanoparticles deposited on aluminum maintained reductive reactivity for more than 3 hours, and produced nitrogen gas as a final reduction product of nitrate-nitrogen.
New technologies will have a large impact on the discovery of new herbicide site of action. Genomics, combinatorial chemistry, and bioinformatics help take advantage of serendipity through tile sequencing of huge numbers of genes or the synthesis of large numbers of chemical compounds. There are approximately $10^{30}\;to\;10^{50}$ possible molecules in molecular space of which only a fraction have been synthesized. Combining this potential with having access to 50,000 plant genes in the future elevates tile probability of discovering flew herbicidal site of actions. If 0.1, 1.0 or 10% of total genes in a typical plant are valid for herbicide target, a plant with 50,000 genes would provide about 50, 500, and 5,000 targets, respectively. However, only 11 herbicide targets have been identified and commercialized. The successful design of novel herbicides depends on careful consideration of a number of factors including target enzyme selections and validations, inhibitor designs, and the metabolic fates. Biochemical information can be used to identify enzymes which produce lethal phenotypes. The identification of a lethal target site is an important step to this approach. An examination of the characteristics of known targets provides of crucial insight as to the definition of a lethal target. Recently, antisense RNA suppression of an enzyme translation has been used to determine the genes required for toxicity and offers a strategy for identifying lethal target sites. After the identification of a lethal target, detailed knowledge such as the enzyme kinetics and the protein structure may be used to design potent inhibitors. Various types of inhibitors may be designed for a given enzyme. Strategies for the selection of new enzyme targets giving the desired physiological response upon partial inhibition include identification of chemical leads, lethal mutants and the use of antisense technology. Enzyme inhibitors having agrochemical utility can be categorized into six major groups: ground-state analogues, group specific reagents, affinity labels, suicide substrates, reaction intermediate analogues, and extraneous site inhibitors. In this review, examples of each category, and their advantages and disadvantages, will be discussed. The target identification and construction of a potent inhibitor, in itself, may not lead to develop an effective herbicide. The desired in vivo activity, uptake and translocation, and metabolism of the inhibitor should be studied in detail to assess the full potential of the target. Strategies for delivery of the compound to the target enzyme and avoidance of premature detoxification may include a proherbicidal approach, especially when inhibitors are highly charged or when selective detoxification or activation can be exploited. Utilization of differences in detoxification or activation between weeds and crops may lead to enhance selectivity. Without a full appreciation of each of these facets of herbicide design, the chances for success with the target or enzyme-driven approach are reduced.
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