• Title/Summary/Keyword: Kinetics model

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Studies on decomposition behavior of oxalic acid waste by UVC photo-Fenton advanced oxidation process

  • Kim, Jin-Hee;Lee, Hyun-Kyu;Park, Yoon-Ji;Lee, Sae-Binna;Choi, Sang-June;Oh, Wonzin;Kim, Hak-Soo;Kim, Cho-Rong;Kim, Ki-Chul;Seo, Bum-Chul
    • Nuclear Engineering and Technology
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    • v.51 no.8
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    • pp.1957-1963
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    • 2019
  • A UVC photo-Fenton advanced oxidation process (AOP) was studied to develop a process for the decomposition of oxalic acid waste generated in the chemical decontamination of nuclear power plants. The oxalate decomposition behavior was investigated by using a UVC photo-Fenton reactor system with a recirculation tank. The effects of the three operational variables-UVC irradiation, H2O2 and Fenton reagent-on the oxalate decomposition behavior were experimentally studied, and the behavior of the decomposition product, CO2, was observed. UVC irradiation of oxalate resulted in vigorous CO2 bubbling, and the irradiation dose was thought to be a rate-determining variable. Based on the above results, the oxalate decomposition kinetics were investigated from the viewpoint of radical formation, propagation, and termination reactions. The proposed UVC irradiation density model, expressed by the first-order reaction of oxalate with the same amount of H2O2 consumption, satisfactorily predicted the oxalate decomposition behavior, irrespective of the circulate rate in the reactor system within the experimental range.

Effect of current density and contact time on membrane fouling in electrocoagulation-MBR and their kinetic studies on fouling reduction rate (전기응집-MBR 공정의 전류밀도와 접촉시간이 막 오염에 미치는 영향과 막 오염 저감 속도론적 고찰)

  • Um, Se-Eun;Chang, In-Soung
    • Journal of Korean Society of Water and Wastewater
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    • v.31 no.4
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    • pp.321-328
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    • 2017
  • 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 $24A/m^2$) 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, $R_t(=R_c+R_f)$ were calculated and compared to those of the controls ($R_0$), which were calculated from the data of experiments without electro-coagulation. A kinetic approach for the fouling reduction rate ($R_t/R_0$) was carried out and the equation ${\rho}^{0.46}_it=7.0$ 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.

A Kinetic Study of Allylchloride Epoxidation using Titanium Silicalite-1 Catalyst (Titanium Silicalite-1 촉매를 이용한 Allylchloride 에폭시화 반응: 속도론적 고찰)

  • Yang, Seung-Tae;Choi, Jung-Sik;Kwon, Young-Chul;Lee, Sang-Wook;Ahn, Wha-Seung
    • Korean Chemical Engineering Research
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    • v.46 no.1
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    • pp.142-146
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    • 2008
  • Titanium silicalite-1 catalyst was prepared using a $SiO_2-TiO_2$ xerogel and applied to allylchloride (ALC) epoxidation by $H_2O_2$ as oxidant in a batch reactor. The reaction temperature was varied from 25 to $55^{\circ}C$, and the concentrations of ALC and $H_2O_2$ were changed from 0.2 to 3 M and from 0.2 to 1.5 M, respectively. The kinetic data obtained were applied to the power rate law, Eley-Rideal, and a Langmuir-Hinshelwood model, and power rate law fits the experimental data best. Activation energy was 27.9 kJ/mol, and the reaction orders with respect to $H_2O_2$ and ALC were determined to be 0.41 and 0.52, respectively.

Kinetic study for the optimization of ginsenoside Rg3 production by heat treatment of ginsenoside Rb1

  • Vo, Hoang Tung;Cho, Jae Youl;Choi, Yong-Eui;Choi, Yong-Soon;Jeong, Yeon-Ho
    • Journal of Ginseng Research
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    • v.39 no.4
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    • pp.304-313
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    • 2015
  • Background: Ginsenoside Rg3 is a promising anticancer agent. It is usually produced by heat treatment of ginseng, in which ginsenoside Rb1 is the major ginsenoside. A kinetic study was conducted to optimize ginsenoside Rg3 production by the heat treatment of ginsenoside Rb1. Methods: Ginsenoside Rb1 was heated using an isothermal machine at $80^{\circ}C$ and $100^{\circ}C$ and analyzed using HPLC. The kinetic parameters were calculated from the experimental results. The activation energy was estimated and used to simulate the process. The optimized parameters of ginsenoside Rg3 production are suggested based on the simulation. Results: The rate constants were $0.013h^{-1}$ and $0.073h^{-1}$ for the degradation of ginsenosides Rb1 and Rg3 at $80^{\circ}C$, respectively. The corresponding rate constants at $100^{\circ}C$ were $0.045h^{-1}$ and $0.155h^{-1}$. The estimated activation energies of degradation of ginsenosides Rb1 and Rg3 were 69.2 kJ/mol and 40.9 kJ/mol, respectively. The rate constants at different temperatures were evaluated using the estimated activation energies, and the kinetic profiles of ginsenosides Rb1 and Rg3 at each temperature were simulated based on the proposed kinetic model of consecutive reaction. The optimum strategies for producing ginsenoside Rg3 from ginsenoside Rb1 are suggested based on the simulation. With increased temperature, a high concentration of ginsenoside Rg3 is formed rapidly. However, the concentration decreases quickly after the reaching the maximal concentration value. Conclusion: The optimum temperature for producing ginsenoside Rg3 should be the highest temperature technically feasible below $180^{\circ}C$, in consideration of the cooling time. The optimum reaction time for heat treatment is 30 min.

An Extraction of Detailed Isoconversional Kinetic Scheme of Energetic Materials using Isothermal DSC (등전환법과 등온 DSC를 이용한 고에너지 물질의 정밀 반응모델 개발)

  • Kim, Yoocheon;Park, Jungsu;Kwon, Kuktae;Yoh, Jai-ick
    • Journal of the Korean Society of Propulsion Engineers
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    • v.20 no.2
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    • pp.46-55
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    • 2016
  • The kinetic analysis of a heavily aluminized cyclotrimethylene-trinitramine(RDX) is conducted using differential scanning calorimetry(DSC), and the Friedman isoconversional method is applied to the DSC experimental data. The pre-exponential factor and activation energy are extracted as a function of the product mass fraction. The extracted kinetic scheme does not assume multiple chemical steps to describe the complex response of energetic materials; instead, a set of multiple Arrhenius factors is constructed based on the local progress of the exothermic reaction. The resulting reaction kinetic scheme is applied to two thermal decomposition tests for validating the reactive flow response of a heavily aluminized RDX. The results support applicability of the present model to practical thermal explosion systems.

On the Use of Standing Oblique Detonation Waves in a Shcramjet Combustor

  • Fusina, Giovanni;Sislian, Jean P.;Schwientek, Alexander O.;Parent, Bernard
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 2004.03a
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    • pp.671-686
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    • 2004
  • The shock-induced combustion ramjet (shcramjet) is a hypersonic airbreathing propulsion concept which over-comes the drawbacks of the long, massive combustors present in the scramjet by using a standing oblique detonation wave (a coupled shock-combustion front) as a means of nearly instantaneous heat addition. A novel shcramjet combustor design that makes use of wedge-shaped flameholders to avoid detonation wave-wall interactions is proposed and analyzed with computational fluid dynamics (CFD) simulations in this study. The laminar, two-dimensional Navier-Stokes equations coupled with a non-equilibrium hydrogen-air combustion model based on chemical kinetics are used to represent the physical system. The equations are solved with the WARP (window-allocatable resolver for propulsion) CFD code (see: Parent, B. and Sislian, J. P., “The Use of Domain Decomposition in Accelerating the Convergence of Quasihyperbolic Systems”, J. of Comp. Physics, Vol. 179, No. 1,2002, pages 140-169). The solver was validated with experimental results found in the literature. A series of steady-state numerical simulations was conducted using WARP and it was deter-mined by means of thrust potential calculations that this combustor design is a viable one for shcramjet propulsion: assuming a shcramjet flight Mach number of twelve at an altitude of 36,000 m, the geometrical dimensions used for the combustor give rise to an operational range for combustor inlet Mach numbers between six and eight. Different shcramjet flight Mach numbers would require different combustor dimensions and hence a variable geometry system in or-der to be viable.

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LIMITED OXIDATION OF IRRADIATED GRAPHITE WASTE TO REMOVE SURFACE CARBON-14

  • Smith, Tara E.;Mccrory, Shilo;Dunzik-Gougar, Mary Lou
    • Nuclear Engineering and Technology
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    • v.45 no.2
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    • pp.211-218
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    • 2013
  • Large quantities of irradiated graphite waste from graphite-moderated nuclear reactors exist and are expected to increase in the case of High Temperature Reactor (HTR) deployment [1,2]. This situation indicates the need for a graphite waste management strategy. Of greatest concern for long-term disposal of irradiated graphite is carbon-14 ($^{14}C$), with a half-life of 5730 years. Fachinger et al. [2] have demonstrated that thermal treatment of irradiated graphite removes a significant fraction of the $^{14}C$, which tends to be concentrated on the graphite surface. During thermal treatment, graphite surface carbon atoms interact with naturally adsorbed oxygen complexes to create $CO_x$ gases, i.e. "gasify" graphite. The effectiveness of this process is highly dependent on the availability of adsorbed oxygen compounds. The quantity and form of adsorbed oxygen complexes in pre- and post-irradiated graphite were studied using Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and Xray Photoelectron Spectroscopy (XPS) in an effort to better understand the gasification process and to apply that understanding to process optimization. Adsorbed oxygen fragments were detected on both irradiated and unirradiated graphite; however, carbon-oxygen bonds were identified only on the irradiated material. This difference is likely due to a large number of carbon active sites associated with the higher lattice disorder resulting from irradiation. Results of XPS analysis also indicated the potential bonding structures of the oxygen fragments removed during surface impingement. Ester- and carboxyl-like structures were predominant among the identified oxygen-containing fragments. The indicated structures are consistent with those characterized by Fanning and Vannice [3] and later incorporated into an oxidation kinetics model by El-Genk and Tournier [4]. Based on the predicted desorption mechanisms of carbon oxides from the identified compounds, it is expected that a majority of the graphite should gasify as carbon monoxide (CO) rather than carbon dioxide ($CO_2$). Therefore, to optimize the efficiency of thermal treatment the graphite should be heated to temperatures above the surface decomposition temperature increasing the evolution of CO [4].

Upregulation of Dendritic Arborization by N-acetyl-D-Glucosamine Kinase Is Not Dependent on Its Kinase Activity

  • Lee, HyunSook;Dutta, Samikshan;Moon, Il Soo
    • Molecules and Cells
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    • v.37 no.4
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    • pp.322-329
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    • 2014
  • N-acetylglucosamine kinase (GlcNAc kinase or NAGK; EC 2.7.1.59) is highly expressed and plays a critical role in the development of dendrites in brain neurons. In this study, the authors conducted structure-function analysis to verify the previously proposed 3D model structure of GlcNAc/ATP-bound NAGK. Three point NAGK mutants with different substrate binding capacities and reaction velocities were produced. Wild-type (WT) NAGK showed strong substrate preference for GlcNAc. Conversion of Cys143, which does not make direct hydrogen bonds with GlcNAc, to Ser (i.e., C143S) had the least affect on the enzymatic activity of NAGK. Conversion of Asn36, which plays a role in domain closure by making a hydrogen bond with GlcNAc, to Ala (i.e., N36A) mildly reduced NAGK enzyme activity. Conversion of Asp107, which makes hydrogen bonds with GlcNAc and would act as a proton acceptor during nucleophilic attack on the ${\gamma}$-phosphate of ATP, to Ala (i.e., D107A), caused a total loss in enzyme activity. The overexpression of EGFP-tagged WT or any of the mutant NAGKs in rat hippocampal neurons (DIV 5-9) increased dendritic architectural complexity. Finally, the overexpression of the small, but not of the large, domain of NAGK resulted in dendrite degeneration. Our data show the effect of structure on the functional aspects of NAGK, and in particular, that the small domain of NAGK, and not its NAGK kinase activity, plays a critical role in the upregulation of dendritogenesis.

Supercritical water oxidation of Dimethyl methylphosphonate(DMMP) (Dimethyl methylphosphonate(DMMP)의 초임계수 산화반응)

  • Lee, Hae-Wan;Ryu, Sam-Gon;Lee, Jong-Chol;Hong, Deasik
    • Korean Chemical Engineering Research
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    • v.44 no.6
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    • pp.636-643
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    • 2006
  • Supercritical water oxidation of DMMP using continuous flow reactor was studied at temperature ranging from 440 to $540^{\circ}C$ and a fixed pressure of 242 bar. The range of residence times in the reactor was from 10 to 26 s, and oxygen excess value varied from -40 to 200%. Destruction efficiencies (DE) of DMMP were greater than 99.7% at $540^{\circ}C$, and increased as the DMMP concentrations were increased. DE of DMMP were significantly affected by oxygen concentration under stoichiometric amount, but showed little difference over stoichiometric amount. On the basis of 30 data with conversions greater than 85%, kinetic correlations for the DE of DMMP were developed. The pre-exponential factor was $(1.10{\pm}0.76){\times}10^6$, and the activation energy was $90.66{\pm}3.87kJ/mol$, and the reaction orders for DMMP and oxygen were $1.02{\pm}0.03$, $0.32{\pm}0.03$, respectively. The model predictions agreed well with the experimental data.

Cu2+ ion reduction in wastewater over RDF-derived char

  • Lee, Hyung Won;Park, Rae-su;Park, Sung Hoon;Jung, Sang-Chul;Jeon, Jong-Ki;Kim, Sang Chai;Chung, Jin Do;Choi, Won Geun;Park, Young-Kwon
    • Carbon letters
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    • v.18
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    • pp.49-55
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    • 2016
  • Refuse-derived fuel (RDF) produced using municipal solid waste was pyrolyzed to produce RDF char. For the first time, the RDF char was used to remove aqueous copper, a representative heavy metal water pollutant. Activation of the RDF char using steam and KOH treatments was performed to change the specific surface area, pore volume, and the metal cation quantity of the char. N2 sorption, Inductively Coupled Plasma-Atomic Emission Spectrometer (ICP-AES), and Fourier transform infrared spectroscopy were used to characterize the char. The optimum pH for copper removal was shown to be 5.5, and the steam-treated char displayed the best copper removal capability. Ion exchange between copper ions and alkali/alkaline metal cations was the most important mechanism of copper removal by RDF char, followed by adsorption on functional groups existing on the char surface. The copper adsorption behavior was represented well by a pseudo-second-order kinetics model and the Langmuir isotherm. The maximum copper removal capacity was determined to be 38.17 mg/g, which is larger than those of other low-cost char adsorbents reported previously.