• Title/Summary/Keyword: Reaction Kinetics Model

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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.

Comparative studies for the performance of a natural gas steam reforming in a membrane reactor (분리막 반응기를 이용한 천연가스 개질반응의 성능에 관한 비교 분석)

  • Lee, Boreum;Lim, Hankwon
    • Journal of the Korean Institute of Gas
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    • v.20 no.6
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    • pp.95-101
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    • 2016
  • For a natural gas steam reforming, comparative studies of the performance in a conventional packed-bed reactor and a membrane reactor, a new conceptual reactor consisting of a reactor with series of hydrogen separation membranes, have been performed. Based on experimental kinetics reported by Xu and Froment, a process simulation model was developed with Aspen $HYSYS^{(R)}$, a commercial process simulator, and effects of various operating conditions like temperature, $H_2$ permeance, and Ar sweep gas flow rate on the performance in a membrane reactor were investigated in terms of reactant conversion and $H_2$ yield enhancement showing improved $H_2$ yield and methane conversion in a membrane reactor. In addition, a preliminary cost estimation focusing on natural gas consumption to supply heat required for the system was carried out and feasibility of possible cost savings in a membrane reactor was assessed with a cost saving of 10.94% in a membrane reactor.

Heteroexpression and Functional Characterization of Glucose 6-Phosphate Dehydrogenase from Industrial Aspergillus oryzae

  • Guo, Hongwei;Han, Jinyao;Wu, Jingjing;Chen, Hongwen
    • Journal of Microbiology and Biotechnology
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    • v.29 no.4
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    • pp.577-586
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    • 2019
  • The engineered Aspergillus oryzae has a high NADPH demand for xylose utilization and overproduction of target metabolites. Glucose-6-phosphate dehydrogenase (G6PDH, E.C. 1.1.1.49) is one of two key enzymes in the oxidative part of the pentose phosphate pathway, and is also the main enzyme involved in NADPH regeneration. The open reading frame and cDNA of the putative A. oryzae G6PDH (AoG6PDH) were obtained, followed by heterogeneous expression in Escherichia coli and purification as a his6-tagged protein. The purified protein was characterized to be in possession of G6PDH activity with a molecular mass of 118.0 kDa. The enzyme displayed maximal activity at pH 7.5 and the optimal temperature was $50^{\circ}C$. This enzyme also had a half-life of 33.3 min at $40^{\circ}C$. Kinetics assay showed that AoG6PDH was strictly dependent on $NADP^+$ ($K_m=6.3{\mu}M$, $k_{cat}=1000.0s^{-1}$, $k_{cat}/K_m=158.7s^{-1}{\cdot}{\mu}M^{-1}$) as cofactor. The $K_m$ and $k_{cat}/K_m$ values of glucose-6-phosphate were $109.7s^{-1}{\cdot}{\mu}M^{-1}$ and $9.1s^{-1}{\cdot}{\mu}M^{-1}$ respectively. Initial velocity and product inhibition analyses indicated the catalytic reaction followed a two-substrate, steady-state, ordered BiBi mechanism, where $NADP^+$ was the first substrate bound to the enzyme and NADPH was the second product released from the catalytic complex. The established kinetic model could be applied in further regulation of the pentose phosphate pathway and NADPH regeneration of A. oryzae to improve its xylose utilization and yields of valued metabolites.

TWO-Point Reactor Kinetics for Large D$_2$O Reflected Systems (다량의 중수반사체 계통에 대한 2-점노 운동방정식)

  • Noh, T.W.;Oh, S.K.;Kim, S.Y.;Kim, D.H.
    • Nuclear Engineering and Technology
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    • v.19 no.3
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    • pp.192-197
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    • 1987
  • Two-point kinetic equations for a compact-core-with-bulky-D$_2$O-reflector system were developed. A unique feature of the system is that certain fission gammas create retarded photoneutrons in the D$_2$O reflector by (r, n) reaction. Coupling effect between the core and the reflector was investigated by simulating power transients with various ramp reactivity insertions. Special attention was paid to the phenomenon associated with spatial separation of photoneutrons and their precursors. Simulations show that accuracy of the two-point model is comparable with that of space-dependent approach. Also it is found that the explicily expressed photoneutron terms in the reflector equation slow down the power transient compared to non-photoneutron expressions. Detectors for reactor power control purpose prefer to be deployed in the core zone to be able to accurately perdict transient power.

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Kinetic Measurement of the Step Size of DNA Unwinding by Bacteriophage T7 DNA Helicase gp4 (T7 박테리오파지 gp4 DNA helicase에 의한 DNA unwinding에서 step size의 반응속도론적 측정)

  • Kim, Dong-Eun
    • Journal of Life Science
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    • v.14 no.1
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    • pp.131-140
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    • 2004
  • T7 bacteriophage gp4 is the replicative DNA helicase that unwinds double-stranded DNA by utilizing dTTP hydrolysis energy. The quaternary structure of the active form of T7 helicase is a hexameric ring with a central channel. Single-stranded DNA passes through the central channel of the hexameric ring as the helicase translocates $5'\rightarrow3'$ along the single-stranded DNA. The DNA unwinding was measured by rapid kinetic methods and showed a lag before the single-stranded DNA started to accumulate exponentially. This behavior was analyzed by a kinetic stepping model for the unwinding process. The observed lag phase increased as predicted by the model with increasing double-stranded DNA length. Trap DNA added in the reaction had no effect on the amplitudes of double-stranded DNA unwound, indicating that the $\tau7$ helicase is a highly processive helicase. Global fitting of the kinetic data to the stepping model provided a kinetic step size of 10-11 bp/step with a rate of $3.7 s^{-1}$ per step. Both the mechanism of DNA unwinding and dTTP hydrolysis and the coupling between the two are unaffected by temperature from $4∼37^{\circ}C$. Thus, the kinetic stepping for dsDNA unwinding is an inherent property of tile replicative DNA helicase.

Adsorption Characteristics of Dimetridazole Antibiotics on Activated Carbon Prepared from Agricultural Waste Citrus Peel (폐감귤박 활성탄을 이용한 항생제 Dimetridazole의 흡착특성)

  • Lee, Chang-Han;Kam, Sang-Kyu;Lee, Min-Gyu
    • Korean Chemical Engineering Research
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    • v.55 no.6
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    • pp.798-806
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    • 2017
  • A activated carbon (WCAC, waste citrus activated carbon) prepared from an agricultural waste citrus peel material generated in Jeju was utilized for the removal of dimetridazole (DMZ) antibiotics in aqueous solution. The adsorption of DMZ on WCAC was investigated with the change of various parameters such as contact time, dosage of WCAC, particle size of WCAC, temperature, pH, and DMZ concentration. The DMZ adsorption capacity increased with increasing temperature and decreasing particle size. Also it was decreased at less than pH 4 but sustained almost constantly at pH 4 or greater. Isotherm parameters were determined from the Langmuir, Freundlich, Redlich-Peterson and Duinin-Radushkevich (D-R) isotherm models. The isotherm data were best described by the Redlich-Peterson isotherm model. And the adsorption kinetics can be successfully fitted to the pseudo-second-order kinetic model. The results of the intra-particle diffusion model suggested that film diffusion and intra-particle diffusion were occurred simultaneously during the adsorption process. Meanwhile, the thermodynamic parameters indicated that the adsorption reaction of DMZ on WCAC was an endothermic and spontaneous process. The experimental results showed that WCAC is a promising and cheap adsorbent for the removal of DMZ antibiotics.

Wet Oxidation of Phenol with Homogeneous Catalysts (균일촉매를 이용한 페놀의 습식산화)

  • Suh, Il-Soon;Ryu, Sung Hun;Yoon, Wang-Lai
    • Korean Chemical Engineering Research
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    • v.47 no.3
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    • pp.292-302
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    • 2009
  • The wet oxidation of phenol has been investigated at temperatures from 150 to $250^{\circ}C$ and oxygen partial pressures from 25.8 to 75.0 bar with initial pH of 1.0 to 12.0 and initial phenol concentration of 10 g/l. Chemical Oxygen Demand COD has bee measured to estimate the oxidation rate. Reaction intermediates have been identified and their concentration profiles have been determined using liquid chromatography. The destruction rate of phenol have shown the first-order kinetics with respect to phenol and the changes in COD during wet oxidation have been described well with the lumped model. The impact of various homogeneous catalysts, such as $Cu^{2+}$, $Fe^{2+}$, $Zn^{2+}$, $Co^{2+}$ and $Ce^{3+}$ ions, on the destruction rate of phenol and COD has also been studied. The homogeneous catalyst of $CuSO_4$ has been found to be the most effective for the destruction of phenol and COD during wet oxidations. The destruction rate of formic acid formed during wet oxidations of phenol have increased as increasing temperature and $CuSO_4$ concentration. The final concentrations of acetic acid which has been formed during wet oxidations and difficult to oxidize have increased with reaction temperature and with decrease in the catalyst load.

Characteristics and Parameters for Adsorption of Carbol Fuchsin Dye by Coal-based Activated Carbon: Kinetic and Thermodynamic (석탄계 활성탄에 의한 Carbol Fuchsin의 흡착 특성과 파라미터: 동력학 및 열역학)

  • Lee, Jong Jib
    • Applied Chemistry for Engineering
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    • v.32 no.3
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    • pp.283-289
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    • 2021
  • 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.

The Amino-Carbonyl Reaction in the Fructose-Glycine Mixture System (Fructose-Glycine 혼합계에 있어서 Amino-Carbonyl 반응)

  • Lee, Jin-Ho;Han, Kang-Wan
    • Korean Journal of Food Science and Technology
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    • v.21 no.3
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    • pp.351-359
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    • 1989
  • This study was conducted to observe the physico-chemical exchange and effect of amino-carbonyl reaction between fructose and glycine . When various buffer solutions were added to equimolar mixture of fructose and glycine at pH 6.0 and $100^{\circ}C$, the browning effect was markedly observed by Mcllvaine buffer. Among the combinations of temperature and reaction time, the deep browning effect was obtained above $100^{\circ}C$, 3hr A marked browning effect obtained above pH 7.0 but little observed below pH 7.0. The browning effect was markedly increased at high fructose concentration. It required 4.0hrs and 32.9hrs to decrease 50% of initial concentration of fructose and glycine at $100^{\circ}C$ and pH 7 but 0.9hrs and 3.8hrs at $120^{\circ}C$, pH 7.0, respectively. The rate constant of fructose and glycine at $100^{\circ}C\;and\;120^{\circ}C$ were $1.78{\times}10^{-1},\;2.11{\times}10^{-2}\;and\;7.74{\times}10^{-1},\;1.83{\times}10^{-1}$, respectively. The formation of HMF was likely to follow the first order kinetics. The addition of 0.1M sodium sulfite, 0.1M sodium bisulfite and 0.1M calcium chloride to equimolar mixture (0.05M) surpressed the reaction up to 76.8%, 76.8% and 96.4%, respectively.

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Adsorption Characteristics and Parameters of Acid Black and Quinoline Yellow by Activated Carbon (활성탄에 의한 Acid Black과 Quinoline Yellow의 흡착특성 및 파라미터)

  • Yi, Kyung Ho;Hwang, Eun Jin;Baek, Woo Seung;Lee, Jong-Jib;Dong, Jong-In
    • Clean Technology
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    • v.26 no.3
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    • pp.186-195
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    • 2020
  • The isothermal adsorption, dynamic, and thermodynamic parameters of Acid black (AB) and Quinoline yellow (QY) adsorption by activated carbon were investigated using the initial concentration, contact time, temperature, and pH of the dyes as adsorption parameters. The adsorption equilibrium data fits the Freundlich isothermal adsorption model, and the calculated Freundlich separation factor values found that activated carbon can effectively remove AB and QY. Comparing the kinetic data showed that the pseudo second order model was within 10% error in the adsorption process. The intraparticle diffusion equation results were divided into two straight lines. Since the slope of the intraparticle diffusion line was smaller than the slope of the boundary layer diffusion line, it was confirmed that intraparticle diffusion was the rate-controlling step. The thermodynamic experiments indicated that the activation energies of AB and QY were 19.87 kJ mol-1 and 14.17 kJ mol-1, which corresponded with the physical adsorption process (5 ~ 40 kJ mol-1). The adsorption reaction was spontaneous because the free energy change in the adsorption of AB and QY by activated carbon was negative from 298 to 318 K. As the temperature increased, the free energy value decreased resulting in higher spontaneity. Adsorption of AB and QY by activated carbon showed the highest adsorption removal rate at pH 3 due to the effect of anions generated by dissociation. The adsorption mechanism was electrostatic attraction.