• Title/Summary/Keyword: catalytic model

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The Roles of Metal Ions and Water Molecules in the Hydrolysis of Bis(p-nitrophenyl)phosphate as a DNA Model Catalyzed by Dinuclear Ni(II) Complex (DNA 모델인 Bis(p-nitrophenyl)phosphate에 대한 2핵 Ni(II) 착 화합물의 촉매 가수분해 반응에서 물 분자와 금속 이온의 역할)

  • Sung, Nack-Do;Yun, Ki-Seob
    • Applied Biological Chemistry
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    • v.48 no.2
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    • pp.115-119
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    • 2005
  • The catalytic hydrolysis reactivities of dinuclear nickel (II) complex, ${\mu}-aquapentaaqua[{\mu}-3,6-bis(6'-methyl-2'-pyridyl)pyridazine]chlorodinickel\;(II)$ trichloride trihydrate (APNT) for bis(p-nitrophenyl) phosphate (BNPP) as a DNA model compound were investigated. The dissociation constants of APNT were $pKa_1=7.9$ and $pKa_2=9.6$, respectively. The hydrolysis rate constant of BNPP compound by APNT was showed the rate enhancement of about 370,000 times in the case of none catalyst at pH 7.0 and $50^{\circ}C$. Based on the findings, we proposed the catalytic cycle for the hydrolysis of BNPP by APNT complex. The metal ions of dinuclear nickel (II) complex significantly enhance the transfer rate of phosphoryl group in the catalytic process and the water molecules as nucleophile and proton transfer agent act in different steps.

Platinum Model Catalysts Dispersed on Alumina with Regular Pores (규칙적 세공을 가진 알루미나에 분산된 백금 모형촉매)

  • 윤천호;임헌성
    • Journal of the Korean institute of surface engineering
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    • v.33 no.4
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    • pp.261-265
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    • 2000
  • Geometrically and chemically well defined Pt/alumina model catalysts have been prepared. To this end, we fabricated electrochemically alumina supports in which pores of constant size, length and shape were regularly distributed over a wide area of the surface. Platinum particles were dispersed on the pore surfaces via organometallic chemical vapor deposition technique using (trimethyl) methylcyclopentadienylplatinum (IV) as a precursor. The chemical composition of the alumina plane surfaces was examined by Auger electron spectroscopy and the adsorption characteristics of the platinum particles were studied by thermal desorption spectroscopy. A variety of industrial catalytic problems are now open for further investigation utilizing the Pt/alumina model catalysts.

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The Development and Implementation of Model-based Control Algorithm of Urea-SCR Dosing System for Improving De-NOx Performance and Reducing NH3-slip (Urea-SCR 분사시스템의 DeNOx 저감 성능 향상과 NH3 슬립저감을 위한 모델 기반 제어알고리즘 개발 및 구현)

  • Jeong, Soo-Jin;Kim, Woo-Seung;Park, Jung-Kwon;Lee, Ho-Kil;Oh, Se-Doo
    • Transactions of the Korean Society of Automotive Engineers
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    • v.20 no.1
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    • pp.95-105
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    • 2012
  • The selective catalytic reduction (SCR) system is a highly-effective aftertreatment device for NOx reduction of diesel engines. Generally, the ammonia ($NH_3$) was generated from reaction mechanism of SCR in the SCR system using the liquid urea as the reluctant. Therefore, the precise urea dosing control is a very important key for NOx and $NH_3$ slip reduction in the SCR system. This paper investigated NOx and $NH_3$ emission characteristics of urea-SCR dosing system based on model-based control algorithm in order to reduce NOx. In the map-based control algorithm, target amount of urea solution was determined by mass flow rate of exhaust gas obtained from engine rpm, torque and $O_2$ for feed-back control NOx concentration should be measured by NOx sensor. Moreover, this algorithm can not estimate $NH_3$ absorbed on the catalyst. Hence, the urea injection can be too rich or too lean. In this study, the model-based control algorithm was developed and evaluated on the numerical model describing physical and chemical phenomena in SCR system. One channel thermo-fluid model coupled with finely tuned chemical reaction model was applied to this control algorithm. The vehicle test was carried out by using map-based and model-based control algorithms in the NEDC mode in order to evaluate the performance of the model based control algorithm.

Simultaneous degradation of nitrogenous heterocyclic compounds by catalytic wet-peroxidation process using box-behnken design

  • Gosu, Vijayalakshmi;Arora, Shivali;Subbaramaiah, Verraboina
    • Environmental Engineering Research
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    • v.25 no.4
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    • pp.488-497
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    • 2020
  • The present study investigates the feasibility of nitrogenous heterocyclic compounds (NHCs) (Pyridine-Quinoline) degradation by catalytic wet peroxidation (CWPO) in the presence of nanoscale zerovalent iron supported on granular activated carbon (nFe0/GAC) using statistical optimization technique. Response surface methodology (RSM) in combination with Box-Behnken design (BBD) was used to optimize the process parameters of CWPO process such as initial pH, catalyst dose, hydrogen peroxide dose, initial concentration of pyridine (Py) and quinolone (Qn) were chosen as the main variables, and total organic carbon (TOC) removal and total Fe leaching were selected as the investigated response. The optimization of process parameters by desirability function showed the ~85% of TOC removal with process condition of initial solution pH 3.5, catalyst dose of 0.55 g/L, hydrogen peroxide concentration of 0.34 mmol, initial concentration of Py 200 mg/L and initial concentration of Qn 200 mg/L. Further, for TOC removal the analysis of variance results of the RSM revealed that all parameter i.e. initial pH, catalyst dose, hydrogen peroxide dose, initial concentration of Py and initial concentration of Qn were highly significant according to the p values (p < 0.05). The quadratic model was found to be the best fit for experimental data. The present study revealed that BBD was reliable and effective for the determination of the optimum conditions for CWPO of NHCs (Py-Qn).

A Study on the Regeneration of Ni Catalyst for Hydrogenation(II) (수소첨가반응용 니켈 폐촉매의 활성재생에 관한 연구 (II))

  • Kim, Jung-Hun;Lee, Gun-Dae;Lee, Ho-In
    • Applied Chemistry for Engineering
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    • v.2 no.1
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    • pp.47-55
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    • 1991
  • Regeneration of carbon-deposited Ni catalyst used for hydrogenation reaction was studied. Deposited carbon was removed by oxidation with various concentrations of oxygen. Activity of the catalysts was tested on aniline hydrogenation as a model reaction. When a carbon-deposited catalyst was treated under oxygen atmosphere, the specific surface area of the catalyst increased and then decreased with the increase of treatment temperature. The treatment temperature which gives maximum specific surface area increased with the decrease of oxygen concentration. Pore size of the support was decreased and sintering of nickel particles was more significant with the increase of oxygen concentration. The catalyst treated under 5 % oxygen concentration recovered its catalytic activity up to 90 % of the initial value, but the treatment under 20 % oxygen concentration gave no significant increase of the catalytic activity. Catalytic activity increased with treatment time when the catalyst was treated under 5 % oxygen concentration, but nearly constant after 1 hour.

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A Pd Doped PVDF Hollow Fibre for the Dissolved Oxygen Removal Process

  • Batbieri G.;Brunetti A.;Scura F.;Lentini F.;Agostino R G.;Kim, M.J.;Formoso V.;Drioli E.;Lee, K.H.
    • Korean Membrane Journal
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    • v.8 no.1
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    • pp.1-12
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    • 2006
  • In semiconductor industries, dissolved oxygen is one of the most undesirable contaminants of ultrapure water. A method for dissolved oxygen removal (DOR) consists in the use of polymeric hollow fibres, loaded with a catalyst and fed with a reducing agent such as hydrogen. In this work, PVDF hollow fibres loaded with Pd were characterized by means of perporometry, scanning electron microscopy (SEM), energy dispersive X-ray (EDX). The hollow fibre analyzed shows a five-layer structure with remarkable morphological differences. An estimation of pore diameters and their distribution was performed giving a mean pore diameter of 100 nm. The permeance and selectivity of the fibres were measured using $H_2,\;N_2,\;O_2$ as single gases, at different operating conditions. An $H_2$ permeance of $37 mmol/m^2s$ was measured and $H_2/O_2$ and $H_2/N_2$ selectivities of ca. 3 were obtained. $H_2$ permeance was 1/3 when a water stream flows in the shell side. Catalytic fibrebehaviour was simulated using a mathematical model for a loop membrane reactor, considering only $O_2$ and $H_2$ diffusive transport inside the membrane and their catalytic reaction. Dimensionless parameters such as the Thiele modulus are employed to describe the system behaviour. The model agrees well with the experimental reaction data.

Design of the Fixed-Bed Catalytic Reactor for the Maleic Anhydride Production (무수마레인산 생산을 위한 고정층 촉매 반응기 설계)

  • Yoon, Young Sam;Koo, Eun Hwa;Park, Pan Wook
    • Applied Chemistry for Engineering
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    • v.10 no.3
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    • pp.467-476
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    • 1999
  • This paper analyzed the behavior of fixed-bed catalytic reactor (FBCR) which synthesizing maleic anhydride(MA) from the selective oxidation of n-butane. The behavior of FBCR describing convection-diffusion-reaction mechanism is examined by using two-dimensional pseudohomogeneous plug-flow transient model, with the kinetics of Langmuir-Hinshelwood type. Prediction model is composed by optimum parameter estimation from temperature profile, yield and conversion of single FBCR on operating condition variations of Sharma's pilot-plant experiment. A double FBCR with same yield and conversion for single FBCR generated a $8.96^{\circ}C$ lower hot spot temperature than a single FBCR. We could predict parametric sensitivity according to the variation of possible operating condition (temperature, concentration, volumetric flow of feed reactant and coolant flow rate) of single and double FBCR. Double FBCR showed the behavior of more operating range than single FBCR. Double FBCR with nonuniform activities could assure safety operation condition for the possible variation of operating condition. Also, double FBCR had slightly higher than the single FBCR in conversion and yield.

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Removal of toxic hydroquinone: Comparative studies on use of iron impregnated granular activated carbon as an adsorbent and catalyst

  • Tyagi, Ankit;Das, Susmita;Srivastava, Vimal Chandra
    • Environmental Engineering Research
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    • v.24 no.3
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    • pp.474-483
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    • 2019
  • In this study, iron (Fe) impregnated granular activated carbon (Fe-GAC) has been synthesized and characterized for various properties. Comparative studies have been performed for use of Fe-GAC as an adsorbent as well as a catalyst during catalytic oxidation of hydroquinone (HQ). In the batch adsorption study, effect of process parameter like initial HQ concentration ($C_o=25-1,000mg/L$), pH (2-10), contact time (t: 0-24 h), temperature (T: $15-45^{\circ}C$) and adsorbent dose (w: 5-50 g/L) have been studied. Maximum HQ adsorption efficiency of 75% was obtained at optimum parametric condition of: pH = 4, w = 40 g/L and t = 14 h. Pseudo-second order model best-fitted the HQ adsorption kinetics whereas Langmuir model best-represented the isothermal equilibrium behavior. During oxidation studies, effect of various process parameters like initial HQ concentration ($C_o:20-100mg/L$), pH (4-8), oxidant dose ($C_{H2O2}:0.4-1.6mL/L$) and catalyst dose (m: 0.5-1.5 g/L) have been optimized using Taguchi experimental design matrix. Maximum HQ removal efficiency of 83.56% was obtained at optimum condition of $C_o=100mg/L$, pH = 6, $C_{H2O2}=0.4mL/L,$ and m = 1 g/L. Overall use of Fe-GAC during catalytic oxidation seems to be a better as compared to its use an adsorbent for treatment of HQ bearing wastewater.

Kinetics of Catalytic Reactions Occurring in a Small Reaction Volume (작은 반응 매질에서 일어나는 촉매 반응 속도에 관한 연구)

  • Kim, Jung-Han;Sung, Jae-Young
    • Journal of the Korean Chemical Society
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    • v.52 no.3
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    • pp.217-222
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    • 2008
  • We investigate the kinetics of diffusion-influenced catalytic reactions occurring in small reaction volume. From a simple exact model study, we find that the reaction rate coefficient decreases with the size of reaction volume. The explicit expression for the average reaction rate constant is presented, which can be regarded as a generalization of well-known Collins-Kimball rate constant into the reactions occurring in a small reaction volume. It turns out that the traditional diffusion influenced reaction dynamics is followed by a single exponential relaxation phase with a rate constant dependent on the reaction volume for the catalytic reactions occurring in small reaction volumes.

Odors Removal by using Manganese Oxide Catalysts (망간산화물 촉매를 이용한 악취제거)

  • Seo, Seong-Gyu;Yoon, Hyung-Sun;Ma, Zhong-Kun;Liu, Yi
    • Journal of Korean Society for Atmospheric Environment
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    • v.26 no.4
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    • pp.443-448
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    • 2010
  • The objective of this study was to assess the catalytic activities of manganese oxide (MnO, $MnO_2$, $Mn_2O_3$, and $Mn_3O_4$) catalysts for odors (acetaldehyde and propionaldehyde) removal. We used a fixed bed reactor as the experimental apparatus and the catalytic performance were carried out over the temperature range of $200{\sim}470^{\circ}C$. The properties and performance of catalysts were characterized by the X-ray diffraction (XRD) and Brunauer Emmett Teller (BET). The catalytic activities of manganese oxide catalysts for acetaldehyde combustion were in the order of MnO < $MnO_2$ < $Mn_2O_3$ < $Mn_3O_4$, and it is similar to that of propionaldehyde combustion. We also confirmed that the reactions have well followed the kinetic model of Power-Rate Law and the reaction order (n) is 1 for both of the acetaldehyde and propionaldehyde combustion. In addition, the reaction activation energy of acetaldehyde and propionaldehyde combustion over $Mn_3O_4$ were found to be $72.42\;kJmol^{-1}$ for 487~503 K and $51.14\;kJmol^{-1}$ for 473~533 K, respectively.