• Title/Summary/Keyword: 흡착 반응 속도론

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Characterization of Arsenic Adsorption onto Hematite (적철석(Hematite) 표면의 비소 흡착 특성)

  • Kim, Seong Hee;Lee, Woo Chun;Cho, Hyen Goo;Kim, Soon-Oh
    • Journal of the Mineralogical Society of Korea
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    • v.25 no.4
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    • pp.197-210
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    • 2012
  • Hematite has been known to be the most stable form of various iron (oxyhydr)oxides in the surface environments. In this study, its properties as an adsorbent were examined and also adsorption of arsenic onto hematite was characterized as well. The specific surface area of hematite synthesized in our laboratory appeared to be $31.8g\;m^2/g$ and its point of zero salt effect, (PZSE) determined by potentiometric titration was observed 8.5. These features of hematite may contribute to high capacity of arsenic adsorption. From several adsorption experiments undertaken at the identical solution concentrations over pH 2~12, the adsorption of As(III) (arsenite) was greater than that of As(V) (arsenate). As of pH-dependent adsorption patterns, in addition, arsenite adsorption gradually increased until pH 9.2 and then sharply decreased with pH, whereas adsorption of arsenate was greatest at pH 2.0 and steadily decreased with the increasing pH from 2 to 12. The characteristics of these pH-dependent adsorption patterns might be caused by combined effects of the variation in the chemical speciation of arsenic and the surface charge of hematite. The experimental results on adsorption kinetics show that adsorption of both arsenic species onto hematite approached equilibrium within 20 h. Additionally, the pseudo-second-order model was evaluated to be the best fit for the adsorption kinetics of arsenic onto hematite, regardless of arsenic species, and the rate constant of As(V) adsorption was investigated to be larger than that of As(III).

Modeling of the Nitrate Adsorption Kinetics onto $ZnCl_2$ Treated Granular Activated Carbon (염화아연으로 표면개질된 입상활성탄의 질산성질소 흡착속도의 모델링 연구)

  • Ji, Min-Kyu;Jung, Woo-Sik;Bhatnagar, Amit;Jeon, Byong-Hun
    • Journal of Soil and Groundwater Environment
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    • v.13 no.3
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    • pp.21-26
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    • 2008
  • Nitrate adsorption from aqueous solutions onto zinc chloride ($ZnCl_2$) treated coconut Granular Activated Carbon (GAC) was studied in a batch mode at two different initial nitrate concentrations (25 and 50 mg/L). The rate of nitrate uptake on prepared media was fast in the beginning, and 50% of adsorption was occurred within 10 min. The adsorption equilibrium was achieved within one hour. The mechanism of adsorption of nitrate on $ZnCl_2$ treated coconut GAC was investigated using four simplified kinetic models : the rate parameters were calculated for each model. The kinetic analysis indicated that pseudo-second-order kinetic with pore-diffusion-controlled was the best correlation of the experimental kinetic data in the present adsorption study.

Kinetics and Mechanism of the Selective Oxidation of Ethylene for Ethylene Oxide over Monolithic Silver Catalyst (모놀리스형 은촉매상에서 에틸렌선택산화반응의 속도론적 고찰)

  • Park, Rho-Bum;Kim, Sang-Chai;Sunwoo, Chang-Sin;Yu, Eui-Yeon
    • Applied Chemistry for Engineering
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    • v.2 no.2
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    • pp.165-174
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    • 1991
  • The kinetics and the mechanism for the selective oxidation of ethylene on the supported monolithic silver catalyst were experimentally investigated in a fixed bed tubular reactor. The formation rates of ethylene oxide and carbon dioxide were measured at the atmospheric pressure with various combinations of partial pressures of ethylene and oxygen at temperature range of $225-300^{\circ}C$, conversion with 1.2-7.5 %, and then the mechanism of the selective oxidation of ethylene was verified. Their formation rates fitted with the Langmuir-Hinshelwood mechnism. The ethylene oxide and carbon dioxide are produced by reation of adsorbed ethylene with monoatomic oxygen adsorbed on the active sites of Ag-surface, and their formation rate equation are expressed as : $R_{EO}={\frac{k_1K_0{^{1/2}}K_EK_SP_{02}{^{3/2}}P_E}{(1+{\sqrt{K_0P_{02}}}+K_EP_E+K_PP_P)^2(1+{\sqrt{K_SP_{02}})^2}}$ $R_C={\frac{k_2K_0{^3}K_EK_S{^{7/2}}P_{02}{^{13/2}}P_E}{(1+{\sqrt{K_0P_{02}}}+K_EP_E+K_PP_P)^7(1+{\sqrt{K_SP_{02}})^7}}$ The activation energies of ethylene oxide and dioxide and carbon dioxide formations can be estimated to be 12.25 and 17.85 Kcal/mol, respectively.

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The Kinetics of Montmorillonite Expansion in the Treatment with Hexadecyltrimethylammonium (HDTMA와 반응하는 몬모릴로나이트의 팽창 속도론)

  • Lee Seung Yeop;Cho Won Jin
    • Journal of the Mineralogical Society of Korea
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    • v.17 no.4
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    • pp.299-307
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    • 2004
  • Surfactant adsorption by two montmorillonite types with different interlayer cations of Ca and Na was characterized by examining the time dependence of surfactant behavior on the clay surfaces. Surfactants with different micelle concentration were conducted in our experiment to observe a nonequilibrium activity of cationic surfactant on the clay over reaction periods ranging from 0.1 min to 11 days. As compared with Ca-montmorillonite (SAz), a more active intrusion of surfactant molecules into the interlayers was found in Na-montmorillonite (SWy). During a short 'initiation' stage, the basal spacing of SWy montmorillonite increased rapidly with logarithmic time. For SAz montmorillonite, however, the abrupt basal spacing increase occurred at the later stage of the reaction. From the result, the difference in the adsorption behavior exhibited by the two montmorillonite types partly results from their intrinsic nature, that is, inorganic cations originally existing on the clay surfaces. Additionally, the micelle concentration of surfactants affects the development of organo-montmorillonite, especially, in the intercalant formation and stabilization under nonequilibrium.

Comparison Study on the Removal of Cationic Dyes from Aqueous Suspension of Maghnia Montmorillonite (Maghnia 산 Montmorillonite 수용액으로부터 양이온 염료의 제거 비교연구)

  • Elaziouti, A.;Laouedj, N.
    • Journal of the Korean Chemical Society
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    • v.54 no.3
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    • pp.300-309
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    • 2010
  • The ability of sodium-exchanged clay particles as an adsorbent for the removal of commercial dyes, Methylene blue (MB) and Malachite green oxalate (MG) from aqueous solutions has been investigated under various experimental conditions. The effect of the experimental parameters, such as pH solution, agitation time, adsorbate concentration and adsorbent dose were examined. Maximum adsorption of dyes, i.e. >90% has been achieved in aqueous solutions using 0.03 g of clay at a pH of 7 and 298 K for both dyes. The adsorption process was a fast and the equilibrium was obtained within the first 5 min. For the adsorption of both MB and MG dyes, the pseudo-second-order reaction kinetics provides the best correlation of the experimental data. The adsorption equilibrium results follow Langmuir and Dubini-Radushkevich (D-R) isotherms with high regression coefficients $R^2$ > 0.98. The mean free energies $E_a$ of adsorption from D-R model were 3.779 and 2.564 kj/mol for MB and MG respectively, which corresponds to a physisorption process.

Adsorption of Arsenic onto Two-Line Ferrihydrite (비소의 Two-Line Ferrihydrite에 대한 흡착반응)

  • Jung, Young-Il;Lee, Woo-Chun;Cho, Hyen-Goo;Yun, Seong-Taek;Kim, Soon-Oh
    • Journal of the Mineralogical Society of Korea
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    • v.21 no.3
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    • pp.227-237
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    • 2008
  • Arsenic has recently become of the most serious environmental concerns, and the worldwide regulation of arsenic fur drinking water has been reinforced. Arsenic contaminated groundwater and soil have been frequently revealed as well, and arsenic contamination and its treatment and measures have been domestically raised as one of the most important environmental issues. Arsenic behavior in geo-environment is principally affected by oxides and clay minerals, and particularly iron (oxy)hydroxides have been well known to be most effective in controlling arsenic. Among a number of iron (oxy)hydroxides, for this reason, 2-line ferrihydrite was selected in this study to investigate its effect on arsenic behavior. Adsorption of 2-line ferrihydrite was characterized and compared between As(III) and As(V) which are known to be the most ubiquitous species among arsenic forms in natural environment. Two-line ferrihydrite synthesized in the lab as the adsorbent of arsenic had $10\sim200$ nm for diameter, $247m^{2}/g$ for specific surface area, and 8.2 for pH of zero charge, and those representative properties of 2-line ferrihydrite appeared to be greatly suitable to be used as adsorbent of arsenic. The experimental results on equilibrium adsorption indicate that As(III) showed much stronger adsorption affinity onto 2-line ferrihydrite than As(V). In addition, the maximum adsorptions of As(III) and As(V) were observed at pH 7.0 and 2.0, respectively. In particular, the adsorption of As(III) did not show any difference between pH conditions, except for pH 12.2. On the contrary, the As(V) adsorption was remarkably decreased with increase in pH. The results obtained from the detailed experiments investigating pH effect on arsenic adsorption show that As(III) adsorption increased up to pH 8.0 and dramatically decreased above pH 9.2. In case of As(V), its adsorption steadily decreased with increase in pH. The reason the adsorption characteristics became totally different depending on arsenic species is attributed to the fact that chemical speciation of arsenic and surface charge of 2-line ferrihydrite are significantly affected by pH, and it is speculated that those composite phenomena cause the difference in adsorption between As(III) and As(V). From the view point of adsorption kinetics, adsorption of arsenic species onto 2-line ferrihydrite was investigated to be mostly completed within the duration of 2 hours. Among the kinetic models proposed so for, power function and elovich model were evaluated to be the most suitable ones which can simulate adsorption kinetics of two kinds of arsenic species onto 2-line ferrihydrite.

A Study on the Sol-Gel Reaction Kinetics of Sodium Silicate Solution (규산(硅酸)나트륨 수용액(水溶液)의 솔-젤 반응속도론적(反應速度論的) 고찰(考察))

  • Kim, Chul-Joo;Yoon, Ho-Sung;Jang, Hee-Dong
    • Resources Recycling
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    • v.17 no.6
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    • pp.34-42
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    • 2008
  • The properties of sodium silicate solution were surveyed by using the yellow silicomolybdic method, and the formation of silica sol from sodium silicate solution and the growth of silica sol were investigated in this study. The $SiO_2$ content of 2 wt% in sodium silicate solution was proper to oxidize sodium silicate with sulfuric acid. After the removal of sodium ions in sodium silicate solution, the pH of silicate solution had to be controlled above 9 for the stabilization of silicate solution. The condensation between silicic acid species and silica nuclei surfaces has been studied at $20{\sim}80^{\circ}C$ and pH 10 in silicate solutions with silica nuclei. The reaction falls into two kinetics regimes, limited at high silicic acid species concentration by polymerization, but at lower concentration by a process whereby deposited silicic acid species condenses further to silica. The overall condensation is first-order in silicic acid species concentration, proceeded toward to pseudo equilibrium concentration, $C_x$, rather than the solubility of amorphous silica. The heat of solution of amorphous silica was 3.34 kcal/mol and exhibits an Arrhenius temperature dependence with an apparent activation energy of 3.16 kcal/mol in the range of $20{\sim}80^{\circ}C$.

Interactions between Hydrodenitrogenation of Pyridine and Hydrodeoxygenation of m-Cresol over sulfided CoMo/γ-Al2O3 Catalyst (황화 CoMo/γ-Al2O3 촉매상에서 수첨탈질반응과 수첨탈산소 반응의 상호작용)

  • Kim, Hak-Soo;Park, Hea-Kyung;Kim, Kyung-Lim
    • Applied Chemistry for Engineering
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    • v.2 no.2
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    • pp.108-118
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    • 1991
  • Interactions between pyridine hydrodenitrogenation (HDN) and m-cresol hydrodeoxygenation(HDO), and the kinetic analysis were studied over sulfided $CoMo/{\gamma}-Al_2O_3$ catalyst at the range of temperatures between 473 K and 723 K, the total pressures between $10{\times}10^5Pa$ and $50{\times}10^5Pa$, and the contact times between 0.0125 g-cat. hr/ml-feed and 0.03g-cat. hr/ml-feed. HDN of pyridine and HDO of m-cresol were inhibited by each other and the inhibition effect of HDO by pyridine is higher than that of HDN by m-cresol. But reactivity of m-cresol is higher than that of pyridine. The rate equations of pyridine and m-cresol were given to be ${\gamma}_{HDN}=k_{HDN}{\cdot}K_pC_p/(1+K_cC_c+K_pC_p)$ and ${\gamma}_{HDO}=k_{HDO}{\cdot}K_cC_c/(1+K_cC_c+K_pC_p)$ in terms of Langmuir-Hinshellwood-Hougen-Watson model. At each temperature, reaction rate constants and adsorption equilibrium constants were determined and activation energies of pyridine HDN and m-cresol HDO are 13.83kcal/mol, respectively and the heat of adsorption are -6.458 and -5.045kcal/mol, respectively.

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Kinetics of Oxidative Coupling of Methane over NaCl/ZnO/α-Al2O3 Catalyst (NaCl/ZnO/α-Al2O3 촉매상에서 메탄의 Oxidative Coupling의 속도론적 고찰)

  • Kim, Sang-Chai;Seo, Ho-Joon;Sunwoo, Chang-Shin;Yu, Eui-Yeon
    • Applied Chemistry for Engineering
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    • v.3 no.2
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    • pp.256-265
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    • 1992
  • The kinetics for the oxidative coupling of methane over NaCl(30wt%)/ZnO(60wt%)/${\alpha}-Al_2O_3$ catalyst was investigated, and then the active oxygen species were discussed. The conversion rate of methane was measured at the atmospheric pressure with various combinations of partial pressure of methane and oxygen at temperature range of $650^{\circ}C{\sim}750^{\circ}C$, at conversions less than with 10%. These rate data were then used to verify the proposed Langmuir-Hinshelwood kinetic equation. The rate limiting step appeared to be the formation of the methyl radicals by the reactin of the adsorbed methane and the adsorbed oxygen, which were adsorbed on the different active sites of the catalyst. The activation energy of the methyl radical formation was estimated to be ca. 39 kcal/mol. From the kinetic studies, the oxygen species respolsible for the formation of methyl radicals was proposed to be diatomic oxygen such as $O{_2}{^{2-}}$ or $O_2{^-}$ on the surface.

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Synthesis of ETBE as an Octane Enhancer for Gasoline over Macroreticular Robin Catalysts (그물구조 수지 촉매상에서 가솔린 옥탄가 향상제인 ETBE 합성)

  • Park, Jin-Hwa;Lee, Jin-Hyung;Kim, Jae-Seung
    • Applied Chemistry for Engineering
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    • v.5 no.5
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    • pp.825-835
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    • 1994
  • Synthesis of ETBE as an octane number enhancer from ethanol and isobutene in a flow reactor under atmospheric pressure was studied. Amberlyst-15 and Amberlyst XN-1010 were used as catalysts within the temperature range of $70-140^{\circ}C$. The activity of Amberlyst 15 was higher than that of Amberlyst XN-1010. The reaction rate data obtained under differential reactor condition were tested by a linear regression method to determine the reaction mechanism and kinetic parameters. The ETBE synthesis reaction seems to be proceeded via the LHHW(Langmuir-Hinshelwood-Hougen-Watson) machanism. The activation energy of the surface reaction was estimated by the reaction rate constants as well as the adsorption equilibrium constants. Apparent activation energies are 18.64 and 24.19kcal/mol for Amberlyst-15 and Amberlyst XN-1010, respectively.

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