• Title/Summary/Keyword: Oxidation kinetics

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Kinetics Study for Wet Air Oxidation of Sewage Sludge (하수슬러지의 습식산화반응에 대한 동력학적 연구)

  • Ahn, Jae-Hwan
    • Journal of Korean Society of Environmental Engineers
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    • v.27 no.7
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    • pp.746-752
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    • 2005
  • In this study, the effect of reaction parameters including reaction temperature, time, and pressure on sludge degradation and conversion to intermediates such as organic acids were investigated at low critical wet air oxidation(LC-WAO) conditions. Degradation pathways and a modified kinetic model in LC-WAO were proposed and the kinetics model predictions were compared with experimental data under various conditions. Results in the batch experiments showed that reaction temperature directly affected the thermal hydrolysis reaction rather than oxidation reaction. The efficiencies of sludge degradation and organic acid formation increased with the increase of the reaction temperature and time. The removal of SS at $180^{\circ}C$, $200^{\circ}C$, $220^{\circ}C$ and $240^{\circ}C$ of reaction temperatures and 10 min of reaction time were 52.6%, 68.3%, 72.6%, and 74.4%, respectively, indicating that most organic suspended solids were liquified at early stage of reaction. At $180^{\circ}C$, $200^{\circ}C$, $220^{\circ}C$ and $240^{\circ}C$ of reaction temperatures and 40 min of reaction time, the amounts of organic acids formed from 1 g of sludge were 93.5 mg/g SS, 116.4 mg/g SS, 113.6 mg/g SS, and 123.8 mg/g SS, respectively, and the amounts of acetic acid from 1 g of sludge were 24.5 mg/g SS, 65.5 mg/g SS, 88.1 mg/g SS, and 121.5 mg/g SS, respectively. This suggested that the formation of sludge to organic acids as well as the conversion of organic acids to acetic acid increased with reaction temperature. Based on the experimental results, a modified kinetic model was suggested for the liquefaction reaction of sludge and the formation of organic acids. The kinetic model predicted an increase in kinetic parameters $k_1$ (liquefaction of organic compounds), $k_2$ (formation of organic acids to intermediate), $k_3$ (final degradation of intermediate), and $k_4$ (final degradation of organic acids) with reaction temperature. This indicated that the liquefaction of organic solid materials and the formation of organic acids increase according to reaction temperature. The calculated activation energy for reaction kinetic constants were 20.7 kJ/mol, 12.3 kJ/mol, 28.4 kJ/mol, and 54.4 kJ/mol, respectively, leading to a conclusion that not thermal hydrolysis but oxidation reaction is the rate-limiting step.

Kinetic Study of Cyclization of High-Tacticity Polyacrylonitrile Heat-Treated under Air Atmosphere via XRD (공기분위기 하에서 열처리된 고입체 규칙성 폴리아크릴로니트릴의 XRD에 의한 환화반응 속도 연구)

  • Xu, Zhi-Xian;Xu, Jing;Xu, Liang-Hua;Dai, Yong-Qiang;Xue, Li-Wei;Jin, Ri-Guang
    • Polymer(Korea)
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    • v.32 no.2
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    • pp.150-156
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    • 2008
  • Two different polyacrylonitrile samples (PANs, triad tacticity fraction is 0.25 and 0.64) were synthesized and used to study the kinetics of cyclization. Polymers were treated at different temperatures between 250 to $300^{\circ}C$ under air atmosphere, and analyzed by X-ray diffractometer. The sharp and strong peak at $2{\theta}=16.5^{\circ}$ corresponds to a lateral repeat distance that is the (100) diffraction in hexagonal lattice, while the peak at $2{\theta}=25.5^{\circ}$ reflects the (101) diffraction. In comparing their areas of different heat treated samples, the cyclization of both PANs was identified as a first-order reaction. The rate constants of cyclization reaction at different temperatures and the active energy parameter were obtained. This results might provide an important effect on pre-oxidation of polyacrylonitrile fiber.

2,4-Dichlorophenol Enzymatic Removal and Its Kinetic Study Using Horseradish Peroxidase Crosslinked to Nano Spray-Dried Poly(Lactic-Co-Glycolic Acid) Fine Particles

  • Dahili, Laura Amina;Nagy, Endre;Feczko, Tivadar
    • Journal of Microbiology and Biotechnology
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    • v.27 no.4
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    • pp.768-774
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    • 2017
  • Horseradish peroxidase (HRP) catalyzes the oxidation of aromatic compounds by hydrogen peroxide via insoluble polymer formation, which can be precipitated from the wastewater. For HRP immobilization, poly(lactic-co-glycolic acid) (PLGA) fine carrier supports were produced by using the Nano Spray Dryer B-90. Immobilized HRP was used to remove the persistent 2,4-dichlorophenol from model wastewater. Both extracted (9-16 U/g) and purified HRP (11-25 U/g) retained their activity to a high extent after crosslinking to the PLGA particles. The immobilized enzyme activity was substantially higher in both the acidic and the alkaline pH regions compared with the free enzyme. Optimally, 98% of the 2,4-dichlorophenol could be eliminated using immobilized HRP due to catalytic removal and partly to adsorption on the carrier supports. Immobilized enzyme kinetics for 2,4-dichlorophenol elimination was studied for the first time, and it could be concluded that competitive product inhibition took place.

Effect of Injection Pressure on Low Temperature Combustion in CI Engines (압축착화 엔진에서 분사압이 저온연소에 미치는 영향)

  • Jang, Jaehoon;Lee, Sunyoup;Lee, Yonggyu;Oh, Seungmook;Lee, Kihyung
    • Journal of ILASS-Korea
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    • v.18 no.1
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    • pp.21-26
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    • 2013
  • Diesel low temperature combustion (LTC) is the concept where fuel is burned at a low temperature oxidation regime so that $NO_x$ and particulate matters (PM) can simultaneously be reduced. There are two ways to realize low temperature combustion in compression ignition engines. One is to supply a large amount of EGR gas combined with advanced fuel injection timing. The other is to use a moderate level of EGR with fuel injection at near TDC which is generally called Modulated kinetics (MK) method. In this study, the effects of fuel injection pressure on performance and emissions of a single cylinder engine were evaluated using the latter approach. The engine test results show that MK operations were successfully achieved over a range of with 950 to 1050 bar in injection pressure with 16% $O_2$ concentration, and $NO_x$ and PM were significantly suppressed at the same time. In addition, with an increase in fuel injection pressure, the levels of smoke, THC and CO were decreased while $NO_x$ emissions were increased. Moreover, as fuel injection timing retarded to TDC, more THC and CO emissions were generated, but smoke and $NO_x$ were decreased.

Development of Reduced Normal Dodecane Chemical Kinetics (축소 노멀 도데케인 화학반응 메커니즘 개발)

  • Lee, Sangyul;Kim, Gyujin;Min, Kyoungdoug
    • Transactions of the Korean Society of Automotive Engineers
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    • v.21 no.2
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    • pp.37-44
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    • 2013
  • Generally, a reduced chemical mechanism of n-heptane is used as chemical fuel of a 3-D diesel engine simulation because diesel fuel consists of hundreds of chemical components and various chemical classes so that it is very complex and large to use for the calculation. However, the importance of fuel in a 3-D simulation increases because detailed fuel characteristics are the key factor in the recent engine research such as homogeneous charged compression ignition engine. In this study, normal paraffin, iso paraffin and aromatics were selected to represent diesel characteristics and n-dodecane was used as a representative normal paraffin to describe the heavy molecular weight of diesel oil (C10~C20). Reduced kinetics of iso-octane and toluene which are representative species of iso paraffin and aromatics respectively were developed in the previous study. Some species were selected based on the sensitivity analysis and a mechanism was developed based on the general oxidation scheme. The ignition delay times, maximum pressure and temperature of the new reduced n-dodecane chemical mechanisms were well matched to the detailed mechanism data.

Simulation of Neutron irradiation Corrosion of Zr-4 Alloy Inside Water Pressure reactors by Ion Bombardment

  • Bai, X.D.;Wang, S.G.;Xu, J.;Chen, H.M.;Fan, Y.D.
    • Journal of the Korean Vacuum Society
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    • v.6 no.S1
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    • pp.96-109
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    • 1997
  • In order to simulate the corrosion behavior of Zr-4 alloy in pressurized water reactors it was implanted (or bombarded) with 190ke V $Zr^+\; and \;Ar^+$ ions at liquid nitrogen temperature and room temperature respectively up to a dose of $5times10^{15} \sim 8\times10^{16} \textrm{ions/cm}^2$ The oxidation behavior and electrochemical vehavior were studied on implanted and unimplanted samples. The oxidation kinetics of the experimental samples were measured in pure oxygen at 923K and 133.3Pa. The corrosion parameters were measured by anodic polarization methods using a princeton Applied Research Model 350 corrosion measurement system. Auger Electron Spectroscopy (AES) and X-ray Photoelectric Spectroscopy (XPS) were employed to investigate the distribution and the ion valence of oxygen and zirconium ions inside the oxide films before and after implantation. it was found tat: 1) the $Zr^+$ ion implantation (or bombardment) enhanced the oxidation of Zircaloy-4 and resulted in that the oxidation weight gain of the samples at a dose of $8times10^{16}\textrm{ions/cm}^2$ was 4 times greater than that of the unimplantation ones;2) the valence of zirconium ion in the oxide films was classified as $Zr^0,Zr^+,Zr^{2+},Zr^{3+}\; and \;Zr^{4+}$ and the higher vlence of zirconium ion increased after the bombardment ; 3) the anodic passivation current density is about 2 ~ 3 times that of the unimplanted samples; 4) the implantation damage function of the effect of ion implantation on corrosion resistance of Zr-4 alloy was established.

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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.

Oxidation Behavior of Simudated Metallic U-Nb Alloys in Air (모의 금속전환체 U-Nb 합금의 공기중 산화거동)

  • Lee Eun-Pyo;Ju June-Sik;You Gil-Sung;Cho il-Je;Kook Dong-Hak;Kim Ho-Dong
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.2 no.4
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    • pp.239-244
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    • 2004
  • In order to enhance an oxidation resistance of the pure uranium metal under air condition, a small quantity of niobium(Nb) which is known to mitigate metal oxidation is added into uranium metal as an alloying element. A simulated metallic uranium alloy, U-Nb has been fabricated and then oxidized in the range of 200 to $300^{\circ}C$ under the environment of the pure oxygen gas. The oxidized quantity in terms of the weight gain(wt%) has been measured with the help of a thermogravimetric analyzer. The results show that the oxidation resistance of the U-Nb alloy is considerably enhanced in comparison with that of the pure uranium metal. It is revealed that the oxidation resistance of the former with the niobium content of 1, 2, 3, and 4 wt% is : 1) 1.61, 7.78, 11.76 and 20.14 times at the temperature of $200^{\circ}C$ ; 2) 1.45, 5.98, 10.08 and 11.15 times at $250^{\circ}C$ ; and 3) 1.33, 4.82, 8.87 and 6.84 times at $300^{\circ}C$ higher than that of the latter, respectively. Besides, it is shown that the activation energy attributable to the oxidation is 17.13~21.92 kcal/mol.

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Kinetics of Photocatalytic Reactions with Porous Carriers Coated with Nano-$TiO_2$ Particles (나노-$TiO_2$ 입자로 코팅된 다공성 담체의 광촉매 반응에 관한 동력학)

  • Park, Seong-Jun;Rittmann, Bruce E.;Bae, Woo-Keun
    • Journal of Korean Society of Environmental Engineers
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    • v.31 no.10
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    • pp.927-932
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    • 2009
  • Toxic and recalcitrant organic pollutants in wastewaters can be effectively treated when advanced oxidation and biodegradation are combined, ideally with intimate coupling, in which both processes occur simultaneously in the same system. One means to achieve intimate coupling is to coat nanoscale $TiO_2$ on the outside of macroporous biofilm carriers. This study investigated the kinetics of photocatalysis with $TiO_2$-coated porous carriers. The carriers were made of polyvinyl alcohol (PVA) and coated with $TiO_2$ using a low-temperature sol-gel process. The $TiO_2$-coated carriers catalyzed the oxidation of methylene blue (MB) effectively under irradiation of UV light. The overall reaction rate with adsorption and photolysis saturated at high MB concentration, and approached the adsorption rate, which was first order for all MB concent rations. This result indicates that adsorbed MB may have slowed photocatalysis by blocking active sites for photocatalysis. The overall kinetics could be described by a quasi-Langmuir model. The estimated maximum specific (per unit mass of $TiO_2$) transformation rate of MB by the $TiO_2$-coated carriers was four times larger than that obtained from slurry-$TiO_2$ reactors. This observation demonstrated that the $TiO_2$ present as a coating on the carriers maintained high efficiency for transforming recalcitrant organic matter via photocatalysis. These findings serve as a foundation for advancement of an intimate coupling of photocatalysis to biodegradation.

Atmospheric Effects on Growth Kinetics and Electronic Properties of Passive Film of Aluminum in Borate Buffer Solution (Borate 완충용액에서 알루미늄의 산화피막의 생성과정과 전기적 성질에 대한 대기의 영향)

  • Kim, Younkyoo
    • Journal of the Korean Chemical Society
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    • v.60 no.3
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    • pp.169-176
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    • 2016
  • In a borate buffer solution, the growth kinetics and the electronic properties of passive film on aluminum were investigated, using the potentiodynamic method, chronoamperometry, and multi-frequency electrochemical impedance spectroscopy. The corrosion of aluminum was heavily influenced by the degree of oxygen concentration because of the increasing reduction current. The oxide film formed during the passivation process of aluminum has showed the electronic properties of n-type semiconductor, which follow from the Mott-Schottky equation. It was found out that the passive film (Al(OH)3) of Al formed in the low electrode potential changes to Al2O3 while the electrode potential increases. The growth kinetics data as measured by chronoamperometry suggests a mechanism in which the growth of the film of Al2O3 is determined by field-assisted transport of ions through the film.