• 제목/요약/키워드: chemical kinetics

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DAEM 분석 방법을 통한 국내 수입탄의 탈휘발화 반응특성 비교연구 (Application of a DAEM Method for a Comparison of Devolatilization Kinetics of Imported Coals)

  • 김량균;송주헌;이병화;장영준;전충환
    • Korean Chemical Engineering Research
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    • 제48권1호
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    • pp.110-115
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    • 2010
  • 본 연구 목적은 두가지 종류의 국내 수입탄에 대한 열분해 반응율을 구하고 이를 비교하는 것이다. 이를 위해 TGA를 통하여 열분해 실험을 수행하였으며, 반응상수 분석은 New DAEM 방법을 이용하였다. 서로 다른 가열속도에서 각각 얻어진 TGA 질량변화 곡선으로부터, 활성화 에너지의 분포함수를 구한 후 최고빈도를 나타내는 활성화 에너지를 평균 활성화 에너지로 결정하였다. 그 결과 석탄의 종류에 따라 상기 반응에 대한 반응속도상수가 확실한 차이를 보였다. 이 같은 New DAEM 분석기법을 통해 얻은 반응상수를 적용시킨 CPD 모델을 가지고 예측한 결과가 TGA 실험치와 비교할 때보다 더 잘 일치함도 확인할 수 있었다.

왕겨의 마이크로파 탄화속도 (Kinetics on the Microwave Carbonization of Rice Chaff)

  • 김지현;유승곤;김동국
    • Korean Chemical Engineering Research
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    • 제43권6호
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    • pp.683-690
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    • 2005
  • 왕겨를 마이크로파로 탄화하고 그의 탄화속도를 기존의 열적 탄화에 의한 탄화속도와 비교하였다. 왕겨를 $300{\sim}600^{\circ}C$에서 각각 30분 동안 열적 탄화하고 그의 탄화속도를 분석한 결과 탄화온도가 증가할수록 질량감소 및 탄화도(C/H 몰비)가 현저히 증가했지만 왕겨에 마이크로파를 조사하면 입사전력과 조사시간이 증가해도 탄화가 일어나지 않았다. 그러나 $600^{\circ}C$에서 30분 동안 탄화시켜 C/H 몰비가 3.0 이상인 탄화왕겨 6 wt%를 왕겨에 혼합시키고 마이크로파를 조사한 결과 탄화가 잘 되었고 그의 속도식은 마이크로파 입사전력 및 조사시간에 의존하였으며 열적 탄화와 마찬가지로 Arrhenius 식으로 잘 표현되었다. 이때 마이크로파 탄화로 얻어진 활성화에너지는 열적 탄화에 비하여 크게 낮은 반면에 반응속도상수는 훨씬 컸다. 이는 마이크로파 흡수촉진 매체, 즉 촉매적 개시제(initiator)로 사용된 탄화왕겨에 대한 마이크로파 에너지의 내부 부피가열 특성에 기인한 것으로 판단된다. 마이크로파 흡수특성에 대한 왕겨의 회분과 탄화왕겨의 탄화도 및 혼합비율에 대한 영향을 검토하였다.

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

  • Xu, Zhi-Xian;Xu, Jing;Xu, Liang-Hua;Dai, Yong-Qiang;Xue, Li-Wei;Jin, Ri-Guang
    • 폴리머
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    • 제32권2호
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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.

Investigation of Cure Kinetics and Storage Stability of the o-Cresol Novolac Epoxy Nanocomposites with Pre-intercalated Phenolic Hardeners

  • Hwang, Tae-Yong;Lee, Jae-Wook;Lee, Sang-Min;Nam, Gi-Joon
    • Macromolecular Research
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    • 제17권2호
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    • pp.121-127
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    • 2009
  • The cure kinetics of the epoxy-layered, silicate nanocomposites were studied by differential scanning calorimetry under isothermal and dynamic conditions. The materials used in this study were o-cresol novolac epoxy resin and phenol novolac hardener, with organically modified layered silicates. Various kinetic parameters, including the reaction order, activation energy, and kinetic rate constants, were investigated, and the storage stability of the epoxy-layered silicate nanocomposites was measured. To synthesize the epoxy-layered silicate nanocomposites, the phenolic hardener underwent pre-intercalation by layered silicate. From the cure kinetics analyses, the organically modified layered silicate decreased the activation energy during cure reaction in the epoxy/phenolic hardener system. In addition, the storage stability of the nanocomposite with the pre-intercalated phenolic hardener was significantly increased compared to that of the nanocomposite with direct mixing of epoxy, phenolic hardener, and layered silicate. This was due to the protective effect of the reaction between onium ions and epoxide groups.

여러 CO2-O2 혼합기체에서 인도산 분말숯의 등온 연소반응 (Combustion Kinetics of Pulverized Indian Coal-Char in Different CO2-O2 Mixture Isothermally)

  • Saravanan, V.;Shivakumar, R.;babu, P. Niruguna;Ramakrishna
    • 대한화학회지
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    • 제53권6호
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    • pp.635-639
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    • 2009
  • 여러 $CO_2-O_2$ 혼합기체에서 인도산 분말숯의 연소반응실험을 수행하였다. 샘플을 분쇄하여 58 마이크론보다 작은 채로 거르고 질소분위기에서 숯으로 만들었다. CPRI 방갈로에 있는 열분석기 (TGA-50)을 사용해 실험을 하였다. $CO_2-O_2$ 혼합기체는 몰비로 (80-20, 60-40, 40-60, 20-80)을 사용하였다. 활성화에너지 (E) 및 지수앞자리인자 (A)을 통합접근 및 수정된 Arrhenius식을 사용해 계산하였다.

Role of Diffusion in the Kinetics of Reversible Enzyme-catalyzed Reactions

  • Szabo, Attila;Zhou, Huan-Xiang
    • Bulletin of the Korean Chemical Society
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    • 제33권3호
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    • pp.925-928
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    • 2012
  • The accurate expression for the steady-state velocity of an irreversible enzyme-catalyzed reaction obtained by Shin and co-workers (J. Chem. Phys. 2001, 115, 1455) is generalized to allow for the rebinding of the product. The amplitude of the power-law ($t^{-1/2}$) relaxation of the free- and bound-enzyme concentrations to steady-state values is expressed in terms of the steady-state velocity and the intrinsic (chemical) rate constants. This result is conjectured to be exact, even though our expression for the steady-state velocity in terms of microscopic parameters is only approximate.

Curing Kinetics of the No-Flow Underfill Encapsulant

  • Jung, Hye-Wook;Han, Sang-Gyun;Kim, Min-Young;Kim, Won-Ho
    • 한국마이크로전자및패키징학회:학술대회논문집
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    • 한국마이크로전자및패키징학회 2001년도 추계 기술심포지움
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    • pp.134-137
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    • 2001
  • The cure kinetics of a cycloalipatic epoxy / anhydride / Co(II) system for a no-flow underfill encapsulant, has been studied by using a differential scanning calorimetry(DSC) under isothermal and dynamic conditions over the temperature range of $160^{\circ}C ~220^{\circ}C$. The kinetic analysis was carried out by fitting dynamic/isothermal heating experimental data to the kinetic expressions to determine the reaction parameters, such as order of reaction and reaction constants. Diffusion-controlled reaction has been observed as the cure conversion increases and successfully analyzed by incorporating the diffusion control term into the rate equation. The prediction of reaction rates by the model equation corresponded well to experimental data at all temperature.

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Kinetics and Optimization of Dimethyl Carbonate Synthesis by Transesterification using Design of Experiment

  • Lee, Kilwoo;Yoo, Kye Sang
    • Korean Chemical Engineering Research
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    • 제56권3호
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    • pp.416-420
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    • 2018
  • A comprehensive kinetic study has been conducted on dimethyl carbonate synthesis by transesterification reaction of ethylene carbonate with methanol. An alkali base metal (KOH) was used as catalyst in the synthesis of DMC, and its catalytic ability was investigated in terms of kinetics. The experiment was performed in a batch reactor at atmospheric pressure. The reaction orders, the activation energy and the rate constants were determined for both forward and backward reactions. The reaction order for forward and backward reactions was 0.87 and 2.15, and the activation energy was 12.73 and 29.28 kJ/mol, respectively. Using the general factor analysis in the design of experiments, we analyzed the main effects and interactions according to the MeOH/EC, reaction temperature and KOH concentration. DMC yield with various reaction conditions was presented for all ranges using surface and contour plot. Furthermore, the optimal conditions for DMC yield were determined using response surface method.

Cybernetic Modeling of Simultaneous Saccharification and Fermentation for Ethanol Production from Steam-Exploded Wood with Brettanomyces custersii

  • Shin Dong-Gyun;Yoo Ah-Rim;Kim Seung-Wook;Yang Dae-Ryook
    • Journal of Microbiology and Biotechnology
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    • 제16권9호
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    • pp.1355-1361
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    • 2006
  • The simultaneous saccharification and fermentation (SSF) process consists of concurrent enzymatic saccharification and fermentation. In the present cybernetic model, the saccharification process, which is based on the modified Michaelis-Menten kinetics and enzyme inhibition kinetics, was combined with the fermentation process, which is based on the Monod equation. The cybernetic modeling approach postulates that cells adapt to utilize the limited resources available to them in an optimal way. The cybernetic modeling was suitable for describing sequential growth on multiple substrates by Brettanomyces custersii, which is a glucose- and cellobiose-fermenting yeast. The proposed model was able to elucidate the SSF process in a systematic manner, and the performance was verified by previously published data.

환원온도가 Pt/MoO3/SiO2 촉매에서 iso-butene 의 골격 이성질화반응에 미치는 영향 (Effect of reduction Temperature on the Skeletal Isomerization of iso-butene over Pt/MoO3/SiO2 Catalyst)

  • 조새정;김성민;김동회;김성수;김진걸
    • 한국산학기술학회:학술대회논문집
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    • 한국산학기술학회 2004년도 추계학술대회
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    • pp.280-283
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    • 2004
  • Effect of H2 spillover rate as function of reduction temperature on reaction kinetics was evaluated. Reaction kinetics including yield, conversion, activation energy and selectivity of 1-butene isomerization over Pt/HxMoO/SiO were measured as reaction temperature was increased. While conversion of 1-butane was decreased, yield of iso-butene was increased. Two kinds of reaction mechanism were proposed from the change of selectivity as function of temperature.

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