• 제목/요약/키워드: activation energy for decomposition

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열중량 분석법을 이용한 Deasphalted Oil의 열분해 특성 분석 (Study on the Pyrolysis Kinetics of Deasphalted Oil Using Thermogravimetric Analysis)

  • 신상철;이정무;이기봉;전상구;나정걸;노남선
    • Korean Chemical Engineering Research
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    • 제50권3호
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    • pp.391-397
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    • 2012
  • 기존 경질 원유 자원의 매장량 고갈과 중국, 인도 등 개발도상국에서의 에너지 수요가 급증하면서 원유 자원의 공급이 수요를 감당하지 못하는 상황이 벌어지고 있고, 따라서 상대적으로 활용도가 낮았던 중질유를 효율적으로 이용하는 방안이 대두되고 있다. 중질유를 활용하기 위해서는 경질화 과정을 거쳐야하는데, 특히 공정이 단순하고 경제적인 열분해 기술이 적합하다고 할 수 있겠다. 본 연구에서는 중질유의 열분해 특성 분석의 기초 자료를 얻기 위해 중질유에서 아스팔텐이 제거된 deasphalted oil(DAO)의 열분해 실험을 수행하였다. DAO는 solvent deasphalting 공정을 통하여 얻어지며 주로 탄소수가 20~40인 물질들로 이루어져 있는데, DAO의 열분해 반응 속도론적 분석 결과와 비교 분석하기 위해 DAO의 평균 탄소수를 갖는 탄소수 30의 단일 물질들($C_{30}H_{62}$, $C_{30}H_{58}O_4S$, $C_{30}H_{63}O_3P$)을 선택하여 추가적인 열분해 실험을 수행하였다. 열분해 실험에서는 열중량 분석기를 이용하여 비등온 열분해 방법(10, 50, $100^{\circ}C$/min)으로 실험을 진행하였고, 열분해 반응을 분석하는 방법으로는 가장 기초적인 Arrhenius 방법을 비롯하여 Ingraham and Marrier 방법, Coats and Redfern 방법, Ozawa-Flynn-Wall 방법을 이용하였다. Arrhenius, Ingraham and Marrier, Coats and Redfern 방법으로 계산된 DAO의 열분해 반응 평균 활성화에너지 값은 72~99 kJ/mol이었다. 그리고 Ozawa-Flynn-Wall 방법으로 분석된 활성화에너지에서는 전환율의 증가에 따라 DAO의 경우 그 상승 폭이 단일 물질들에 비해 크게 나타났다.

Sievert's type 자동장치에 의한 마그네슘 수소화합물의 열분석 (Thermal Analysis of Mg Hydride by Sievert's Type Automatic Apparatus)

  • 한정섭;박경덕
    • 대한금속재료학회지
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    • 제48권12호
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    • pp.1123-1129
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    • 2010
  • In order to apply the Sievert's type automatic apparatus to thermal analysis of hydrogen absorbing materials, the dehydrogenation of the Mg-H system was investigated. As the initial wt% of hydrogen was increased to 4.4, the peak temperature of evolution rate shifted to higher temperature. However, with the initial wt% of hydrogen higher than 4.4, peak temperature of evolution rate did not change. The peak temperatures of evolution rate obtained by automatic apparatus were almost the same as those measured by a manual apparatus. As the heating rate was increased, the peak temperatures increased; the peak temperatures for heating rates 1, 2 and 3 K/min were 664, 687 and 702 K, respectively. The activation energy for the decomposition of Mg hydride was 101 kJ/mol. The Sievert's type automatic apparatus can be successively applied to the thermal analysis of metal hydride.

Kinetic Analysis for the Catalytic Pyrolysis of Polyethylene Terephthalate Over Cost Effective Natural Catalysts

  • Pyo, Sumin;Hakimian, Hanie;Kim, Young-Min;Yoo, Kyung-Seun;Park, Young-Kwon
    • 공업화학
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    • 제32권6호
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    • pp.706-710
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    • 2021
  • In the current research, thermal and catalytic thermogravimetric (TG) analysis of polyethylene terephthalate (PET) over natural zeolite (NZ), olivine, bentonite, HZSM-5, and HAl-MCM-41 were investigated using a TG analyzer and model-free kinetic analysis. Catalytic TG analysis of PET was carried out at multi-heating rates, 10, 20, 30, and 40 ℃/min, under nitrogen atmosphere. Apparent activation energy (Ea) values for the thermal and catalytic pyrolysis of PET were calculated using Flynn-Wall-Ozawa method. Although natural catalysts, NZ, olivine, and bentonite, could not lead the higher PET decomposition efficiency than synthetic zeolites, HZSM-5 and HAl-MCM-41, maximum decomposition temperatures on the differential TG (DTG) curves for the catalytic pyrolysis of PET, 436 ℃ over olivine, 435 ℃ over bentonite, and 434 ℃ over NZ, at 10 ℃/min, were definitely lower than non-catalytic pyrolysis. Calculated Ea values for the catalytic pyrolysis of PET over natural catalysts, 177 kJ/mol over olivine, 168 kJ/mol over bentonite, and 171 kJ/mol over NZ, were also not lower than those over synthetic zeolites, however, those were also much lower than the thermal decomposition, suggesting their feasibility as the proper and cost-effective catalysts on the pyrolysis of PET.

센서 패키지용 고분자 접착제의 열화 거동 분석 (Kinetic Analyses on Thermal Degradation of Epoxy Based Adhesive for Packaging Application)

  • 김영국;이윤선
    • 마이크로전자및패키징학회지
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    • 제24권1호
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    • pp.67-73
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    • 2017
  • 열중량 분석(Thermogravimetry)을 이용하여 열화시간 경과에 따른 접착 소재의 열에 대한 열화 특성을 분석하였다. 실험에는 여섯 가지의 온도 승온률에서 측정된 데이터를 이용하여 열화에 따른 동적 반응을 분석하였다. 이 데이터를 바탕으로 아레니우스 방정식을 이용하여 활성 에너지와 비례 상수 등 모델에 필요한 계수를 계산하였다. 또한 열화거동을 예측하는 방정식으로는 무게 감소에 따른 간단한 n차 방정식을 이용하였다. 구해진 예측 모델은 실험 데이터와 비교하여 검증하였다. 계산 결과 각 승온률에 따라 활성화 에너지의 크기가 다름에 따라 평균값을 사용하여 계산한 결과는 낮은 승온률인 경우에는 잘 예측하였지만 높은 승온률인 경우에는 측정값과 차이를 보였다. 이와 같은 문제를 해결하기 위해 지수함수 급수를 이용한 새로운 모델링 방법이 처음 시도되었으며 예측된 결과는 승온률에 관계없이 실험 데이터와 잘 일치하였다.

Applications of Time-Temperature Integrator (TTI) as a Quality Indicator of Grounded Pork Patty

  • Chun, Ji-Yeon;Choi, Mi-Jung;Lee, Seung Ju;Hong, Geun-Pyo
    • 한국축산식품학회지
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    • 제33권4호
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    • pp.439-447
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    • 2013
  • Time-temperature integrators (TTIs) are simple and cost-efficient tools which may be used to predict food quality. Enzymatic TTIs are devised to indicate food quality in the form of color alterations from green to red, based on the cumulative impacts of temperature and time period on the enzymatic reactions. In this study, the quality of ground beef patties was investigated for the parameters of pH levels, color, VBN, water holding capacity, and total microbial counts, depending on various storage temperatures (5, 15, and $25^{\circ}C$). TTIs were attached to the surface of the ground beef patties in order to evaluate the degree of correlating colorimetric changes with the determined quality parameters. Through the Arrhenius equation, activation energy and constant reaction rates of TTI, VBN, and total microbial counts were calculated as to observe the relationship between enzymatic reactions of the TTI and food spoilage reactions of the ground beef patties. VBN and total microbial counts were already increased to reach decomposition index (VBN: 20, total microbial count: 7-8 Log CFU/g) of meat at middle stage of storage period for each storage temperature. Although activation energy of TTI enzymatic reactions and food spoilage reactions of the ground beef patties were similar, the change of TTI color was not a coincidence for food spoilage at $5^{\circ}C$ and $15^{\circ}C$ of storage temperature. It was suggested that TTI should be designed individually for storage temperature, time, type of meat, or decomposition index of meat.

RPSO 알고리즘을 이용한 탄화 재료의 열분해 물성치 추정 (Estimation of the Properties for a Charring Material Using the RPSO Algorithm)

  • 장희철;박원희;윤경범;김태국
    • 한국유체기계학회 논문집
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    • 제14권1호
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    • pp.34-41
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    • 2011
  • Fire characteristics can be analyzed more realistically by using more accurate properties related to the fire dynamics and one way to acquire these fire properties is to use one of the inverse property estimation techniques. In this study two optimization algorithms which are frequently applied for the inverse heat transfer problems are selected to demonstrate the procedure of obtaining pyrolysis properties of charring material with relatively simple thermal decomposition. Thermal decomposition is occurred at the surface of the charring material heated by receiving the radiative energy from external heat sources and in this process the heat transfer through the charring material is simplified by an unsteady 1-dimensional problem. The basic genetic algorithm(GA) and repulsive particle swarm optimization(RPSO) algorithm are used to find the eight properties of a charring material; thermal conductivity(virgin, char), specific heat(virgin, char), char density, heat of pyrolysis, pre-exponential factor and activation energy by using the surface temperature and mass loss rate history data which are obtained from the calculated experiments. Results show that the RPSO algorithm has better performance in estimating the eight pyrolysis properties than the basic GA for problems considered in this study.

($Zn_{x}Fe_{3-x}O_{4-{\delta}}$를 이용한 이산화탄소의 분해 (Decomposition of Carbon Dioxide using $Zn_{x}Fe_{3-x}O_{4-{\delta}}$)

  • 양천모;조영구;임병오
    • 한국응용과학기술학회지
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    • 제17권1호
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    • pp.55-61
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    • 2000
  • $Zn_{x}Fe_{3-x}O_{4}(0.00.<X<0.08)$ was synthesized by air oxidation method for the decomposition of carbon dioxide. We investigated the characteristics of catalyst, the form of methane by gas chromatograph after decomposition of carbon dioxide and kinetic parameter. $Zn_{x}Fe_{3-x}O_{4}(0.00.<X<0.08)$ was spinel type structure. The surface areas of catalysts($Zn_{x{Fe_{3-x}O_{4}(0.00.<X<0.08)$) were $15{\sim}27$ $m^{2}/g$. The shape of $Zn_{0.003}Fe_{2.997}O_{4}$ was sphere. The optimum temperature for the decomposition of carbon dioxide into carbon was $350^{\circ}C$. $Zn_{0.003}Fe_{2.997}O_{4}$ showed the 85% decomposition rate of carbon dioxide and the degree of reduction by hydrogen(${\delta}$) of $Zn_{0.003}Fe_{2.997}O_{4}$ was 0.32. At $350^{\circ}C$, the reaction rate constant and activation energy of $Zn_{0.003}Fe_{2.997}O_{3.68}$ for the decomposition of carbon dioxide into carbon were 3.10 $psi^{1-{\alpha}}/min$ and 0.98 kcal/mole respectively. After the carbon dioxide was decomposed, the carbon which was absorbed on the catalyst surface was reacted with hydrogen and it became methane.

스피넬상 마그네타이트를 이용한 $CO_2$ 분해의 최적조건 (The Optimum of $CO_2$ Decomposition using Spinel Phase Magnetite)

  • 류대선;홍필선;이풍헌;김순태
    • 한국세라믹학회지
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    • 제38권10호
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    • pp.901-907
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    • 2001
  • 이산화탄소($CO_2$)분해를 위해 $0.2M-FeSO_4{\cdot}7H_{2}O$와 0.5 M-NaOH를 사용하여 공기산화법으로 magnetite를 합성하였다. 합성한 magnetite를 2시간 동안 수소($H_2$)로 환원하여 325, 350, 375, 400, $425^{\circ}C$에서 이산화탄소의 분해반응을 실시하였다. 실험결과 $350^{\circ}C$에서 이산화탄소의 분해율이 88%로 가장 우수한 것으로 나타났으며, magnetite를 이용한 이산화탄소의 분해에 대한 활성화에너지는 30.96 kJ/mol이였다. 이산화탄소의 분해 후 촉매 표면의 탄소와 수소가 반응하여 메탄을 생성하였다.

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Poly(n-butyl methacrylate)의 열분해에 관한 연구 (Study on the Thermal Degradation of Poly(n-bulyl methacrylate))

  • 곽기철;설수덕;손진언
    • Elastomers and Composites
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    • 제23권3호
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    • pp.213-222
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    • 1988
  • The thermal decomposition of poly(n-butyl methacrylate)(Pn-BMA) was studied using a dynamic and isothermal thermogravimetry in nitrogen gas with 50ml/min at several heating rates from 1 to $20^{\circ}C/min$, and at several heating temperature from 320 to $370^{\circ}C$. The mathematical techniques used for calculation of activation energy were Kissinger, Anderson, Chatterjee-Conrad, Friedman, Fuoss, Ozawa and isolthermal method. The range of activation energies obtained using the several techniques was between 43 and 51Kcal/mol except Chatterjee-Conrad and this range agreed with each other very well. The thermal degradation of Pn-BMA was considered to be carried out by main chain scission.

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메틸메타크릴레이트의 환경친화적인 광중합 및 열분해특성 (A Characteristics of Environmental Fraternitive Photopolymerization and Thermal Degradation on Methyl Methacrylate)

  • 주영배;이내우;최재욱;강돈오;설수덕
    • 한국안전학회지
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    • 제16권3호
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    • pp.68-75
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    • 2001
  • Photopolymerization, the utilization of electromagnetic radiation(or light) as the energy source for polymerization of functional monomers, oligomers is the basis of important commercial processes with broad applicability, including photoimaging and RV curing of coatings and inks. The objective of this study is to investigate the characteristics of environmental fraternitive photopolymerization of methyl methacrylate(MMA). This work is the first step to continue further research about alkyl methacrylate. The experiment was done in aqueous solution under the influence of photo-initiator concentration(0.05-0.25mol/l), light intensity (5000-9000 ${\mu}J/cm^2$) and monomer concentration(2-6mol/l). Methyl methacrylate was polymerized to high conversion ratio using hydrogen peroxide($H_2O_2$) and the kinetics model we have obtained is as follows. $R_p=k_p[S]^{0.41}[M]^{0.62}[L]^{2.45} exp(53.64/RT$). The differential method of thermogravimetric analysis(Friedman method) was used to obtain value of activation energy on decomposition reaction. The average value of it res 45.4Kca1/mol.

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