• Applied Chemistry for Engineering
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• v.4 no.2
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• pp.365-372
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• 1993

$CO_2$ methanation was performed over Ni supported on cation-exchanged Y zeolites under atmospheric pressure at $250{\sim}550^{\circ}C$ and $H_2/CO_2$ mole ratio of 4. Adsorption strength between carbon dioxide and nickel was found to be Influenced by the cation exchanged in the zeolite. TPD(Temperature-programmed desorption) results show that the adsorption strength decreases in the order of Ni/NaY>Ni/MaY>Ni/HY. TPSR(Temperature-programmed surface reaction) results indicate that enhanced methanation activity is obtained when the adsorption strength between carbon dioxide and nickel is stroing. As the reduction temperature increases, the methantion activity of the catalyst increase. From this result the larger size nickel particle seems advantageous for $CO_2$ methanation reaction. The maximum activity is obtained when nickel loading is 3.3wt%. Carbon monoxide is produced as a by-product throughout the reaction temperature range, and as the contact time increases, the selectivity to methane increases and the selectivity to carbon monoxide decreases steadily. Thus methane seems to be produced from $CO_2$ via CO as an intermediate species. In the temperature range of $410{\sim}450^{\circ}C$, the methane production rate is found to be dependent on the orders of 3.3~-0.5 and 1.4~3.6 with respect to $CO_2$ and $H_2$ partial pressures, respectively. This clearly shows that $CO_2$ and $H_2$ are competing for adsorption sites and as the reaction temperature increases, it becomes increasingly difficult for $H_2$ to be adsorbed on the catalyst surface.

• Applied Chemistry for Engineering
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• v.22 no.6
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• pp.653-657
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• 2011

Conversion characteristics of $CH_4$ and $CO_2$ was studied using an atmospheric pressure plasma for the preparation of synthesis gas composed of $H_2$ and CO. The effects of delivered power, total gas flow rate, and gas residence time in the reactor on the conversion of $CH_4$ and $CO_2$ were evaluated in a plasma reactor with the type of dielectric barrier discharge. The increase of reactor temperature did not affect on the increase of conversion if the temperature does not reach to the appropriate level. The conversion of $CH_4$ and $CO_2$ largely increased with increasing the delivered power. As the $CH_4/CO_2$ ratio increased, the $CH_4$ conversion decreased, whereas the $CO_2$ conversion increased. Generally, the $CH_4$ convesion was higher than the $CO_2$ conversion through the variation of the process parameters.

• Journal of Energy Engineering
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• v.23 no.2
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• pp.62-73
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• 2014

This research was focused to apply response surface methodology for optimization of bio-methane production by biogas upgrading process. Methane concentration(Y1) and methane efficiency(Y2) on biogas upgrading process were mathematically described as being modeled by the use of the Box-Behnken design on response surface methodology. The results of ANOVA(analysis of variance) about models, the probability value of the methane concentration and methane recovery response surface model are 0.0001 and 0.0001, respectively and coefficient of determination($R^2$) are 0.9788 and 0.9710, respectively. The response surface model is proved of high reliability and suitability. The operation pressure had the greatest influence to methane concentration than other operation parameters and the PSA rotary valve velocity had the greatest influence to methane recovery than other operation parameters. Optimal condition of biogas upgrading process for production of $100Nm^3/hr$ bio-methane were operation pressure 8.0bar and outlet flow rate 31.55RPM, respectively. At that operation condition the methane concentration of bio-methane was 97.13% and methane recovery in biogas upgrading process was 75.89%.

• Clean Technology
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• v.28 no.2
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• pp.154-162
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• 2022

Microstructured Al@Al₂O₃ and Al@Ni-Al LDH (LDH = layered double hydroxide) core-shell metal-ceramic composites are prepared by hydrothermal reactions of aluminum (Al) metal substrates. Controlled hydrothermal reactions of Al metal substrates induce the hydrothermal dissolution of Al ions at the Al-substrate/solution interface and reconstruction as porous metal-hydroxides on the Al substrate, thereby constructing unique metal-ceramic core-shell composite structures. The morphology, composition, and crystal structure of the core-shell composites are affected largely by the ions in the hydrothermal solution; therefore, the critical physicochemical and surface properties of these unique metal-ceramic core-shell microstructures can be modulated effectively by varying the solution composition. A Ni/Al@Al₂O₃ catalyst with highly dispersed catalytic Ni nanoparticles on an Al@Al₂O₃ core-shell substrate was prepared by a controlled reduction of an Al@Ni-Al LDH core-shell prepared by hydrothermal reactions of Al in nickel nitrate solution. The reduction of Al@Ni-Al LDH leads to the exolution of Ni ions from the LDH shell, thereby constructing the Ni nanoparticles dispersed on the Al@Al₂O₃. The catalytic properties of the Ni/Al@Al₂O₃ catalyst were investigated for CO₂ methanation reactions. The Ni/Al@Al₂O₃ catalyst exhibited 2 times greater CO₂ conversion than a Ni/Al₂O₃ catalyst prepared by conventional incipient wetness impregnation and showed high structural stability. These results demonstrate the high effectiveness of the design and synthesis methods for the metal-ceramic composite catalysts derived by hydrothermal reactions of Al metal substrates.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.111.2-111.2
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• 2011

최근 지구온난화로 인해 국제적으로 이산화탄소 저감에 대한 연구가 진행되고 있으며 특히, 이산화탄소의 분리 및 유용물질 전환 등의 다양한 방법에 대한 연구가 활발히 이루어지고 있다. 이산화탄소를 메탄으로 전환시키는 생물학적 반응은 acetotrophic methanogen, hydrogenotrophic methanogen 등의 미생물이 관여한다. 본 연구에서는 hydrogenotrohpic methanogen을 이용하여 메탄으로 전환하고자 하였다. 이를 위해 이산화탄소와 수소의 체류시간에 대한 연구를 진행하였으며, 선행 연구로 혐기성슬러지의 혼합배양균으로부터 hydrogenotrophic methanogen을 우점종화 하기 위해 고정층 반응기를 이용하여 이산화탄소와 수소 가스를 주입하여 고농도로 배양하였다. 그 결과, 반응기내의 이산화탄소의 메탄전환 균주로써 수소를 환원제로 이용하는 hydrogenotrophic methanogen이 배양되었음을 확인하였다. 이산화탄소와 수소가스의 체류시간에 따른 이산화탄소의 생물학적 메탄 전환 실험 결과, 약 4시간에서 이산화탄소의 저감률이 99%이었으며, 체류시간이 2시간, 1.5시간인 경우 이산화탄소의 저감률은 각각 71%, 68% 이었다.

• Applied Chemistry for Engineering
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• v.18 no.3
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• pp.239-244
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• 2007

For the simultaneous methane recovery and $CO_2$-stripping, we have been developed dual vent auto circulation bubble lift column reactor, and evaluate optimum conditions for monoethanolamine (MEA) solutions as a $CO_2$ absorbent. At the 5 wt% MEA solution, we investigated the pH change during $CO_2$-stripping and absorption reaction, $CO_2$-stripping rate with reaction time, methane recovery efficiency for various inflow rates of air, $CO_2$-stripping rate for flow liquid over flow height, and $CO_2$-stripping dependency on the temperature of absolvent solutions. The suggested optimum conditions for $CO_2$ recovery with MEA in the dual vent auto circulation bubble lift column reactor were 40 mm over flow liquid height, 1.5 L/min of air inflow rate, and $25^{\circ}C$ of absorbent solution temperature.

• Applied Chemistry for Engineering
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• v.16 no.3
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• pp.337-341
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• 2005

This paper reports the study on coking rate and carbon formation route as a function of reaction temperature using the Ni catalysts in the $CO_2$ reforming of methane. In this paper, carbon deposition on catalysts and its kinetics during reforming reaction were studied by using a thermogravimetric analyzer. Kinetic studies show that reaction orders of carbon formation obtained 1.33 ($CH_4$) and -0.52 ($CO_2$) by experiments on partial pressure of reactant gas, respectively. On the basis of model equation, the kinetic parameters for the coking reaction at different temperatures indicated that methane decomposition dominated carbon formation at lower temperatures ($<600^{\circ}C$), while $CH_4$decomposition and Boudouard reactions become significant for coking in the temperature range of $600{\sim}700^{\circ}C$.

• 한국신재생에너지학회:학술대회논문집
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• 2007.06a
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• pp.779-783
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• 2007

본 연구에서는 가스화공정과 수성가스 전환공정, $CO_2$ 분리공정, 메탄화 공정을 주요 구성으로 한 대체(또는 합성)천연가스(SNG, Substitute or Synthetic Natural Gas)제조공정을 대상으로 석탄, 석탄 촤, 바이오매스 등의 다양한 고체시료를 적용하였을 경우 각 시료의 가스화 반응을 통해 얻어진 합성가스를 이용한 SNG 제조 공정 특성을 파악하고자 하였다. 석탄, 석탄 촤, 바이오매스를 적용한 SNG 공정해석 결과 가스화 공정, 수성가스 전환 공정, 메탄화 공정의 운전 용도가 각 800도, 450도, 300도이고, 수성가스 전환 공정 출구의 합성가스 $H_2$/CO ratio(mol basis)가 3인 조건에서 SNG/Feed ratio는 석탄, 석탄 촤, 바이오매스가 각각 0.35, 0.34, 0.08로 나타났고. SNG Efficiency(%) 는석탄, 석탄 촤 바이오매스에 대해서 각각 61.2%. 48.2%, 17.5%로 나타났다. 또한, 석탄 촤를 대상으로 가스화 공정에서의 산화제 투입 조건 및 스팀 투입조건의 변화에 따른 합성가스 발생 특성을 살펴보았다.

• 한국신재생에너지학회:학술대회논문집
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• 2009.11a
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• pp.232-232
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• 2009

최근 WGS반응용 Pt 촉매의 성능 향상을 위한 다양한 담체 및 조촉매(Promotor) 개발에 대한 연구가 활발하게 진행되고 있다. 선행 연구결과, 입방(Cubic)구조를 가지는 $Ce_{0.8}Zr_{0.2}O_2$ 담체는 정방 입계(Tetragonal)구조를 가지는 $Ce_{0.2}Zr_{0.8}O_2$ 담체 또는 혼합산화물(Mixed oxide)구조를 가지는 $Ce_{0.5}Zr_{0.5}O_2$ 담체 보다 높은 활성과 안전성을 가진다. 이것은 촉매의 성능 향상이 Ce-$ZrO_2$의 결정구조에 의존한다는 것을 나타낸다. 따라서 WGS 반응에서 Ce/Zr 비에 따라 변화된 담체 특성이 Pt 촉매의 활성에 영향이 있을 것으로 예상되며 실험결과 1% Pt/$CeO_2$ 촉매가 가장 높은 활성을 나타내었다. 따라서 Pt/Ce-$ZrO_2$ 촉매의 성능 향상을 위해 Ce-$ZrO_2$ 담체에 조촉매인 Ni을 첨가하여 촉매적 활성을 비교하여 보았다. 촉매는 2%의 Pt과 15%의 Ni로 고정하였고 Ce/Zr 비를 제조변수로 하였다. 제조된 모든 담체는 공침법(Co-precipitation)을 사용하여 제조하였으며 $500^{\circ}C$에서 6시간 소성하였다. Pt 촉매는 함침법 (Incipient wetness impregnation)으로 담지 시켰다. 2% Pt/Ce-$ZrO_2$ 촉매와 2% Pt/15% Ni-Ce-$ZrO_2$ 촉매는 저온영역($200^{\circ}{\sim}320^{\circ}C$)에서 비슷한 CO 전환율을 나타내었으나 고온영역($360^{\circ}C{\sim}400^{\circ}C$)에서는 2% Pt/15% Ni-Ce-$ZrO_2$ 촉매가 더 높은 CO의 전환율을 나타내었다. 이것은 Ni의 영향으로 고온에서 부반응인 메탄화 반응(Methanation reaction)이 생긴 것으로 판단되어 메탄($CH_4$)의 선택도를 살펴본 결과 2% Pt/15% Ni-Ce-$ZrO_2$ 촉매가 고온영역($360^{\circ}{\sim}400^{\circ}C$)에서 급격하게 증가하는 것으로 나타나 메탄화 반응이 일어난 사실을 증명한다.

• Clean Technology
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• v.24 no.2
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• pp.99-104
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• 2018

In this work, we performed the methanation reaction using synthesis gas ($H_2/CO_2$) for the process to produce synthetic natural gas (SNG) for $4^{th}$ methanation reactor in SNG process proposed by RIST-IAE. Experimental conditions were changed with temperature, pressure and space velocity. At this time, $CO_2$ conversion, $CH_4$ selectivity and $H_2$ concentration after reaction were investigated. As a result, $CH_4$ selectivity by the $CO_2$ methanation increased with lower space velocity and higher pressure. On the other hand, in the case of temperature, the maximum value was shown at $320^{\circ}C$. From these results, it was found that the optimum condition of the fourth reactor suitable for the SNG process was obtained.