• Transactions of the Korean hydrogen and new energy society
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• v.32 no.5
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• pp.388-400
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• 2021

Power to gas (P2G) is one of the energy storage technologies that can increase the storage period and storage capacity compared to the existing battery type. One of P2G technology produces hydrogen by decomposing water from renewable energy (electricity) and the other produces CH4 by reacting hydrogen with CO2. This study is an experimental study to produce CH4 by reacting CO2 of biogas with hydrogen using a 40 wt% Ni-Mg-Al catalyst and a commercial catalyst. Catalyst characteristics were analyzed through H2-TPR, XRD, and XPS instruments of 40% Ni catalyst and commercial catalyst. The effect on the CO2 conversion rate and CH4 selectivity was analyzed, and the activities of a 40% Ni catalyst and a commercial catalyst were compared. As a result of experiment, In the case of a 40 wt% catalyst, the maximum CO2 conversion rate showed 77% at the reaction temperature of 400℃. Meanwhile, the commercial catalyst showed a maximum CO2 conversion rate of 60% at 450℃. When 50% of CO was added to the CO2 methanation reaction, the CO2 conversion rate was increased by about 5%. This is considered to be due to the atmosphere in which the CO reaction can occur without the process of converting to CH4 after forming carbon and CO as intermediates in terms of the CO2 mechanism on the catalyst surface.

• Clean Technology
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• v.28 no.2
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• pp.182-192
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• 2022

This study provides an overview of the production costs of methane and hydrogen via water electrolysis-based hydrogen production followed by a methanation based methane production technology utilizing CO₂ from external sources. The study shows a comparative way for economic optimization of green methane generation using excess free electricity from renewable sources. The study initially developed the overall process on the Aspen Plus simulation tool. Aspen Plus estimated the capital expenditure for most of the equipment except for the methanation reactor and electrolyzer. The capital expenditure, the operating expenditure and the feed cost were used in a discounted cash flow based economic model for the methane production cost estimation. The study compared different reactor configurations as well. The same model was also used for a hydrogen production cost estimation. The optimized economic model estimated a methane production cost of $11.22/mcf when the plant is operating for 4000 hr/year and electricity is available for zero cost. Furthermore, a hydrogen production cost of $2.45/GJ was obtained. A sensitivity analysis was performed for the methane production cost as the electrolyzer cost varies across different electrolyzer types. A sensitivity study was also performed for the changing electricity cost, the number of operation hours per year and the plant capacity. The estimated levelized cost of methane (LCOM) in this study was less than or comparable with the existing studies available in the literature.

• Korean Chemical Engineering Research
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• v.56 no.6
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• pp.871-877
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• 2018

Storing the surplus energy from renewable energy resource is one of the challenges related to intermittent and fluctuating nature of renewable energy electricity production. $CO_2$ methanation is well known reaction that as a renewable energy storage system. $CO_2$ methanation requires a catalyst to be active at relatively low temperatures ($250-500^{\circ}C$) and selectivity towards methane. In this study, the catalytic performance test was conducted using a pressurized bubbling fluidized bed reactor (Diameter: 0.025 m and Height: 0.35 m) with $Ni/{\gamma}-Al_2O_3$ (Ni70%, and ${\gamma}-Al_2O_3$30%) catalyst. The range of the reaction conditions were $H_2/CO_2$ mole ratio range of 4.0-6.0, temperature of $300-420^{\circ}C$, pressure of 1-9 bar, and gas velocity ($U_0/U_{mf}$) of 1-5. As the $H_2/CO_2$ mole ratio, temperature and pressure increased, $CO_2$ conversion increases at the experimental temperature range. However, $CO_2$ conversion decreases with increasing gas velocity due to poor mixing characteristics in the fluidized bed. The maximum $CO_2$ conversion of 99.6% was obtained with the operating condition as follows; $H_2/CO_2$ ratio of 5, temperature of $400^{\circ}C$, pressure of 9 bar, and $U_0/U_{mf}$ of 1.4-3.

• 한국신재생에너지학회:학술대회논문집
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• 2006.11a
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• pp.485-488
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• 2006

고분자전해질형 연료전지(PEMFC)는 다른 연료전지에 비해 소형전원에서부터 분산용전원에 이르기 까지 넓은 응용범위를 가지고 있다. 이러한 PEMFC의 응용범위 중 메탄올 개질반응을 통하여 발생된 수소를 이용하는 휴대용 PEMFC 시스템의 경우, 개질 시 발생하는 일산화탄소가 백금촉매를 피독시켜 연료전지의 성능을 저하시키는 주요 원인이다. 따라서 연료전지의 성능저하를 막기 위해서는 개질가스의 일산화탄소의 농도를 10ppm이하로 낮추는 것이 요구된다. 본 연구에서는 이러한 개질가스의 일산화탄소 농도를 낮추기 위한 반응기를 설계 및 제작하였으며, 상용촉매를 사용하여 CO저감 성능실험을 하였다. 또한, PROX 촉매 및 methanation 촉매를 조합하여 사용함으로써 $140^{\circ}C{\sim}190^{\circ}C$ (약 $50^{\circ}C$)의 온도범위에서 일산화탄소의 농도 10ppm이하의 결과를 나타내었다.

• Journal of Korean Society for Atmospheric Environment
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• v.15 no.2
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• pp.183-190
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• 1999

Magnetite was synthesized with $FeSO_4$, and NaOH for the decomposition of carbon dioxide and for the study of the methane formation. The chemical equivalent ratio was changed from 0.5 to 1.50 for the magnetite synthesis. The chemical equivalent ratio was fixed in 1.00, and Nickel chloride and Rhodium chloride equally added and synthesized with the ratio was of 0.10~10.00 mole%. The crystal strucure of the synthesized magnetite was measured XRD. Putting synthesized magnetite in the reactor and using hydrogen gas oxygen-deficient magnetite was made. Injecting carbon dioxide in the reactor, the decomposition reaction was experimented. The formation of methane was confirmed injecting hydrogen gas in the reactor after carbon dioxide was decomposed.

• Journal of the Korea Organic Resources Recycling Association
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• v.2 no.2
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• pp.3-17
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• 1994

The inhibitory effect of sodium ion on the anaerobic degradation of food waste was studied by an anaerobic batch toxicity assay and inhibition model. The anaerobic degradation activity of food waste spiked with over $2g\;Na^+/L$ of sodium ion was severely inhibited at the initial stage of the exposure. The inhibition response of anaerobic microorganisms on the sodium ion estimated from the methane production was differed according to the concentration of sodium ion. The relative acclimation time(RAT) and methanation rate(RMR), defined as the ratios of initial lag time and maximum methane production rate of the sample spiked with sodium ion to the control. respectively, were used to evaluate the acclimation and inhibitory effects quantitatively on the anaerobic microorganisms. When sodium ion was increased from $2g\;Na^+/L$ to $20g\;Na^+/L$, the RAT was exponentially increased from 18.9 to 90. but the RMR was linearly decreased from 0.97 to 0.02. The effects of sodium ion for the maximum methanation rate, first order kinetic constant and ultimate methane production were well evaluated by a generalized nonlinear expression model. it could be described by the uncompetitive inhibition mode. The sodium ion concentration causing 50% inhibition of methanation activity was about $11g\;Na^+/L$, and the critical sodium ion beyond to compelete inhibition was 20 to $21g\;Na^+/L$. The presented results could be used to obtain the design or operation parameters of the anaerobic process treating food waste of high salt.

• 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.

• Korean Chemical Engineering Research
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• v.51 no.4
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• pp.443-454
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• 2013

Various metal ions (transition and base metals) incorporated MCM-41 catalysts can be synthesized using colloidal and soluble silica with non-sodium involved process. Transition metal ion-typically $V^{5+}$, $Co^{2+}$, and $Ni^{2+}$-incorporated MCM-41 catalysts were synthesized by isomorphous substitution of Si ions in the framework. Each incorporated metal ion created a single species in the silica framework, single-site solid catalyst, showing a substantial stability in reduction and catalytic activity. Radius of pore curvature effect was investigated with Co-MCM-41 by temperature programmed reduction (TPR). The size of metallic Co clusters, sub-nanometer, could be controlled by a proper reduction treatment of Co-MCM-41 having different pore size and the initial pH adjustment of the Co-MCM-41 synthesis solution. These small metallic clusters showed a high stability under a harsh reaction condition without serious migration, resulting from a direct anchoring of small metallic clusters to the partially or unreduced metal ions on the surface. After a complete reduction, partial occlusion of the metallic cluster surface by amorphous silica stabilized the particles against aggregations. As a probe reaction of particle size sensitivity, carbon single wall nanotubes (SWNT) were synthesized using Co-MCM-41. A metallic cluster stability test was performed by CO methanation using Co- and Ni-MCM-41. Methanol and methane partial oxidations were carried out with V-MCM-41, and the radius of pore curvature effect on the catalytic activity was investigated.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.117-117
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• 2010

석탄 가스화에서 유도된 합성가스는 합성반응 공정을 통하여 합성석유, 메탄올(& DME), 합성천연가스(SNG) 등의 다양한 화학원료를 제조할 수 있어 이의 활용이 점차적으로 확대될 것이다. 이 중 SNG 공정의 경우, 석탄가스화기에서 생산된 합성가스는 집진, 탈황, 수성가스전환($H_2$/CO 비를 조절), $CO_2$ 제거 등의 공정을 거쳐 메탄화 반응기로 유도되는데, 메탄화 반응에서 $CO_2$가 반응에 참여하면 탄소포집 및 저장(CCS)의 부담을 크게 줄일 수 있어 이에 대한 관심이 커지고 있다. 특히, 상업용으로 활용되고 있는 단열반응기를 직렬로 연결할 경우, 메탄화반응의 발열로 인한 반응기내의 온도 상승으로 $CO_2$가 생성되는데 이후의 2차 또는 3차의 단열반응기에서 $CO_2$ 수소화반응이 진행되면 최종 생성물인 메탄의 수율이 증가하며, 뿐만아니라 생성물 중 포함된 수소의 농도를 낮출 수 있는 장점을 가지게 된다. 따라서, 본 연구에서는 Ni계 촉매를 사용하여 풍부한 $H_2$ 분위기에서 Fe를 첨가하여 이의 함량이 $CO_2$ 수소화반응의 탄소 전환율과 생성되는 메탄의 수율에 미치는 영향을 고찰하였다.

• 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.