• Korean Chemical Engineering Research
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• v.46 no.3
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• pp.581-584
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• 2008

The catalyst carriers of the mesoporous layer compounds were prepared to carry out the partial oxidation of methane(POM) to hydrogen. The catalytic activities of POM to hydrogen were investigated over Ru(3)/SPK and Ru(3)/SPM catalyst in a fixed bed flow reactor under atmosphere. In addition, the catalysts and carriers were characterized by BET, TEM, TPR. The BET surface areas of the silica-pillared $H^+-kenyaite$(SPK) and the silica-pillared $H^+-magadite$(SPM) were $760m^2/g$ and $810m^2/g$, repectively, and the average pore sizes were 3.0 nm and 2.6 nm, repectively. The nitrogen adsorption isotherms were type IV with developed hysteresis. The TEM showed that the mesoporous layer compounds were formed well. The Ru(3)/SPK and the Ru(3)/SPM catalyst were obtained high hydrogen yields(90%, 87%), and were kept constant high hydrogen yields even about 60 hours at 973 K, $CH_4/O_2=2$, $1.25{\times}10^{-5}g-Cat.hr/ml$. The TPR peaks of Ru(3)/SPK and the Ru(3)/SPM catalyst showed the similar reducibilities around 453 K and 413 K. It could be suggested that SPK and SPM had the physicochemical properties as oxidation catalyst carries from these analysis data.

• Proceedings of the KSME Conference
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• 2007.05b
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• pp.2232-2237
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• 2007

Steam reforming and catalytic reforming of $CH_4$ conversion to produce synthesis gas require both high temperatures and high pressure. Non-thermal plasma is considered to be a promising technology for the hydrogen rich gas production from methane. In this study, three phase AC GlidArc plasma system was employed to investigate the effects of gas composition, gas flow rate, catalyst reactor temperature and applied electric power on the $CH_4$ and $H_2$ yield and the product distribution. The studied system consisted of three electrode and it connected AC generate power system different voltages. In this study, air was used for the partial oxidation of methane. The results showed that increasing gas flow rate, catalyst reactor temperature, or electric power enhanced $CH_4$ conversion and $H_2$ concentration. The reference conditions were found at a $O_2$/C molar ratio of 0.45, a feed flow rate of 4.9 ${\ell}$/min, and input power of 1kW for the maximum conversions of $CH_4$ with a high selectivity of $H_2$ and a low reactor energy density.

• Journal of the Korean Applied Science and Technology
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• v.22 no.1
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• pp.56-61
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• 2005

Methanol was synthesized by homogeneous and catalytic reactions of partial oxidation of methane. The effect of pressure, temperature and oxygen concentration on methanol synthesis was investigated. The catalyst used was Bi-Cs-Mg-Cu-Mo mixed oxide. The partial oxidation reaction was carried out in a fixed bed reactor at 20${\sim}$46 bar and $450{\sim}480^{\circ}C$ and oxygen concentration of 5.3${\sim}$7.7mol%. The results were compared with results of homogeneous reaction performed at the same conditions. Methane conversions of the homogeneous and catalytic reactions increased with temperature. Methanol selectivity of the homogeneous reaction decreased with increasing temperature. However, the methanol selectivity of catalytic reaction increased with temperature. For both homogeneous and catalytic reactions, the methane conversions were around 5%. This may be due to the low oxygen concentration. Methanol selectivity of the catalytic reaction was higher than that of homogeneous one.

• Journal of the Korean Applied Science and Technology
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• v.27 no.1
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• pp.29-36
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• 2010

The effects of La addition to Ni/$CeO_2$ methane partial oxidation catalysts were investigated. Catalysts were prepared by the impregnation and urea methods. In the preparation of catalysts, La content was changed from 1 wt% to 3wt%. Catalysts that contain 2wt% La showed the highest methane conversion of about 80% and CO selectivity of 84% and $H_2$ selectivity of 70%. This result may be stemmed from that, when La content is 2wt%, a fluorite oxide-type structure is well formed and carbon deposition is also decreased. Among the catalysts, 2.5wt% Ni/Ce(La)Ox showed the highest catalytic activity. From the experiment of changing reaction temperature with 2.5wt% Ni/Ce(La)Ox catalyst, it was found that the optimum reaction temperature is $750^{\circ}C$ and at this temperature methane conversion was about 90%, CO and $H_2$ selectivities were 94 and 80%, respectively.

• Transactions of the Korean hydrogen and new energy society
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• v.18 no.2
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• pp.132-139
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• 2007

Popular techniques for producing synthesis gas by converting methane include steam reforming and catalyst reforming. However, these are high temperature and high pressure processes limited by equipment, cost and difficulty of operation. Low temperature plasma is projected to be a technique that can be used to produce high concentration hydrogen from methane. It is suitable for miniaturization and for application in other technologies. In this research, the effect of changing each of the following variables was studied using an AC Glidarc system that was conceived by the research team: the gas components ratio, the gas flow rate, the catalyst reactor temperature and voltage. Glidarc plasma reformer was consisted of 3 electrodes and an AC power source. And air was added for the partial oxidation reaction of methane. The result showed that as the gas flow rate, the catalyst reactor temperature and the electric power increased, the methane conversion rate and the hydrogen concentration also increased. With $O_2/C$ ratio of 0.45, input flow rate of 4.9 l/min and power supply of 1 kW as the reference condition, the methane conversion rate, the high hydrogen selectivity and the reformer energy density were 69.2%, 36.2% and 35.2% respectively.

• Journal of the Korean Applied Science and Technology
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• v.23 no.3
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• pp.223-229
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• 2006

Methanol and formaldehyde were produced directly by the partial oxidation of methane over mixed oxide catalysts. The catalysts were composed of Mo and Bi with late-transition metals, such as Mn, Fe, and Co. The reaction was carried out at $450^{\circ}C$, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by $O_2-TPD$ and BET apparatus. Among the catalysts used, the catalyst composed of 1:1:2.5 molar ratio of Mo:Bi:Mn showed the best methane conversion and methanol selectivity. The change in ratio of methane to oxygen affected at the conversion and selectivity, and the most proper ratio was 10:1.5. Methane conversion, methanol and formaldehyde selectivities increased with the surface areas of the catalysts. From the $O_2-TPD$ result, it was found that the oxygen species responsible for this reaction might be the lattice oxygen species desorbed at high temperature around $800^{\circ}C$.

• 한국신재생에너지학회:학술대회논문집
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• 2010.11a
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• pp.143-143
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• 2010

GTL(Gas-to-Liquids)공정 중 합성가스 제조공정(Reforming Process)인 ATR(Auto-Thermal Reforming), SCR(Steam Carbon Reforming), POx(Partial Oxidation)의 시뮬레이션 연구를 수행하였다. Reforming 공정에서 생산된 합성가스는 GTL 합성유 제조공정인 FT(Fischer-Thropsch) 반응기로 주입되며, 합성유 생산에 최적의 효율을 보이는 H2/CO 비(합성가스에 포함된 반응물비)는 2.0으로 알려져 있다. FT공정은 합성가스를 원료로 고온 및 고압 반응을 거쳐 GTL 공정의 최종 생산품인 FT합성유를 제조하는 공정이다. 본 연구에서는 FT공정 효율 극대화를 위해 reforming 공정에서 생성되는 합성가스 내 H2/CO의 비를 2로 수렴토록 모사조건을 설정하였으며, 상기 조건을 만족하는 reforming 공정들의 운전 온도 및 feed 조성을 분석하고 비교하고자 한다. 현재 GTL 플랜트관련 산업계에 적용 혹은 주 연구대상인 reforming 공정으로는 ATR, SCR, POx 공정이 있다. ATR 공정은 $850{\sim}1100^{\circ}C$에서 메탄, 스팀 및 산소를 원료로 활용하여 H2 및 CO를 생산하는 공정으로 발열/흡열 반응이 상존하여 에너지 비용이 낮지만 공정구조 상 열회수설비 및 ASU(Air Separation Unit)이 필요하기에 CAPEX(초기설비 설치비용)가 높은 편이다. SCR공정은 CH4, Steam 및 CO2를 연료로 하기에 이산화탄소가 일정부분 포함된 가스전에도 적용이 가능하나 공정 운전 중 지속적으로 외부에서 열을 공급해야 하기에 에너지 투입비용이 높은편이며, 탄소침적의 문제가 있어 대용량 플랜트에는 적합하지 않다. POx공정은 약 $1,500^{\circ}C$의 고온에서 CH4가 O2에 의해 부분 산화되는 방식으로 촉매가 필요없어 설비비가 타 공정에 비해 저렴하나 생산가스의 H2/CO비가 다소 낮아 전체적인 GTL 공정효율이 저하되는 단점이 있다. 상기 세 공정은 GTL 산업계에서 실증 및 효율증대를 위해 주로 연구되는 공정이기에 본 연구의 분석대상으로 설정하였다. 본 연구에서는 상용공정모사기인 Aspen Plus를 활용하여 reforming 공정별로 FT합성공정의 최적 조건(H2/CO=2)을 만족하는 합성가스 생산조건 분석 및 비교를 수행할 예정이다. 운전조건인 공정 운전온도 및 feed 가스조성 등을 모사하기 위해 합성가스 reforming 공정을 모델링하고 공급유량 및 압력 등의 운전변수는 GTL국책과제 1단계 연구수행 결과를 토대로 선정하고자 한다. GTL공정의 경우, 설비의 운전조건이나 연료가스의 구성 및 유량에 따라 적합한 reforming 공정이 다르기에 본 시뮬레이션 결과를 향후 GTL 플랜트 공정모델 설계시 reforming 공정선정에 참고자료로 활용하고자 한다.

• 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.224.2-224.2
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• 2010

연료개질기는 연료전지 시스템의 핵심 구성요소 중의 하나로 도시가스로부터 수소를 생산하는 역할을 담당한다. 연료개질기는 주로 탈황, 수증기 개질, 수성가스 전이, 선택적 산화 반응의 4단계로 구성되어 있으며 이 중 상온 탈황부분을 제외한 나머지 부분은 일체화 설계를 통해 제작된다. 탈황의 경우 도시가스에 포함된 부취제인 황화합물를 제거하여 후단에 위치한 촉매층이 황에 의해 피독되는 것을 막는 역할을 하며 주로 상온흡착식 탈황제를 사용한다. 황이 제거된 도시가스는 물과 함께 연료개질기로 도입되어 수증기 개질반응을 통하여 수소, 일산화탄소, 이산화탄소 및 소량의 메탄과 미반응 수증기로 구성된 개질가스로 전환된다. 이후의 수성가스 전이반응에서는 일산화탄소가 물과 반응하여 수소 생산량을 늘리며 동시에 일산화탄소의 농도를 낮추게 된다. 또한 고분자 전해질 연료전지에 공급되는 개질가스는 선택적 산화반응을 통하여 일산화탄소의 농도를 10ppm이하로 유지하게 된다. 이러한 기능의 연료개질기 개발의 주요 이슈로는 컴팩트화 및 고효율화이며 이 두가지 요소를 고려하여 연료개질기를 설계하여야 한다. 연료전지 시스템의 전체부피를 줄이기 위한 노력의 일환으로 연료개질기의 컴팩트화가 요구되는데 가정용 연료전지 기술 선진국인 일본 제품의 경우 $1Nm^3/h$급 연료개질기의 부피는 20L정도로 알려져 있다. 또한 연료전지 시스템의 효율은 연료개질기의 개질효율과 연료전지 스택의 발전효율의 곱으로 계산되기 때문에 연료개질기의 연료개질 효율은 전체 시스템의 효율에 직접적으로 영향을 미치게 된다. 한국에너지기술연구원에서는 수소생산량 기준 $1Nm^3/h$급 연료개질기의 개발을 완료하였으며 크기 및 효율면에서 선진국 제품과 비교하여 동등 또는 우위의 수준을 달성하였다. 연료개질기 내부의 혼합 및 분배 구조를 개선하고 각 촉매층의 최적 배치를 통해 연료개질기의 부피를 최소화 하였으며 연료개질기 내부에서 고온부위와 저온부위 사이의 최적 열교환을 통해 열효율을 극대화 시켰다. 현재 개발된 $1Nm^3/h$급 개질기의 단열 후 부피는 13.5L 그리고 단독운전 시 열효율은 80%(LHV)로 측정되었다. 또한 $1Nm^3/h$급의 연료개질기의 스케일-업 설계를 통하여 수소생산량 3, $5Nm^3/h$ 규모의 연료개질기를 개발하였으며 성능평가가 진행 중이다.

• Journal of the Korean Ceramic Society
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• v.40 no.6
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• pp.594-600
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• 2003

L $a_{0.7}$S $r_{0.3}$G $a_{0.6}$F $e_{0.4}$ $O_{3-}$$\delta$/ perovskite-type mixed conducting membranes, which could permeate oxygen selectively, have been fabricated and the microstructural features developed by varying the sintering conditions have been analyzed. The effects of surface modification and the membrane thickness on oxygen permeability have been evaluated under He/air environment. With increasing a grain boundary fraction, the overall oxygen permeability decreased. The syngas (CO+ $H_2$) has been produced by partial oxidation reaction of methane with the oxygen permeated through the membrane. Methane conversion and syngas yield have been evaluated as functions of the compositional ratio of feed gas and reaction temperature. In long-term duration test for 600 h, under C $H_4$+He/air environment, L $a_{0.7}$S $r_{0.3}$G $a_{0.6}$F $e_{0.4}$ $O_{3-}$$\delta$/ membrane showed a highly stable performance.