• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.71.2-71.2
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• 2013

천연가스를 화학적 전환에 의해 부가가치를 높이기 위해서는 리포밍에 의해 합성가스(CO/H2)를 경유하는 간접전환경로가 현재로서는 가장 현실적인 방법이라 할 수 있다. 천연가스를 이용한 합성가스 제조기술은 수증기개질법(SRM), 이산화탄소 개질법(CDR, dry reforming), 부분산화법, 촉매 부분 산화법, 자열개질법 등으로 구분되며, 최근에는 각각의 제조방법의 장점을 고려하여 혼합개질법 또는 일련의 리포머 조합 방법이 개발되고 있다. CDR은 촉매 하에서 메탄과 이산화탄소의 직접접촉에 의해 반응이 일어나며, 수소와 일산화탄소의 비가 같은 합성가스가 제조된다. SRM에 비하여 고온에서 반응이 일어나고 전환율이 더 낮으므로 에너지 소비가 상대적으로 높다. 하지만, SRM과 함께 사용하면 합성가스 비율을 F-T합성이나 메탄올 합성에 적절한 비율로 조절이 가능한 장점이 있으며, 온실가스를 저감시킬 수 있는 전환기술로도 각광받고 있다. 본 발표에서는 최근의 CDR을 이용한 가스로부터 합성석유(GTL)와 메탄올을 고효율로 생산하는 기술 개발 동향에 대해서 소개하고자 한다.

• Journal of Institute of Convergence Technology
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• v.12 no.1
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• pp.19-23
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• 2022

Interest in hydrogen production to respond to climate change is increasing. Until now, hydrogen has been mainly produced through the SMR (Steam Methane Reforming) process using natural gas. A large amount of CO₂ is emitted in the hydrogen production process through SMR, and the gas flow including CO₂ generated in the SMR process has different characteristics for each emission source, so it is important to apply a suitable CO₂ capture process. In the case of PSA tail gas or synthesis gas, the applicability of an amine-based process has been confirmed or demonstrated close to a commercial level. However, in the case of the flue gas generated from the reformer, it is still difficult to apply the conventional amine-based process because the partial pressure of CO₂ is relatively low. Energy-saving innovative absorbents such as phase separation absorbents can be a solution to these difficulties.

• Korean Chemical Engineering Research
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• v.47 no.2
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• pp.243-247
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• 2009

This study is purposed to analyze thermodynamic properties on the hydrogen production by ethylene glycol steam reforming. Various reaction conditions of temperatures(300~1,600 K), feed compositions(steam/carbon= 0.5~4.5), and pressures(1~30 atm) were applied to investigate the effects of the reaction conditions on the thermodynamic properties of dimethyl ether steam reforming. An endothermic steam reforming competed with an exothermic water gas shift reaction and an exothermic methanation within the applied reaction condition. Hydrogen production was initiated at the temperature of 400 K and the production rate was promoted at temperatures exceeding 500 K. An increase of steam to carbon ratio(S/C) in feed mixture over 1.0 resulted in the increase of the water gas shift reaction, which lowered the formation of carbon monoxide. The maximum hydrogen yield with minimizing loss of thermodynamic conversion efficiency was achieved at the reaction conditions of a temperature of 900 K and a steam to carbon ratio of 3.0.

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.155-155
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• 2011

용융탄산염 연료전지(MCFC)는 $650^{\circ}C$에서 작동하는 고온형 연료전지 시스템이다. 이 시스템은 천연가스 등을 개질하여 생산된 수소를 바로 전기로 생산할 수 있는 시스템으로 열효율이 높으며, 현재 대체 발전시스템으로 각광을 받고 있다. MCFC는 개질방식에 따라 내부개질 방식과 외부개질 방식이 있다. 내부개질 방식은 수소를 생산하는 개질기가 스택내부에 장착된 형식으로 천연가스를 스택내부에서 개질하여 바로 전기를 생산하는 방식이다. 이 내부개질반응에 사용되는 촉매로는 알루미나에 고함량 (약 50 wt.%)으로 담지된 니켈(Ni) 계열촉매이 주로 쓰이고 있다. 이 고함량으로 담지된 촉매는 대부분 높은 활성을 보인다. 비교적 낮은 온도 운전조건 (약 $580{\sim}620^{\circ}C$)을 가지는 MCFC 내부개질에 적용하기 위해서는 활성점인 니켈을 최대한 담지체에 고르게 분산 시켜야한다. 이를 위해서 MgO를 이용하여 촉매의 활성점을 높게 분산시키는 연구를 진행 하였다. 촉매를 제조하는 방법으로 요소(urea)를 이용한 균일용액침전법을 이용하였다. 니켈함량은 50 wt.%로 고정을 한 다음, MgO 양과 $Al_2O_3$ 양을 각각 0 ~ 45 wt.%와 5 ~ 50 wt.%로 조절하면서 촉매를 제조하여 그 특성들을 분석하였다. 물성을 비교하기 위해서, X-선 회절분석 (XRD) 및 TPR, 물리화학흡착 실험을 하였다. 촉매의 활성을 살펴보기 위해서, fresh 상태 및 피독 상태에서 메탄수증기 개질활성 실험을 실시하였다. MgO 함량이 없거나 적은 촉매에서는 높은 BET surface area와 작은 NiO, metallic Ni 결정 크기가 나타났다. 반면 MgO 함량이 높은 촉매에서 낮은 BET surface area와 비교적 큰 NiO, metallic Ni 결정 크기가 나타났다. 또한 XRD 분석에서 MgO 함량이 증가할 수 록 MgO 결정 피크가 명확히 나타났으며, $MgAl_2O_4$ 피크는 나타나지 않았다. TPR 분석에서 촉매들의 환원 피크를 측정한 결과, 저함량의 MgO를 포함한 촉매는 $700^{\circ}C$ 부근에 환원 피크가 관찰되었고 MgO가 고함량인 촉매는 환원 피크가 $400^{\circ}C$ 부근에서 관찰되었다. 촉매의 초기 fresh 상태에서의 활성은 고함량 MgO를 포함한 Ni-90M10A 샘플을 제외하고 모든 촉매가 거의 비슷하게 나타났다. 그러나 $K_2CO_3$ 피독 상태에서는 MgO 함량이 증가할 수 록 활성이 좋지 않았음을 알 수 있었다. 따라서 MgO가 소량 포함된 촉매의 경우 fresh 상태에서는 우수한 물성과 활성을 보이지만, 피독상태에서는 MgO가 포함되지 않은 Ni-$Al_2O_3$ 촉매가 우수한 활성을 보였다.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.40 no.12
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• pp.793-799
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• 2016

In a hybrid fuel cell system, low-temperature reforming technology, which uses waste heat as a heat source, is applied to improve system efficiency. A low temperature reformer is required to optimize geometry in low thermal conditions so that the reformer can achieve the proper methane conversion rate. This study analyzed internal temperature distributions and the reaction patterns of a reformer by considering the change of the shape factor on the limited heat supply condition. Unlike the case of a high temperature reformer, analysis showed that the reaction of a low temperature reformer takes place primarily in the high temperature region of the reactor exit. In addition, it was confirmed that the efficiency can be improved by reducing the GHSV (gas hourly space velocity) or increasing the heat transfer area in the radial direction. Through reacting characteristic analysis, according to change of the aspect ratio, it was confirmed that a low temperature reformer can improve the efficiency by increasing the heat transfer in the radial direction, rather than in the longitudinal direction.

• Membrane Journal
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• v.15 no.2
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• pp.105-113
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• 2005

Silica membranes were prepared on a porous metal sheet by ultrasonic spray pyrolysis method for gas separation at high temperatures. In order to improve the permselectivity, silica was deposited in the sol-gel derived $silica/\gamma-alumina$ intermediate layer by pyrolysis of tetraethyl orthosilicate (TEOS) at 873 K. The pyrolysis with forced cross flow through the porous wall of the support was very effective in plugging mesopores, Knudsen diffusion regime, that were left unplugged in the membranes. At permeation temperature of 523 K, the silica/alumina composite membrane showed $H_2/N_2$ and water/methanol selectivity as high as 17 and 16, respectively, by molecular sieve effect.

• Journal of Hydrogen and New Energy
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• v.17 no.3
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• pp.248-254
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• 2006

The promotion effects of noble metals upon the activity and reducibility in steam methane reforming over $Ni/MgAl_2O_4$ catalysts were investigated. While $Ni/MgAl_2O_4$ catalysts require the pre-reduction by $H_2$, the noble metal-added catalysts show high catalytic activities without pre-treatment. According to $CH_4$-TPR, the addition of noble metal makes the $Ni/MgAl_2O_4$ catalyst easily reducible. The reduction degree of NiO in the noble metal-added catalysts after using at $650^{\circ}C$ without pre-reduction was $15{\sim}20%$, and was lower than that in the $H_2$-reduced $Ni/MgAl_2O_4$ catalyst(reduction degree=27%). The enhancement of the catalytic activity over noble metal-added catalysts results from easier reducibility by addition of noble metal and the synergy effect between noble metal and Ni.

• Journal of Hydrogen and New Energy
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• v.23 no.1
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• pp.73-82
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• 2012

A 2-dimensional heterogeneous reactor model was developed and simulated for a tube reactor of packed bed where the steam-$CO_2$ combined reforming reaction of natural gas proceeded to produce synthesis gas. Under the reactor feeding rate, 45 $Nm^3$/h, of the reactant gas stream, the 2-dimensional heterogeneous reactor model showed the similar results to those from the ASPEN simulator although there were some discrepancies between the two in the temperature and the $H_2$/CO ratio of the reformed gas at the reactor exit. The calculated enthalpy difference between the reformed gas at the reactor exit and the reactant gas fed to the reactor was closely correspondent to the total amount of heat transferred to the reactor interior from the furnace. This supports that the 2-dimensional heterogeneous reactor model was reasonably established and the numerical solution was properly obtained.

• Journal of Hydrogen and New Energy
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• v.24 no.2
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• pp.113-120
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• 2013

A steam reformer is a chemical reactor to produce high purity hydrogen from fossil fuel. In the steam reformer, since endothermic steam reforming is heated by exothermic combustion of fossil fuel, the heat transfer between two reaction zones dominates conversion of fossil fuel to hydrogen. Steam Reforming is complex chemical reaction, mass and heat transfer due to the exothermic methane/air combustion reaction and the endothermic steam reforming reaction. Typically, a steam reformer employs burner to supply appropriate heat for endothermic steam reforming reaction which reduces system efficiency. In this study, the heat of steam reforming reaction is provided by anode-off gas combustion of stationary fuel cell. This paper presents a optimization of heat transfer effect and average temperature of cross-section using two-dimensional models of a coaxial cylindrical reactor, and analysis three-dimensional models of a coaxial cylindrical steam reformer with chemical reaction. Numerical analysis needs to dominant chemical reaction that are assumed as a Steam Reforming (SR) reaction, a Water-Gas Shift (WGS) reaction, and a Direct Steam Reforming(DSR) reaction. The major parameters of analysis are temperature, fuel conversion and heat flux in the coaxial reactor.

• Journal of Hydrogen and New Energy
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• v.18 no.1
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• pp.12-25
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• 2007

Numerical simulation of the natural gas steam reforming process for on-site hydrogen production in a $H_2$ fueling station was conducted on the basis of process material and heat balances. The effects of reforming parameters on the process efficiency of hydrogen production were investigated, and set-point values of each of the parameters to minimize the sizes of unit process equipments and to secure a stable operability of the reforming process were suggested. S/C ratio of the reforming reactants was found to be a crucial parameter in the reforming process mostly governing both the hydrogen production efficiency and the stable operability of the process. The operation of the process was regarded to be stable if the feed water(WR) as a reforming reactant could evaporate completely to dry steam through HRSG. The optimum S/C ratio was 3.0 where the process efficiency of hydrogen production was maximized and the stable operability of the process was secured. The optimum feed rates of natural gas(NGR) and WR as reforming reactants and natural gas(NGB) as a burner fuel were also determined for the hydrogen production rate of $27\;Nm^3/h$.