• Journal of the Korea Organic Resources Recycling Association
• /
• v.26 no.4
• /
• pp.5-10
• /
• 2018

In this study, the effect of physico-chemical factors (e.g., pressure, electrolyte, and organic matter) in the gas hydrate deposit on CH4-CO2 replacement process was investigated experimentally. The higher initial pressure during gas injection led the higher reaction rate at the first time, but finally it did not. Electrolytes and organic matter have some effects on reforming process after dissociation of gas hydrate. It is expected that further research using real marine sediments with actual gas hydrate will enable the development of technologies applicable to the characteristics of domestic seabed geology. Ultimately, it is expected that it will be possible to recover and utilize methane as an organic resource through application of domestic gas hydrate deposit in the Ulleung Basin, East Sea.

• Korean Chemical Engineering Research
• /
• v.56 no.2
• /
• pp.169-175
• /
• 2018

This study deals with a process for the recovery of hydrogen isotopes from methane ($CQ_4$) and water ($Q_2O$) containing tritium in the nuclear fusion exhaust gas (Q is Hydrogen, Deuterium, Tritium). Steam Methane Reforming and Water Gas Shift reactions are used to convert $CQ_4$ and $Q_2O$ to $Q_2$ and the produced $Q_2$ is recovered by the subsequent Pd membrane. In this study, one circulation loop consisting of catalytic reactor, Pd membrane, and circulation pump was applied to recover H components from $CH_4$ and $H_2O$, one of $CQ_4$ and $Q_2O$. The conversion of $CH_4$ and $H_2O$ was measured by varying the catalytic reaction temperature and the circulating flow rate. $CH_4$ conversion was 99% or more at the catalytic reaction temperature of $650^{\circ}C$ and the circulating flow rate of 2.0 L/min. $H_2O$ conversion was 96% or more at the catalytic reaction temperature of $375^{\circ}C$ and the circulating flow rate of 1.8 L/min. In addition, the amount of $CQ_4$ generated by Korean Demonstration Fusion Power Plant (K-DEMO) in the future was predicted. Then, the treatment process for the $CQ_4$ was proposed and HAZOP (hazard and operability) analysis was conducted to identify the risk factors and operation problems of the process.

• Korean Chemical Engineering Research
• /
• v.56 no.4
• /
• pp.496-523
• /
• 2018

The objective of this study is to evaluate the economic feasibility of two fast pyrolysis and biooil upgrading (FPBU) plants including feed drying, fast pyrolysis by fluidized-bed, biooil recovery, hydro-processing for biooil upgrading, electricity generation, and wastewater treatment. The two FPBU plants are Case 1 of an FPBU plant with steam methane reforming (SMR) for $H_2$ generation (FPBU-HG, 20% yield), and Case 2 of an FPBU with external $H_2$ supply (FPBUEH, 25% yield). The process flow diagrams (PFDs) for the two plants were constructed, and the mass and energy balances were calculated, using a commercial process simulator (ASPEN Plus). A four-level economic potential approach (4-level EP) was used for techno-economic analysis (TEA) under the assumption of sawdust 100 t//d containing 40% water, 30% equity, capital expenditure equal to the equity, $H_2$ price of $1050/ton, and hydrocarbon yield from dried sawdust equal to 20 and 25 % for Case 1 and 2, respectively. TCI (total capital investment), TPC (total production cost), ASR (annual sales revenue), and MFSP (minimum fuel selling price) of Case 1 were $22.2 million, $3.98 million/yr, $4.64 million/yr, and $1.56/l, respectively. Those of Case 2 were $16.1 million, $5.20 million/yr, $5.55 million/yr, and $1.18/l, respectively. Both ROI (return on investment) and PBP (payback period) of Case 1(FPBU-HG) and Case 2(FPBU-EH) were the almost same. If the plant capacity increases into 1,500 t/d for Case 1 and Case 2, ROI would be improved into 15%/yr.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2012.02a
• /
• pp.267-267
• /
• 2012

$TiO_2$-Ni inverse catalysts were prepared using atomic layer deposition (ALD) process and catalytic $CO_2$ reforming of methane (CRM) reaction over catalysts (either bare Ni or $TiO_2$ coated-Ni particles) were performed using a continuous flow reactor at $800^{\circ}C$. $TiO_2$-Ni inverse catalyst showed higher catalytic reactivity at initial stage of CRM reactions at $800^{\circ}C$ comparing to bare Ni catalysts. Moreover, catalytic activity of $TiO_2$/Ni catalyst was kept high during 13 hrs of the CRM reactions at $800^{\circ}C$, whereas deactivation of bare Ni surface was started within 1hr under same conditions. The results of surface analysis using SEM, XPS, and Raman showed that deposition of graphitic carbon was effectively suppressed in a presence of $TiO_2$ nanoparticles on Ni surface, thereby improving catalytic reactivity and stability of $TiO_2$/Ni catalytic systems. We suggest that utilizing decoration effect of metal catalyst with oxide nanoaprticles is of great potential to develop metal-based catalysts with high stability and reactivity.

• Journal of the Korean Applied Science and Technology
• /
• v.20 no.3
• /
• pp.230-236
• /
• 2003

Synthesis gas is commercially produced by a steam reforming process. However, the process is highly endothermic and energy-consuming. Thus, this study was conducted to produce synthesis gas by the partial oxidation of methane to decrease the energy cost. Supported Ni catalysts were prepared by the impregnation method. To examine the activity of the catalysts, a differential fixed bed reactor was used, and the reaction was carried out at $750{\sim}850^{\circ}C$ and 1 atm. The fresh and used catalysts were characterized by XRD, XPS, TGA and AAS. The highest catalytic activity was obtained with the 13wt% Ni/MgO catalyst, with which methane conversion was 81%, and $H_2$ and CO selectivities were 94% and 93%, respectively. 13wt% Ni/MgO catalyst showed the best $MgNiO_2$ solid solution state, which can explain the highest catalytic activity of the 13wt% Ni/MgO catalyst.

• Transactions of the Korean hydrogen and new energy society
• /
• v.33 no.6
• /
• pp.660-673
• /
• 2022

In achieving carbon neutrality and the hydrogen economy, the estimation of H₂ cost is critical in terms of CCU technologies. This study analyzes LCOH of hydrogen produced by the carbon utilization unit with methane reforming and CO₂ from thermal power plant. LCOH for H₂ made with CO is estimated in three ways of Joint Cost Allocations with financial performance risk assessment. Regarding cost analysis, the zero value of LCOH is $6,003/ton. We found that the CCU technology has economic feasibility in terms of profitability. The sensitivity analysis result shows that the input ratio is more influential to the LCOH than other variables. Risk analysis presents the baseline price of zero value of LCOH - $8,408/ton, which is higher than the cost analysis - $6,003/ton. Mainly, the price variability of natural gas primarily affects the LCOH. The study has significant value in analyzing the financial performance risks as well as the cost of H₂ produced by a Plasma-based CCU system.

• Korean Chemical Engineering Research
• /
• v.51 no.3
• /
• pp.319-324
• /
• 2013

The partial oxidation reaction of methane was investigated to produce syngas with $Ni/CeO_2-ZrO_2$, $Ni-Ru/CeO_2-ZrO_2$ and $Ni-Pd/CeO_2-ZrO_2$ catalysts. Honeycomb metallic monolith was applied in order to obtain high catalytic activity and stability in partial oxidation reforming. The catalysts were characterized by XRD and FE-SEM. The influence of various catalysts on syngas production was studied for the feed ratio (O/C), GHSV and temperature. Among the catalysts used in the experiment, the $Ni-Pd/CeO_2-ZrO_2$ catalyst showed the highest activity. The 99% of $CH_4$ conversion was obtained at the condition of T=$900^{\circ}C$, GHSV=10,000 $h^{-1}$ and feed ratio O/C=0.55. It was confirmed that $H_2$ yield increased slightly as O/C ratio increased, while CO yield remained almost constant. Also, $CH_4$ conversion decreased as GHSV increased. It was found that the safe range of GHSV for high $CH_4$ conversion was estimated to be less than 10,000 $h^{-1}$.

• Korean Chemical Engineering Research
• /
• v.45 no.6
• /
• pp.656-662
• /
• 2007

Fuel reformer using plasma and shift reactor for CO oxidation were designed and manufactured as $H_2$ supply device to operate a polymer electrolyte membrane fuel cell (PEMFC). $H_2$ selectivity was increased by non-thermal plasma reformer using GlidArc discharge with Ni catalyst simultaneously. Shift reactor was consisted of steam generator, low temperature shifter, high temperature shifter and preferential oxidation reactor. Parametric screening studies of fuel reformer were conducted, in which there were the variations of the catalyst temperature, gas component ratio, total gas ratio and input power. and parametric screening studies of shift reactor were conducted, in which there were the variations of the air flow rate, stema flow rate and temperature. When the $O_2/C$ ratio was 0.64, total gas flow rate was 14.2 l/min, catalytic reactor temperature was $672^{\circ}C$ and input power 1.1 kJ/L, the production of $H_2$ was maximized 41.1%. And $CH_4$ conversion rate, $H_2$ yield and reformer energy density were 88.7%, 54% and 35.2% respectively. When the $O_2/C$ ratio was 0.3 in the PrOx reactor, steam flow ratio was 2.8 in the HTS, and temperature were 475, 314, 260, $235^{\circ}C$ in the HTS, LTS, PrOx, the conversion of CO was optimized conditions of shift reactor using simulated reformate gas. Preheat time of the reactor using plasma was 30 min, component of reformed gas from shift reactor were $H_2$ 38%, CO<10 ppm, $N_2$ 36%, $CO_2$ 21% and $CH_4$ 4%.

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

• Korean Chemical Engineering Research
• /
• v.61 no.2
• /
• pp.296-301
• /
• 2023

Solid oxide fuel cell has received more attention recently due to the fuel flexibility via internal reforming. Commonly used Ni/YSZ anode, however, can be easily deactivated by carbon coking in hydrocarbon fuels. The carbon deposition problem can minimize by developing alternative perovskite anode. This study is focused on improving conductivity and catalytic activity of the perovskite anode by introducing rGO (reduced graphene oxide). Sr_0.92Y_0.08TiO₃(SYT) anode with perovskite structure was synthesized with 1wt% of rGO. The presence of rGO during anode fabricating process and cell operation is confirmed through XPS and Raman analysis. The maximum power density of rGO/SYT anode improved to 3 times in H₂ and 6 times in CH₄ comparing to that of SYT anode due to the high electrical conductivity and good catalytic activity for CH₄.