• Journal of Industrial and Engineering Chemistry
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• v.68
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• pp.196-208
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• 2018

The effect of channel-system of zeolite on methanol-to-DME reaction was studied. Results revealed that channels size and topology affect catalyst lifetime, type and location of coke precursors. FER and MFI showed the best resistance towards coke deposition, whilst fast deactivation was observed on MOR. Although the higher concentration and strength of acid sites, FER structure formed a lower coke amount, preferably located within the pores, while coke cluster deposited on the external surface of MOR. Analysis of acid sites distribution and strength was performed during deactivation-regeneration process. Coke location assessment was also supported by molecular simulations.

• 한국신재생에너지학회:학술대회논문집
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• 2008.05a
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• pp.487-490
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• 2008

Temperature programmed oxidation (TPO) is used to characterize coke species deposited on commercial nickel catalyst, C11-PR during propane pre-reforming. Propane pre-reforming performed under various condition, S/C from 1.5 to 2.5 and temperature from $350^{\circ}C$ to $450^{\circ}C$. There are three kinds of coke species detected by TPO: (i) reactive coke, (ii) coke deposited on metal site and (iii) coke deposited on acid support. Coke deposited on metal and support are minimized although reactive coke is generated at temperature of $400^{\circ}C$ and S/C of 2.0. Reactive coke is expected to remove easily below temperature of $200^{\circ}C$. Therefore, optimized pre-reforming condition for propane is $400^{\circ}C$ and S/C of 2.0.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.128-128
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• 2013

Fabrication of heterogeneous catalysts using Atomic Layer Deposition (ALD) has recently been attracting attention of surface chemists and physicists. In this talk, I will present recent results about structures and chemical activities of various catalysts prepared by ALD, particularly focusing on Ni-based catalysts. Ni has been considered as potential catalysts for $CO_2$ reforming of methane (CRM); however, Ni often undergoes rapid decrease in catalytic activity with time, and therefore, application of Ni as catalysts for CRM has been regarded as difficult so far. Deactivation of Ni catalysts during CRM reaction is from either coke formation on Ni surface or sintering of Ni particles during reaction. Two different strategies have been used for enhancing stability of Ni-based catalysts; $TiO_2$ nanoparticles were deposited on micrometer-size Ni particles by ALD, which turned out to reduce coke formation on Ni surfaces. Ni nanoparticles deposited by ALD on mesoporous silica showed high activity and long-term stability from CRM without coke deposition and sintering during CRM reaction. Ni-based catalysts have been also used for oxidation of toluene, which is one of the most notorious gases responsible for sick-building syndrome. It was shown that onset-temperature of Ni catalysts for toluene oxidation is as low as $120^{\circ}C$. At $250\circ}C$, total oxidation of toluene to $CO_2$ with a 100% conversion was found.

• Korean Chemical Engineering Research
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• v.59 no.2
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• pp.232-238
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• 2021

The development of a low cost catalyst with high performance and small amount of carbon deposition on catalyst from toluene steam reforming were investigated by using coal ash as a support material. Ni-loaded coal ash catalyst showed similar catalytic activity for toluene steam reforming compared with the Ni/Al2O3. At 800 ℃, the toluene conversion was 77% for Ni/TAL, 68% for Ni/KPU and 78% for Ni/Al2O3. Ni/TAL showed similar toluene conversion to Ni/Al2O3. However, Ni/KPU produced higher hydrogen yield at relatively lower toluene conversion. Ni/KPU catalyst showed a remarkable ability of suppressing the carbon deposition. The difference in coke deposition and hydrogen yield is due to the composition of KPU ash (Ca and Fe) which increase coke resistance and water gas shift reaction. This study suggests that coal ash catalysts have great potential for the application in the steam reforming of biomass tar.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.727-730
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• 2009

Highly active and stable nano-sized Ni catalysts supported on MgO-$Al_2O_3$ calcined from hydrotalcite-like materials have been successfully developed with a strong metal to support interaction (SMSI) to enhance the coke resistance in combined $H_2O$ and $CO_2$ reforming of $CH_4$ (CSCRM) for syngas ($H_2$/CO=2) production. The change of the surface area and NiO crystallite size with varying the pre-calcination temperature of support and Mgo content was investigated in relation to the coke resistance. As increasing the pre-calcination temperature, the surface area decreases and the metal to support interaction becomes weak. As a consequence, the coke deposition was more severe on catalysts pre-calcined at high temperature. It was concluded that highly dispersed Ni metal in the surface of Ni/MgO-$Al_2O_3$ catalyst (MgO=30 wt%) pre-calcined at $800^{\circ}C$ had a strong metal to support interaction (SMSI) resulting in an increase of coke resistance and high activity.

• Journal of Industrial and Engineering Chemistry
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• v.68
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• pp.69-78
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• 2018

A study has been carried out of the regenerability of a commercial Ni catalyst used in the steam reforming of the volatiles from biomass pyrolysis (gases and bio-oil), determining the evolution of the reaction indices (conversion, product yields and $H_2$ production) in successive reaction-regeneration cycles. The causes of catalyst deactivation (coke deposition and Ni sintering) have been ascertained characterizing the deactivated and regenerated catalysts by TPO, TEM, TPR and XRD. Catalyst activity is not fully recovered by coke combustion in the first cycles due to the irreversible deactivation by Ni sintering, but the catalyst reaches a pseudo-stable state beyond the fourth cycle, reproducing its behaviour in subsequent cycles.

• Korean Chemical Engineering Research
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• v.46 no.4
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• pp.813-818
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• 2008

Various additives were added in small amounts on Ni/YSZ anode of SOFC (solid oxide fuel cell) in order to improve reactivity and to inhibit deactivation due to coke deposition during methane reforming using a low mole ratio steam ($H_2O/CH_4=1.5$) at $800^{\circ}C$. Ni/YSZ catalysts added with various perovskites did not show any improvement but exhibited a gradual decrease in the methane conversion. K-doped Ni/YSZ showed a steady increase and maintenance of the conversion up to 42 hours, after which there was an abrupt deactivation of catalyst owing to potassium loss by volatilization. Addition of 5% of $K_2Ti_2O_5$ on Ni/YSZ showed a stable maintenance of the conversion without K loss, and was able to prevent coke formation during a long time operation. Deactivation of catalyst during the reaction was mainly caused by the accumulation of graphidic carbon on the catalyst surface.

• 한국신재생에너지학회:학술대회논문집
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• 2008.05a
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• pp.247-250
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• 2008

Biomass gasification is a promising technology for producing a fuel gas which is useful for power generation systems. In biomass gasification processes, tar formation often causes some problems such as pipeline plugging. Thus, proper tar treatment is necessary. So far, nickel (Ni)-based catalysts have been intensively studied for the catalytic tar removal. However, the deactivation of Ni-based catalysts takes place because of coke deposition and sintering of Ni metal particles. To overcome these problems, we have been using ruthenium (Ru)-based catalyst for tar removal. It is reported by Okada et al., that a Ru/$Al_2O_3$ catalyst is very effective for preventing the carbon deposition during the steam reforming of hydrocarbons. Also, this catalyst is more active than the Ni-based catalyst at a low steam to carbon ratio (S/C). Benzene was used for the tar model compound because it is the main constituent of biomass tar and also because it represents a stable aromatic structure apparent in tar formed in biomass gasification processes. The steam reforming process transforms hydrocarbons into gaseous mixtures constituted of carbon dioxide ($CO_2$), carbon monoxide (CO), methane ($CH_4$) and hydrogen ($H_2$).

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

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.159.1-159.1
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• 2011

Partial oxidation reformer was fabricated and operated using commercial transportation fuels. Fuel injector and heating coil were used for fuel atomization and startup, respectively. The reformer was designed to produce syngas for $150{\sim}200W_e$ class solid oxide fuel cell. The reformer was operated in the $O_2$/C range between 0.6 and 0.8 while the capacity was fixed at $150W_e$. The temperature range in catalyst bed was between $500^{\circ}C$ and $900^{\circ}C$. Only 83% fuel was converted to $H_2$, CO, $CO_2$ and $CH_4$ at the operating conditions. The lowest temperature increase to $700^{\circ}C$ when the reformer was operated at $200W_e$, Although the temperature profiles was improved, fuel conversion was 88%. On the other hand, fuel was completely converted when micro-reactor operated at the same condition. This difference maybe due to aromatic compounds formation at homogeneous region. In addition, a significant amount of coke deposition was observed at vent line. Homogeneous reaction depends on the degree of mixing. For this purpose, two fluid nozzle and Ultra sonic injector were compared to investigate the effect of atomization. Sauter mean diameter(SMD) of Ultra sonic injector was lower than two-fluid nozzle at test condition. However, conversion efficiency and fuel conversion were not improved by using two-fluid nozzle. these results imply that the temperature of homogeneous reaction region should be controlled to prevent coke formation.