• Applied Chemistry for Engineering
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• v.8 no.4
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• pp.685-693
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• 1997

We have studied the reforming of carbon dioxide with methane over various supported nickel catalysts. The nickel supported on natural zeolite showed the highest activity and the nickel on acidic support showed higher activity and slow deactivation compared to nickel on basic support. The activity of nickel on natural zeolite increased with increasing loading ratio and showed almost constant activity above 10wt.% loading of nickel. The conversion and yield of products were affected by the mole ratio of reactants and the highest yields of CO and $H_2$ were obtained at $CH_4/CO_2=1$. The deactivation of catalyst was caused by deposition of coke which was formed by the decomposition of methane. The shape of coke was shown to be whisker tripe carbon, and it brought out the slow deactivation of catalyst.

• Journal of Energy Engineering
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• v.2 no.2
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• pp.208-214
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• 1993

Pyrolysis of bituminous coal has been carried out in a two-stage fixed bed reactor to produce high heating value gas(7000 kcal/N㎥) for industrial or town gas usage. The effects of coke catalyst, pyrolysis temperature (468∼565$^{\circ}C$), and catalytic cracking temperature (700∼850$^{\circ}C$) on the product gas properties from pyrolysis of bituminous coal have been determined. From pyrolysis of Dong Jin coal with coke, the carbon deposition on catalyst is found to be less than 5% of product tar and approximately 15% of total energy iii the parent coal can be recovered as high heating value gas. Oil composition in the product tar from the two-stage pyrolysis is higher than that from low-temperature pyrolysis. The tar produced from pyrolysis below 516$^{\circ}C$ can be easily catalytically cracked but, the tar produced above 565$^{\circ}C$ cannot be cracked easily with catalyst. From the product gas analysis, the catalytic cracking temperature should be maintained below 800$^{\circ}C$ since cracking speed of ethylene increases remarkably with the cracking temperature above 800$^{\circ}C$.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.58.2-58.2
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• 2012

Heavy hydrocarbon reforming is a core technology for "Dirty energy smart". Heavy hydrocarbons are components of fossil fuels, biomass, coke oven gas and etc. Heavy hydrocarbon reforming converts the fuels into $H_2$-rich syngas. And then $H_2$-rich syngas is used for the production of electricity, synthetic fuels and petrochemicals. Energy can be used efficiently and obtained from various sources by using $H_2$-rich syngas from heavy hydrocarbon reforming. Especially, the key point of "Dirty energy smart" is using "dirty fuel" which is wasted in an inefficient way. New energy conversion laboratory of KAIST has been researched diesel reforming for solid oxide fuel cell (SOFC) as a part of "Dirty energy smart". Diesel is heavy hydrocarbon fuels which has higher carbon number than natural gas, kerosene and gasoline. Diesel reforming has difficulties due to the evaporation of fuels and coke formation. Nevertheless, diesel reforming technology is directly applied to "Dirty fuel" because diesel has the similar chemical properties with "Dirty fuel". On the other hand, SOFC has advantages on high efficiency and wasted heat recovery. Nippon oil Co. of Japan recently commercializes 700We class SOFC system using city gas. Considering the market situation, the development of diesel reformer has a great ripple effect. SOFC system can be applied to auxiliary power unit and distributed power generation. In addition, "Dirty energy smart" can be realized by applying diesel reforming technology to "Dirty fuel". As well as material developments, multidirectional approaches are required to reform heavy hydrocarbon fuels and use $H_2$-rich gas in SOFC. Gd doped ceria (CGO, $Ce_{1-x}Gd_xO_{2-y}$) has been researched for not only electrolyte materials but also catalysts supports. In addition, catalysts infiltrated electrode over porous $La_{0.8}Sr_{0.2}Ga_{0.8}Mg_{0.2}O_3-{\delta}$ and catalyst deposition at three phase boundary are being investigated to improve the performance of SOFC. On the other hand, nozzle for diesel atomization and post-reforming for light-hydrocarbons removal are examples of solving material problems in multidirectional approaches. Likewise, multidirectional approaches are necessary to realize "Dirty energy smart" like reforming "Dirty fuel" for SOFC.

• Applied Chemistry for Engineering
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• v.17 no.3
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• pp.235-242
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• 2006

Liquid phase alkylation of biphenyl (BP) was studied over large pore zeolites. Selective formation of the least bulky products, 4,4'-diisopropylbiphenyl (4,4'-DIPB) occurred only in the isopropylation of BP over some large pore molecular sieves. H-mordenites (MOR) gave the highest selectivity among them. The dealumination of MOR enhanced catalytic activity and the selectivity of 4,4'-DIPB because of the decrease of coke-deposition. Non-selective catalysis occurs on external acid sites over MOR with the low $SiO_2/Al_2O_3$ ratio because severe coke-deposition deactivates the acid sites inside the pores by blocking pore openings. The selectivity of DIPB isomers was changed with reaction temperature. Selective formation of 4,4'-DIPB was observed at moderate temperatures such as $250^{\circ}C$, whereas the decrease of the selectivity of 4,4'-DIPB occurred at higher temperatures as $300^{\circ}C$. However, 4,4'-DIPB was almost exclusive isomer in the encapsulated DIPB isomers inside the pores even at high temperatures. These decreases of the selectivity of 4,4'-DIPB are due to the isomerization of 4,4'-DIPB on the external acid sites. Some 12-membered molecular sieves, such as SSZ-24, MAPO-5 (M:Mg, Zn, Si), SSZ-31, and ZSM-12, which have straight channels, gave 4,4'-DIPB with moderate to high selectivity; however; SSZ-55, SSZ-42, and MAPO-36 (M: Mg, Zn) gave lower selectivity because of cages in 12-membered one dimensional channels. Three dimensional H-Y and Beta zeolites also yield 4,4'-DIPB in low yield because of their wide circumstances for the isopropylation of BP. The increasing the size of alkylating agent enhanced the shape-selective alkylaiton even for the zeolites, such as UTD-1. The ethylation of BP to ethylbiphenyls (EBPs) and diethylbiphenyls (DEBPs) over MOR was non-selective. The ethylation of BP to EBPs was controlled kinetically. However, there was difference in reactivity of EBPs and DEBPs for their further ethylation. 4-EBP was ethylated preferentially among the isomers, although the formation of 4,4'-DEBP was less selective. The least bulky 4-EBP and 4,4'-DEBP have the highest reactivity among EBPs and DEBPs for the ethylation to polyethylbiphenyls (PEBPs). These results show that the environments of MOR pores are too loose for shape selective formation of the least bulky isomers, 4-EBP and 4,4'-DEBP in the ethylation of BP, and that MOR pores have enough space for the further ethylation of 4,4'-DEBP.

• 한국신재생에너지학회:학술대회논문집
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• 2008.05a
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• pp.511-512
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• 2008

For the $CO_2$ reforming of $CH_4$, Ni catalyst was supported on La-hexaaluminate or on $\gamma$-$Al_2O_3$. The catalytic activities of Ni/La-hexaaluminate catalysts were measured at $700^{\circ}C$ using gas chromatography (GC) for 72 h, and the reaction was maintained up to 72 hfor the investigation of catalyst deactivation. The surface of each catalyst after 72 h reaction was investigated using SEM and TEM, and the composition of the carbon deposits was investigated by using EA, TPO and TGA. Ni/La-hexaaluminate shows higher resistance to coke deposition than conventional Ni/$Al_2O_3$ which seems to be due to strong interaction between Ni and the support material. As a result of the reforming reaction, various types of carbon deposits were created on catalyst surface and the amounts of them were much smaller in the case of La-hexaaluminate than on $Al_2O_3$.

• Proceedings of the Korean Society of Propulsion Engineers Conference
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• 2009.11a
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• pp.93-96
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• 2009

Advances in high speed flight technologies and engine efficiencies increase heat load on the aircraft. As the temperature of air flow is too high to cool the structure at hypersonic flight speeds, it is necessary to utilize the aircraft fuel as the primary coolant. By undergoing endothermic reaction, such as thermal decomposition or catalytic decomposition, aircraft fuels have heat sink potential. These fuels are called endothermic fuels. The endothermic reaction can be improved by catalysts, but limited by coke deposition. In this study the essential technologies of endothermic fuels are described, and intended to be used for basic research.

• Journal of the Korean Applied Science and Technology
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• v.37 no.4
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• pp.723-732
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• 2020

The spent RHDS (Residue HydroDeSulfurization) catalyst is deactivated mainly by deposition of various contaminants such as coke, sulfur and vanadium on the surface of catalyst. To eliminate those contaminants, the following remanufacturing process was conducted. The first, heavy oil on the surface of the spent RHDS catalyst was removed by kerosene and dehydrated. The second, the high temperature incineration was carried out to eliminate coke and sulfur components deposited on the surface of spent RHDS catalyst. The third, the excessive quantity of Vanadium deposited on the surface of catalyst was removed by leaching process as follows: ultrasonic agitation was carried out at 50℃, for 10 seconds with 0.5% and 1% oxalic acid solution. The purpose of this process is to find out regenerated RHDS catalyst can be used as SCR catalyst for NOx reduction by controlling the vanadium residual content of the regenerated RHDS catalyst through leaching process. The composition of regenerated RHDS catalyst was analyzed by XRF and the NOx reduction efficiency was also measured by continuous catalytic fixed bed reactor. As the result, regenerated catalyst, with 0.5% oxalic acid, ultrasonic agitation in 10 seconds, showed the most stable NOx reduction efficiency. Also, in comparison with commercial SCR catalyst, the NOx reduction performance of regenerated catalyst was similar to that of commercial SCR catalyst at the temperature 375℃ and higher whereas was lower than commercial SCR catalyst at the temperature range between 200~250℃. Therefore, it was confirmed that the regenerated catalyst as powder form wash coated on the surface of metal corrugated substrate can be used for commercial SCR catalyst.

• Applied Chemistry for Engineering
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• v.8 no.3
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• pp.543-549
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• 1997

The direct reaction of carbon dioxide($CO_2$) with butane($C_4H_{10}$) to obtain synthesis gas and hydrocarbon compounds have been studied on nickel loaded catalysts. In the reaction of $CO_2$ with $C_4H_{10}$, Ni loaded catalysts showed similar activity with Pt catalyst and Coke deposition on the catalyst was severe by dehydrogenation of butane. The main products were carbon monoxide and hydrogen, when alumina and Y type zeolite were used as a support. Instead, a great deal of aromatic hydrocarbons were obtained on the Ni loaded ZSM-5 catalyst. The conversion of $CO_2$ increased with the increasing molar ratio of $CO_2$/$C_4H_{10}$ on Ni/ZSM-5, Ni/NaY and Ni/alumina catalyst, but the conversion decreased again from the ratio of 2. The value of $CO_2$ conversion was the highest at the 5wt% of Ni loading on ZSM-5 catalyst. A part of cokes deposited on the catalysts diminished when only $CO_2$ gas or water steam flowed into the reactor. The coke deposited on the catalysts was very reactive and it may be an important intermediate for the carbon dioxide reforming reaction.

• Environmental Engineering Research
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• v.22 no.1
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• pp.19-30
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• 2017

Direct catalysis of vapors from vacuum pyrolysis of biomass was performed on MCM-41 to investigate the effects of operating parameters including catalyzing temperature, catalyzing bed height and system pressure on the organic yields. Optimization of organic phase yield was further conducted by employing response surface methodology. The statistical analysis showed that operating parameters have significant effects on the organic phase yield. The organic phase yield first increases and then decreases as catalyzing temperature and catalyzing bed height increase, and decreases as system pressure increases. The optimal conditions for the maximum organic phase yield were obtained at catalyzing temperature of $502.7^{\circ}C$, catalyzing bed height of 2.74 cm and system pressure of 6.83 kPa, the organic phase yield amounts to 15.84% which is quite close to the predicted value 16.19%. The H/C, O/C molar ratios (dry basis), density, pH value, kinematic viscosity and high heat value of the organic phase obtained at optimal conditions were 1.287, 0.174, $0.98g/cm^3$, 5.12, $5.87mm^2/s$ and 33.08 MJ/kg, respectively. Organic product compositions were examined using gas chromatography/mass spectrometry and the analysis showed that the content of oxygenated aromatics in organic phase had decreased and hydrocarbons had increased, and the hydrocarbons in organic phase were mainly aliphatic hydrocarbons. Besides, thermo-gravimetric analysis of the MCM-41 zeolite was conducted within air atmosphere and the results showed that when the catalyst continuously works over 100 min, the index of physicochemical properties of bio-oil decreases gradually from 1.15 to 0.45, suggesting that the refined bio-oil significantly deteriorates. Meanwhile, the coke deposition of catalyst increases from 4.97% to 14.81%, which suggests that the catalytic activity significantly decreases till the catalyst completely looses its activity.

• Journal of the Korean Electrochemical Society
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• v.10 no.2
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• pp.110-115
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• 2007

Solid oxide fuel cell(SOFC) has high fuel flexibility due to its high operating temperatures. Hydrocarbonaceous fuels such as diesel has several advantages such as high energy density and established infrastructure for fuel cell applications. However diesel reforming has technical problems like coke formation in a reactor, which results in catastrophic failure of whole system. Performance degradation of diesel autothermal reforming (ATR) leads to increase of undesirable hydrocarbons at reformed gases and subsequently degrades SOFC performance. In this study, we investigate the degradation of SOFC performance(OCV, open circuit voltage) under hydrocarbon(n-Butane) feeds and characteristics of diesel performing under various ratios of reactants($H_2O/C,\;O_2/C$ molar ratios) for improvement of SOFC performance. Especially we achieved relatively high performance of diesel ATR under $H_2O/C=0.8,\;O_2/C=3$ condition.