• Journal of the Korean Chemical Society
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• 제32권1호
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• pp.22-29
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• 1988

The reaction of methanol-water mixture to $CO_2$ and $H_2$ on alkaline earth metal-copper-zinc oxide has been studied in the temperature range of 150 ${\sim}\;300^{\circ}C$. Generally the addition of the alkaline earth metal to Cu/ZnO resulted in an enhancement of selectivity for $CO_2$ formation and a reduction of catalytic activity. Measurable activities were found from 150$^{\circ}C$, 200$^{\circ}C$, and 250$^{\circ}C$ on Mg/Cu/ZnO, Ca/Cu/ZnO, and Ba/Cu/ZnO respectively. However, the highest selectivity for $CO_2$ formation was observed in Ba/Cu/ZnO catalyst at 250$^{\circ}C$. The effect of alkaline earth metal or ZnO on the reactivity was investigated using temperature programmed desorption of $CO_2$ or temperature programmed reduction with $H_2$ over catalysts respectively. It was found that $CO_2$ interacts more strongly in the sequence of MgO < CaO < BaO and ZnO decereases the reduction temperature of CuO. From the results, it was suggested that ZnO activates $H_2$ in the redox process of Cu component and alkaline earth metals adsorbs $CO_2$ in the catalytic process.

• Applied Chemistry for Engineering
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• 제4권2호
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• pp.365-372
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• 1993

$CO_2$ methanation was performed over Ni supported on cation-exchanged Y zeolites under atmospheric pressure at $250{\sim}550^{\circ}C$ and $H_2/CO_2$ mole ratio of 4. Adsorption strength between carbon dioxide and nickel was found to be Influenced by the cation exchanged in the zeolite. TPD(Temperature-programmed desorption) results show that the adsorption strength decreases in the order of Ni/NaY>Ni/MaY>Ni/HY. TPSR(Temperature-programmed surface reaction) results indicate that enhanced methanation activity is obtained when the adsorption strength between carbon dioxide and nickel is stroing. As the reduction temperature increases, the methantion activity of the catalyst increase. From this result the larger size nickel particle seems advantageous for $CO_2$ methanation reaction. The maximum activity is obtained when nickel loading is 3.3wt%. Carbon monoxide is produced as a by-product throughout the reaction temperature range, and as the contact time increases, the selectivity to methane increases and the selectivity to carbon monoxide decreases steadily. Thus methane seems to be produced from $CO_2$ via CO as an intermediate species. In the temperature range of $410{\sim}450^{\circ}C$, the methane production rate is found to be dependent on the orders of 3.3~-0.5 and 1.4~3.6 with respect to $CO_2$ and $H_2$ partial pressures, respectively. This clearly shows that $CO_2$ and $H_2$ are competing for adsorption sites and as the reaction temperature increases, it becomes increasingly difficult for $H_2$ to be adsorbed on the catalyst surface.

• Journal of the Korea Academia-Industrial cooperation Society
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• 제17권5호
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• pp.709-716
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• 2016

Recently, the operating conditions of the various mechanical structures have become more severe and the running time has become longer as the development of plant equipment increases with the introduction of high technology. Thus, the reliability of the system and its accessories is becoming a problem. Normally, synthetic natural gas (SNG) plants use 1.25Cr-0.5Mo or 2.25Cr-1Mo heat resistant steel according to the operating conditions. In this study, a lab-scale reactor was set up using 1.25Cr-0.5Mo steel, in order to carry out corrosion tests for producing synthetic natural gas. The corrosive characteristics were investigated under 1st-methanator operating conditions and fundamental data about the durability and reliability were obtained by using the experimental test. The analysis of results obtained on the durability of the reactor under emission and injection compositions showed that the hydrogen embrittlement caused by hydrogen and the oxidation corrosion caused by H2O had the most effect on the durability of 1.25Cr-0.5Mo steel in the SNG reactor. However, the hydrogen embrittlement and oxidation corrosion occurred simultaneously under emission conditions, so that the corrosion of the material increased suddenly after a long operating time. Besides, the corrosion of the 1.25Cr-0.5Mo steel under the injection composition was faster than that under the emission composition.

• Proceedings of the Korean Vacuum Society Conference
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• 한국진공학회 2009년도 제38회 동계학술대회 초록집
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• pp.234-234
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• 2010

최근 CMOS 소자 크기가 축소됨에 따라 소스와 드레인 영역에서의 접촉저항을 줄이기 위하여, 실리사이드 공정이 많이 연구되고 있다. 실리사이드 물질로서 NiSi는 낮은 저항률과 낮은 실리콘 소모, 낮은 공정온도, 등의 장점을 가지고 있다. 그러나, 실리사이드 형성으로 인한 나노소자의 소오스/드레인에서정션(junction) 누설전류의 증가는 큰 문제가 되므로 실리콘과 실리사이드 계면의 특성이 중요하다. 본 연구에서는 니켈을 이용한 실리사이드 형성시 계면 활성제인 에틸 요오드를 이용하여 실험을 진행하였다. 금속 유기 전구체인 MABONi을 사용하여 ALD 방식으로 증착 한 니켈 박막과 니켈 핵 형성시 계면활성제인 에틸요오드의 처리 방법에 따른 Ni-silicide 박막의 특성을 비교, 분석하였다. 먼저 자연산화막을 건식식각으로 제거한 뒤, 첫 번째 샘플에서는 10회의 주기로 초기 니켈을 증착한 뒤, 에틸요오드로 니켈의 표면 위를 처리하고, 다시 200회의 주기로 니켈을 증착하였으며, 두 번째는 첫 번째 방식에서 에틸요오드 주입 시 동시에 수소도 함께 주입하였다. 세 번째는 비교를 위해 에틸요오드 처리를 하지 않고 니켈 박막만을 증착 하였다. 이어서, 각 샘플을 급속 열처리 장비에서 $400^{\circ}C$부터 $900^{\circ}C$까지 각각 30sec간 열처리를 진행후, 반응하지 않은 잔여 니켈을 제거한 후, XRD(x-ray diffraction), AES(auger), 그리고 4-point probe 등을 이용하여 형성된 실리사이드의 특성을 분석하였다. 에틸요오드와 함께 수소를 주입한 경우 계면에서의 산소 불순물과 카본 성분이 효과적으로 제거되어 $400^{\circ}C$에서 $2.9{\Omega}/{\Box}$ 의 낮은 면저항을 가지는 NiSi가 형성되었고 모든 온도구간에서 다른 샘플에 비하여 가장 낮은 면저항 분포를 보였다. 이는 분해 흡착된 요오드에 의한 계면 특성 향상과 카본 성분이 포함된 잔여물들이 수소처리에 의해 효율적으로 제거되어 실리사이드의 특성이 향상되었기 때문이다. 계면활성제를 사용하지 않은 경우에는 $500^{\circ}C$에서 NiSi가 형성되었다. 반면에 에틸요오드로만 표면을 처리한 경우에는 니켈과 실리콘 계면에서의 카본 성분에 의하여 silicidation 이 충분히 일어나지 않았다. 이러한 결과는 향후 45nm 이하의 CMOS 공정상에서 소스와 드레인의 낮은 누설전류를 가지고, 접촉저항을 줄이기 위한 니켈 실리사이드 형성에 큰 도움을 줄 것으로 기대된다.

• Journal of the Korea Academia-Industrial cooperation Society
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• 제20권4호
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• pp.458-463
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• 2019

Palladium (Pd) is widely used as a catalyst and noxious gas sensing materials. Especially, various researches of Pd based hydrogen gas sensor have been studied due to the noble property, Pd can be adsorbed hydrogen up to 900 times its own volume. In this study, palladium oxide (PdO) nanostructures were grown on Si substrate ($SiO_2(300nm)/Si$) for 3 to 5 hours at $230^{\circ}C{\sim}440^{\circ}C$ using thermal chemical vapor deposition system. Pd powder (source material) was vaporized at $950^{\circ}C$ and high purity Ar gas (carrier gas) was flown with the 200 sccm. The surface morphology of as-grown PdO nanostructures were characterized by field-emission scanning electron microscopy(FE-SEM). The crystallographic properties were confirmed by Raman spectroscopy. As the results, the as-grown nanostructures exhibit PdO phase. The nano-cube structures of PdO were synthesized at specific substrate temperatures and specific growth duration. Especially, PdO nano-cube structrures were uniformly grown at $370^{\circ}C$ for growth duration of 5 hours. The PdO nano-cube structures are attributed to vapor-liquid-solid process. The nano-cube structures of PdO on graphene nanosheet can be applied to fabricate of high sensitivity hydrogen gas sensor.

• Korean Chemical Engineering Research
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• 제53권1호
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• pp.31-38
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• 2015

At present, carbon dioxide ($CO_2$) emission, which causes global warming, is a major issue all over the world. To reduce $CO_2$ emission directly, commercial deployment of $CO_2$ separation processes has been attempted in industrial plants, such as power plant, oil refinery and steelmaking plant. Besides, several studies have been done on indirect reduction of $CO_2$ emission from recycle of reducing gas (carbon monoxide or hydrogen containing gas) in the plants. Unlike many competing gas separation technologies, pressure swing adsorption (PSA) and membrane filtration are commercially used together or individually to separate a single component from the gas mixture. However, there are few studies on operation of sequential separation process of multi-component gas which has more than two target gas products. In this paper, process simulation model is first developed for two available configurations: $CO_2$ PSA-CO PSA-$H_2$ PSA and $CO_2$ PSA-CO PSA-$H_2$ membrane. Operation optimization and economic evaluation of the processes are also performed. As a result, feed gas contains about 14% of $H_2$ should be used as fuel than separating $H_2$, and $CO_2$ separation should be separated earlier than CO separation when feed gas contains about 30% of $CO_2$ and CO. The simulation results can help us to find an optimal process configuration and operation condition for separation of multicomponent gas with $CO_2$, CO, $H_2$ and other gases.

• Journal of the Mineralogical Society of Korea
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• 제20권4호
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• pp.313-325
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• 2007

In order to have better insights into adsorption of organic molecules on kaolinite surfaces, we performed quantum chemical calculations of interaction between three different model clusters of kaolinite siloxane surfaces and benzyl alcohol, with emphasis on the effect of size and lattice topology of the cluster on the variation of electron density and magnetic shielding tensor. Model cluster 1 is an ideal silicate tetrahedral surface that consists of 7 hexagonal rings, and model cluster 2 is composed of 7 ditrigonal siloxane rings with crystallographically distinct basal oxygen atoms in the cluster, and finally model cluster 3 has both tetrahedral and octahedral layers. The Mulliken charge analysis shows that siloxane surface of model cluster 3 undergoes the largest electron density transfer after the benzyl alcohol adsorption and that of model cluster 1 is apparently larger than that of model cluster 2. The difference of Mulliken charges of basal oxygen atoms before and after the adsorption is positively correlated with hydrogen bond strength. NMR chemical shielding tensor calculation of clusters without benryl alcohol shows that three different basal oxygen atoms (O3, O4, and O5) in model cluster 2 have the isotropic magnetic shielding tensor as $228.2{\pm}3.9,\;228.9{\pm}3.4,\;and\;222.3{\pm}3.0ppm$, respectively. After the adsorption, the difference of isotropic chemical shift varies from 1 to 5.5 ppm fer model cluster 1 and 2 while model cluster 2 apparently shows larger changes in isotropic chemical shift. The chemical shift of oxygen atoms is also positively correlated with electron density transfer. The current results show that the adsorption of benzyl alcohol on the kaolinite siloxane surfaces can largely be dominated by a weak hydrogen bonding and electrostatic force (charge-charge interaction) and demonstrate the importance of the cluster site and the lattice topology of surfaces on the adsorption behavior of the organic molecules on clay surfaces.

• Applied Chemistry for Engineering
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• 제5권5호
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• pp.808-818
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• 1994

Effects of ceria additive on the activity and thermal aging behavior of supported Ru catalysts were investigated using Ru/${\gamma}$-$Al_2O_3$and Ru/$CeO_2$-${\gamma}$-$Al_2O_3$. The catalysts were characterized by $^{129}Xe$-NMR and $H_2$ chemisorption. The cataltic activity for conversion of CO, HC and $NO_x$ was measured using simulated automobile engine exhausts under lean, rich and stoichiometric conditions. For both fresh and aged catalysts, Ru/$CeO_2$-${\gamma}$-$Al_2O_3$ was more active than Ru/${\gamma}$-$Al_2O_3$ for all three pollutants. Results of $^{129}Xe$-NMR and $H_2$ chemisorption indicated that sintering of Ru particles occurred to the same extent for both catalysts during the thermal aging process. After thermal aging at 673K, however, the catalytic activity of the aged Ru/$CeO_2$-${\gamma}$-$Al_2O_3$ was substantially higher than that of the fresh one, while the activity of Ru/${\gamma}$-$Al_2O_3$ decreased after the thermal aging. This finding may suggest new active sites were created during the thermal aging, probably in the vicinity of the interface between Ru and Ce. For more quantitative investigation of the effect of a cation such as Ce on the thermal aging of Ru metal particles, Ru catalysts supported on cation-exchanged Y-zeolites were used as the model catalysts. The results indicated that when Ba, Ca, La, Y or Ce was used for the cation exchange, the exchanged cation did not affect the thermal aging behavior of Ru in Y-zeolite, as evidenced by $^{129}Xe$-NMR and EXAFS.

• Applied Chemistry for Engineering
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• 제22권5호
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• pp.532-539
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• 2011

The physical and chemical properties of the dried low rank coals (LRCs) before and after the surface treatment using ozone and ammonia were characterized in this study. The contents of moisture, volatiles, fixed carbon and ash consisting of dried LRCs before the surface treatment were about 2.0, 44.8, 44.9 and 8.9%, respectively. Also, it was composed of carbon of 62.66%, hydrogen of 4.33%, nitrogen of 0.94%, oxygen of 27.01% and sulfur of 0.09%. The dried LRCs was surface-treated with the various dry methods using gases such as ozone at room temperature, ammonia at $200^{\circ}C$ and then the dried LRCs before and after the surface treatment were characterized by the various analysis methods such as FT-IR, TGA, proximate and elemental analysis, caloric value, ignition test, adsorption of $H_2O$ and $NH_3-TPD$. As a result, the oxygen content increased and the calorific value, ignition temperature and the contents of carbon and hydrogen relatively decreased because the oxygen-contained functional groups were additionally generated by the surface oxidation with ozone which plays a role as an oxidant. Also, its $H_2O$ adsorption ability got higher because the hydrophilic oxygen-contained functional groups were additionally generated by the surface oxidation with ozone. On the other hand, it was confirmed that the dried LRCs after the surface treatment with $NH_3$ at $200^{\circ}C$ have the decreased oxygen content, but the increased calorific value, ignition temperature and contents of carbon and hydrogen because of the decomposition of oxygen-contained functional groups the on the surface. In addition, the $H_2O$ adsorption ability was lowered bucause the surface of the dried LRCs might be hydrophobicized by the loss of the hydrophilic oxygen-contained functional groups. It was concluded that the various physico-chemical properties of the dried LRCs can be changed by the surface treatment.

• Journal of the Mineralogical Society of Korea
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• 제15권1호
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• pp.1-10
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• 2002

The present study is focused on the granite weathering and soil formation, and the heavy metal contamination in soils in the Onsan industrial area. For profile study, soil sampling was conducted on each depth and experimental analyses have been conducted on those samples. X-ray diffraction analyses show that clay minerals consist mainly of kaolin minerals, vermiculite, and minor illite. Most of kaolin minerals in the lower kiwi of the profile consist of halloysite as confirmed by formamide intercalation, but the content of halloysite decreases gradually toward the surface since it has been transformed to kaolinite in the upper part of the profile. Thermal treatment by heating at $110^{\circ}C,\;300^{\circ}C,\;and\;550^{\circ}C$ shows a diffuse and broad peak the between 10 and $14\;{\AA}$ region in X-ray diffractograms. This suggests the possible existence of the hydroxy-Al interlayerecl vermiculite. Na-citrate extraction method reaconfirms this result showing transition of $14\;{\AA}$ peak to $10\;{\AA}$ In by removing the interlayer materials and restoring the vermiculite to its original state. The occurrence of hydroxy-Al interlayered vermiculite is also supported by soil pH distribution room 3.9 In the lower part to 3.6 in the upper part of the profile. Sequential extraction experiment was conducted to investigate the states of heavy metals in soils. The experiment shows that relatively high amounts of heavy metals are concentrated in the upper part of the profile and that most of them are bound to Fe/Mn oxides and organic matters while less concentration in clay minerals. The result indicates that most of heavy metal pollutants are concentrated in the surface soil and that the low concentrations of heavy metals in clays are mainly due to the low adsorption capacities of clay minerals such as kaolin minerals and hydroxy-Al interlayered vermiculite in acidified soil condition.