• Korean Chemical Engineering Research
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• v.55 no.2
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• pp.270-274
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• 2017

Formic acid has been known as one of key sources of hydrogen. Among various monometallic catalysts, hydrogen can be efficiently produced on Pd catalyst. However, the catalytic activity of Pd is gradually reduced by the blocking of active sites by CO, which is formed from the unwanted indirect oxidation of formic acid. One of promising solutions to overcome such issue is the design of alloy catalyst by adding other metal into Pd since alloying effect (such as ligand and strain effect) can increase the chance to mitigate CO poisoning issue. In this study, we have investigated formic acid deposition on the bimetallic $Pd/Pd_3Fe$ core-shell nanocatalyst using DFT (density functional theory) calculation. In comparison to Pd catalyst, the activation energy of formic acid dehydrogenation is greatly reduced on $Pd/Pd_3Fe$ catalyst. In order to understand the importance of alloying effects in catalysis, we decoupled the strain effect from ligand effect. We found that both strain effect and ligand effect reduced the binding energy of HCOO by 0.03 eV and 0.29 eV, respectively, compared to the pure Pd case. Our DFT analysis of electronic structure suggested that such decrease of HCOO binding energy is related to the dramatic reduction of density of state near the fermi level.

• Clean Technology
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• v.20 no.2
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• pp.116-122
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• 2014

Various types of MOFs (metal-organic frameworks) were prepared via hydrothermal and post-grafting methods and applied as catalysts for the synthesis of jasminaldehyde, one of the representative perfume intermediates, by Aldol condensation of benzaldehyde with heptanal. Although both acid and base sites could catalyze the reaction, the catalytic performance was strongly dependent on the physical properties as well as the nature of functionalization on MOFs. While the use of sulfonated MOF catalysts led to decrease of jasminaldehyde selectivity regardless of MOFs used, the selectivity change was found to rely on the MOF types in the case of the amine-functionalization. Among the catalysts tested, MIL-101 shows the best catalytic performance, which may suggest that MIL-101 has suitable acid properties to promote the Aldol condensation and the large pore of MIL-101 is also advantageous to alleviate the diffusion problem of bulky products.

• Proceedings of the Membrane Society of Korea Conference
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• 1992.10a
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• pp.43-44
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• 1992

촉매막반응기란 반응기와 분리막이 동시에 하나의 과정으로 결합된 unit로, 촉매막반응기를 사용할 경우 가역 반응에서 막을 통한 생성물의 선택적 제거는 화학 평형이동을 유발시켜 열역학적으로 얻을수 있는 평형 전환율보다 높은 전환유을 얻을 수 있다. 본 연구는 이러한 촉매막반응기의 성능에 대한 실험적 연구로, 산 촉매하에서 일어나는 MTBE 분해반응을 12-텅스토인산 촉매상에서 수행하였다.

• Journal of the Korean Wood Science and Technology
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• v.40 no.6
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• pp.389-396
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• 2012

In this study, we investigated the kinetics of acid-catalyzed hydrolysis of xylan over a 60 min at $120^{\circ}C$. Sulfuric, oxalic and maleic acids were used as acid catalyst for hydrolysis. The calculated degradation rate constants ($k_1$) showed a correlation with the acid concentration, meaning that the stronger the acid, the higher the xylan degradation rate. Among sulfuric, oxalic and maleic acid catalyzed hydrolysis, the xylan degradation rate to xylose was highest with sulfuric acid. At equivalent solution pH, acid catalyzed hydrolysis was proportional to $H^+$ concentration. The $k_1$ of dicarboxylic acid such as oxalic and maleic acid was higher than that of sulfuric acid at same pH values during hydrolysis.

• Applied Chemistry for Engineering
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• v.8 no.2
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• pp.211-219
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• 1997

Liquid or gas phase alkylation of isobutane with 1-butene for i-octane production was carried out over Cs- or $NH_4$-exchanged $H_3PW_{12}O_{40}$. Pretreatment temperature of the catalyst played an important role on the catalytic activity of heteropoly acids in the liquid phase alkylation. Cation-exchanged $H_3PW_{12}O_{40}$ showed a better total yield and i-octane selectivity than the mother acid in the liquid phase alkylation, and $(NH_4)_{2.5}H_{0.5}PW_{12}O_{40}$ was more efficient than $Cs_{2.5}H_{0.5}PW_{12}O_{40}$ in terms of i-octane selectivity. It was found that the acidic property (deactivation of acid sites) of the catalyst was closely related to the catalytic activity of Cs- or $NH_4$-exchanged $H_3PW_{12}O_{40}$ in the gas phase alkylation. $C_5-C_7$ were mainly formed in the early stage of gas phase alkylation due to the strong acidic property of the catalyst, whereas $C_8$ and $+C_9$ were mainly produced as the reaction proceeded due to the deactivation of acid sites. $Cs_{2.5}H_{0.5}PW_{12}O_{40}$ showed the highest total yield in the gas phase alkylation among the catalysts examined.

• Clean Technology
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• v.19 no.3
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• pp.313-319
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• 2013

To produce biodiesel efficiently from fish oil containing 4% free fatty acid, esterification and trans-esterification were carried out with Vietnam catfish oil, which was kindly provided from GS-bio company. Heterogeneous solid acid catalysts such as Amberlyst-15 and Amberlyst BD-20 and sulfuric acid as homogeneous acid catalyst were used for the esterification of free fatty acids in the fish oil. Sulfuric acid showed the highest removal efficiency of free fatty acid and the shortest reaction time among three acid catalysts. The base catalysts for trans-esterification such as KOH, $NaOCH_3$ and NaOH were compared with each other and KOH was determined to be the best transesterification catalyst. Some solid material, which assumed to be saponified product from glycerol and biodiesel, were observed to form in the fish oil biodiesel when using $NaOCH_3$ and NaOH as the transesterification catalyst. The initial acid value of fish oil was proven to have a negative effect on biodiesel conversion. Of the three catalysts, KOH catalyst transesterification was shown to have high content of FAME and the optimal ratio of methanol/oil ratio was identified to be 9:1.

• Applied Chemistry for Engineering
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• v.29 no.2
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• pp.185-190
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• 2018

The dimer of bicyclo [2.2.1] hepta-2,5-diene (norbornadiene) can be used as a high-energy-density fuel. The purpose of this study is to investigate the effect of Co loading on the acid properties of HY zeolite catalyst and the catalytic activity in norbornadiene dimerization. When the cobalt was loaded on the HY zeolite catalyst, the amount of acid sites did not change, but the acid strength weakened. This can be attributed to the decrease in $Br{\ddot{o}}nsted$ acid site and the increase in Lewis acid site. The norbornadiene conversion and yield of norbornadiene dimer over the Co/HY catalyst showed higher than those over the HY zeolite catalyst. The higher activity of the Co/HY catalyst can be ascribed to the higher amount of Lewis acid sites over the Co/HY catalyst. Density and calorific values of the norbornadiene dimer prepared by using the Co/HY catalyst agreed well with the known values in the literature. It was confirmed that the norbornadiene dimer prepared in this study can be used as a high-energy-density fuel.

• Journal of the Korean Chemical Society
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• v.54 no.1
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• pp.131-136
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• 2010

Iron aluminophosphates (FeAlP) with different percentage of iron were synthesized and characterized for their surface and bulk properties. The catalytic activity was determined in the transesterification of diethyl malonate with benzyl alcohol. Benzyl ethylmalonate and dibenzyl malonate were obtained as the only products. FeAlP with 0.025 mole % of iron was found to be distinctly different in its textural and catalytic properties. Formation of diester was found to be favored by the acid sites of intermediate strength. The presence of hydrated alumina and the polycondensed phosphates in the materials reduced the catalytic activity of iron aluminophosphates in transesterification reaction.

• Korean Chemical Engineering Research
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• v.46 no.1
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• pp.194-199
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• 2008

In this study, the effective method to esterify the free fatty acids in jatropha oil was examined. Compared to other plant oils, the acid value of jatropha oil was remarkably high, 11.5 mgKOH/g. So direct transesterification by a base catalyst was not suitable for the oil. After the free fatty acids were esterified with methanol, jatropha oil was transesterified. The activities of four solid acid catalysts were tested and Amberlyst-15 showed the best activity for the esterification. After constructing the experiment matrix based on RSM and analyzing the statistical data, the optimal esterification conditions were determined to be 6.79% of methanol and 17.14% of Amberlyst-15. After the pretreatment, jatropha biodiesel was produced by the transesterification using KOH in a pressurized batch reactor. Jatropha biodiesel produced could meet the major specifications of Korean biodiesel standards; 97.35% of FAME, 8.17 h of oxidation stability, 0.125% of total glycerol and $0^{\circ}C$ of CFPP.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.224.1-224.1
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• 2010

본 연구에서는 천연가스 수증기 개질반응에 니켈 촉매가 코팅된 금속 구조체 촉매를 적용하여 수소를 생산하였다. 금속구조체 촉매는 기존 펠릿 촉매가 충진 된 촉매반응기에 비해 열 및 물질 전달 특성이 우수하여 이를 여러 개질반응에 적용하고자하는 연구가 수행되어 왔다. 하지만, 기존 금속구조체 촉매의 개발에 있어 촉매와 금속 지지체간의 안정한 결합을 통한 열안정성 확보에 대한 문제는 여전히 해결과제로 남아 있다. 따라서, 본 연구에서는 니켈 촉매를 금속 지지체에 안정하게 부착하기 위한 금속 지지체 표면 처리 방법을 개발하였으며 금속 구조체의 형상에 상관없이 균일한 표면처리가 가능하였다. 개발된 표면 처리방법을 적용한 금속 구조체 촉매는 촉매와 금속지지체간의 결합력 향상으로 인해 120시간 이상 안정한 반응활성을 보였다. 또한, 빠른 공간속도에서도 펠릿촉매와 표면처리를 적용하지 않은 금속 구조체 촉매에 비해 높은 촉매 활성을 보였다. 뿐만 아니라, 본 연구에서 개발된 표면처리를 모노리스와 폼을 비롯한 다양한 형상의 금속구조체 촉매에 적용하여 기하학적 표면 특성에 따른 촉매의 활성 차이를 살펴보았다. 겉보기 표면적이 넓은 금속구조체일 수록 촉매의 고분산 코팅에 유리하여 높은 활성을 보였다.