• Applied Chemistry for Engineering
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• v.19 no.5
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• pp.559-567
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• 2008

SAPO-34 is a well-known catalyst for methanol to olefins (MTO) process, but is rapidly deactivated by coke formation. It is necessary to improve the catalyst lifetime of SAPO-34 for MTO process. In the present work, SAPO-34 catalysts were synthesized with a variety of structure directing agent, and the physicochemical properties of the catalysts were examined by $N_2$-isotherm, XRD, SEM, and $NH_3$-TPD. It was found that mixed structure directing agents, especially DEA and TEAOH, gave well developed SAPO-34 crystal structure and reduced the crystal size and moderated acidity of SAPO-34 under the same synthetic conditions as that of various structure directing agents. Also, we could find that SAPO-34 catalyst prepared by mixed templates of DEA and TEAOH had the superior catalytic activity and the longer lifetime in MTO reaction.

• Clean Technology
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• v.30 no.2
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• pp.145-156
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• 2024

Carbon has a large specific area and excellent chemical stability, so research on its use as a catalyst support is actively conducted. When using carbon as a support, the pretreatment process is essential. Through pretreatment of carbon, the growth of metal nanoparticles can be controlled and the bonding strength between the support and metal particles can be improved. In this study, carbon was pretreated for surface modification and 5 wt% Pd/C catalysts were synthesized using it as a support. Catalytic activity was evaluated through phenol hydrogenation. To compare with nitric acid, which is commonly used in carbon pretreatment, carbon pretreatment was performed using organic acid. Pd/C treated with gluconic acid showed the highest activity, with 94.93% phenol conversion and 92.76% cyclohexanone selectivity. Therefore, it is expected that pretreatment of the carbon support using organic acid will not only overcome the disadvantages of inorganic acid treatment but also improve catalyst performance.

• Korean Chemical Engineering Research
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• v.48 no.5
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• pp.583-588
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• 2010

Esterification of free fatty acid with methanol to biodiesel was investigated in a batch reactor using various solid acid catalysts, such as polymer cation-exchanged resins with sulfuric acid functional group(Amberlyst-15, Dowex 50Wx8), acidic ionic liquids (ILs)-modified silica gels respectively with $-SO_3H$ and $-SO_2Cl$ functional group ($SiO_2-[ASBI][HSO_4]$, $SiO_2-[ASCBI][HSO_4]$) and grafted silica gels respectively with $-SO_3H$ and $-SO_2Cl$ functional group ($SiO_2-R-SO_3H$, $SiO_2-R-SO_2Cl$). The effects of reaction time, temperature, reactant concentration(molar ratio of methanol to oleic acid), and catalyst amount were studied. Allylimidazolium-based ILs on modified silica gels were superior to other tested solid acid catalysts. Especially, the performance of $SiO_2-[ASBI][HSO_4]$ (immobilized by grafting of 3-allyl-1-(4-sulfobutyl)imidazolium hydrogen sulfate on silica gel) was better than that of a widely known Amberlyst-15 catalyst at the same reaction conditions. A high conversion yield of 96% was achieved in the esterification reaction of the simulated cooking oil at 353 K for 2 h. The high catalytic activity of $SiO_2-[ASBI][HSO_4]$ was attributed to the presence of strong Brønsted acid sites from the immobilized functional groups. The catalyst was recovered and the biodiesel product was separated by simple processes such as decantation and filtration.

• Applied Chemistry for Engineering
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• v.5 no.1
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• pp.139-148
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• 1994

The partial oxidation of methane with nitrous oxide on silica-supported metal-oxygen cluster compounds, known as heteropoly acids, has been studied. The effects of several variables such as reaction temperature, partial pressure of reactants, residence time, loading of the catalysts, and pretreatment temperature, on the conversion and product distribution were observed. The kinetics also has been studied. The conversion and yield of formaledehyde show maximum values at a loading of 20 wt%. The apparent reaction order of methane conversion is ca. 1.0 with respect to $CH_4$ and ca. 0.4 with respect to $N_2O$. In addition, the apparent activation energy is 30.78 kcal/mole. The addition of small quantities methane whereas water introduced to the reactant decreased the activity of catalyst under present study.

• Clean Technology
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• v.16 no.3
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• pp.220-228
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• 2010

Four Keggin-type heteropolyacids, $H_nXM_{12}O_{40}$(X = P and Si, M = W and Mo) that were substituted with heteroatom and polyatom were applied to the dehydration reaction of fructose to 5-hydroxymethylfurfural (HMF). The results showed that the acid became stronger when the heteroatom and polyatom were substituted with P and W than the cases of Si and Mo, respectively. However, the amount of acidic sites increased with the decrease in the acid strength, resulting in the change of the catalytic activity of heteropolyacids in the dehydration reaction. The experimental results revealed that four different heteropolyacids produced similar amounts of HMF via the dehydration reaction of fructose due to the counterbalancing effect between the amount of active sites, which is related to the catalytic activity of heteropolyacids, and the softness of polyanion. In addition, it was observed that the prepared heteropolyacids showed good structural stability after heat treatment at $200^{\circ}C$.

• Applied Chemistry for Engineering
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• v.28 no.2
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• pp.165-170
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• 2017

An efficient synthetic process for bio-based adipic acid, a monomer for nylon 66, was developed from galactose. Galactaric acid, prepared from a mild oxidation of galactose using a Pt catalyst, was successfully converted to muconate, a key intermediate for adipic acid, by an efficient microwave-assisted DODH (deoxydehydration) reaction. The high efficiency of the microwave-assisted reaction greatly reduced the overall reaction time to 30 min. and resulted in an excellent yield of 97% of muconate. The catalytic hydrogenation of muconate followed by the acidic hydrolysis successfully produced the desired adipic acid in high purity after recrystallization.

• Korean Chemical Engineering Research
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• v.50 no.2
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• pp.251-256
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• 2012

Etherification of n-butanol to di-n-Butyl Ether was carried out over Keggin $H_{3+x}PW_{12-x}Nb_xO_{40}$ (x=0, 1, 2, 3) and $H_{6+x}P_2W_{18-x}Nb_xO_{62}$ (x=0, 1, 2, 3) Wells-Dawson heteropolyacid catalysts. Niobium-substituted Keggin and Wells-Dawson heteropolyacid catalysts with different niobium content were prepared. Successful preparation of the catalysts was confirmed by FT-IR, ICP-AES, and $^{31}P$ NMR analyses. Their acid properties were determined by $NH_3$-TPD (Temperature-Programmed Desorption) measurements. Heteropolyacid catalysts showed different acid properties depending on niobium content in both series. The correlation between acid properties of heteropolyacid catalysts and catalytic activity was then established. Acidity of Keggin and Wells-Dawson heteropolyacid catalysts decreased with increasing niobium content, and conversion of n-butanol and yield for di-n-butyl ether increased with increasing acidity of the catalysts, regardless of the identity of heteropolyacid catalysts (without heteropolyacid structural sensitivity). Thus, acidity of heteropolyacid catalysts served as an important factor determining the catalytic performance in the etherification of n-butanol to di-n-Butyl Ether.

• Korean Chemical Engineering Research
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• v.47 no.1
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• pp.96-104
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• 2009

In order to lower a reaction temperature with high conversions for simultaneous catalytic reduction of NO and $N_2O$ over Pd-Rh supported mixed metal oxide honeycomb catalysts, $H_2$ or CO was utilized as a reductant. When using the reductants, the effects of reaction conditions were examined in NO and $N_2O$ conversions, where reaction temperatures, concentrations of the reductants and oxygen and the concentration ratio of $N_2O$ to NO were varied. In using $H_2$ reductant, larger than 50% of NO and $N_2O$ conversions was observed at the temperatures below $200^{\circ}C$ in absence of $O_2$. In using CO reductant, NO and $N_2O$ conversions increased from the temperatures higher than $200^{\circ}C$ and $300^{\circ}C$, respectively. However, in use of both reductants, NO and $N_2O$ conversions decreased with increasing oxygen concentration. As a result, $H_2$ reductant could reduce simultaneously NO and $N_2O$ at relatively lower reaction temperature than CO. Also, NO and $N_2O$ conversions were less influenced by using $H_2$ reductant than CO one. Concentration ratio between NO and $N_2O$ did not affect their conversions regardless the type of reductants. Pretreatment of the catalyst in $H_2$ was more effective in simultaneous reduction of NO and $N_2O$ at low reaction temperature than that in $O_2$.

• 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.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.251.1-251.1
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• 2010

바이오디젤은 동식물성 기름과 메탄올의 트랜스에스테르화 반응에 의해 생산되는 지방산메틸에스테르(FAME, fatty acid methyl esters)로서, 트랜스에스테르화 공정에는 KOH, NaOH, $NaOCH_3$등의 균질계 화학촉매를 이용한 방법, 무촉매 공정인 초임계 메탄올 이용 방법, 그리고 효소촉매를 이용한 방법이 있다. 초임계 공정은 에너지 소비와 장치비가 커서 경제성이 떨어지는 것으로 보고되며 화학촉매 공정은 반응 효율이 높다는 장점을 가지고 있지만, 반응 및 정제단계가 복잡하고 정제과정에 폐수를 발생시키는 문제점을 가지고 있다. 고정화 효소를 사용하는 효소 공정은 에너지 비용의 절감, 후 처리 공정의 단순화, 고 순도의 글리세롤을 얻을 수 있는 장점이 있지만, 반응 속도가 느리고 효소 가격이 비싸다는 단점이 있어 현재까지 상업화되지 못하고 있다. 반응속도가 높고 재사용이 가능한 효소 촉매 공정 개발을 위해 본 연구에서는 Candida rugosa, Rizhopus oryzae 2종을 실리카에 동시 고정화하였다. 고정화 Lipase의 제조는 실리카겔을 과산화수소를 이용하여 전처리를 하고 Acetone과 3-APTES의 혼합용액을 첨가한 후 실리카겔과 (silanization)을 진행 하였다. 그리고 glutaraldehyde를 첨가 하여 공유 결합을 형성 한 후에 증류수를 사용하여 실리카겔을 회수하여 lipase(Rizhopus oryzae, Candida rugosa 10% 용액)를 고정화 하였다. 고정화 효소의 효소 활성을 측정한 결과 3000-3500 Unit(${\mu}mol/g{\cdot}min$)으로 측정되었다. 제조된 고정화 효소를 이용하여 Canola Oil을 바이오디젤로 전환하는 실험을 진행하였으며 생성물로부터 고정화 효소를 분리한 후에 상층의 에스테르층을 취하여 수세한 뒤 원심분리하여 FAME 함량을 측정한 결과 83%의 바이오디젤을 얻을 수 있었다. 그리고 효소 촉매 트랜스에스테르화 반응의 Enzyme, Water, Methanol 투입량의 반응 변수들에 대하여 반응표면분석법(Response Surface Methodology)을 적용하여 최적 반응조건을 도출하는 연구를 수행하였다.