• Title/Summary/Keyword: Methanol conversion

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Phenol Hydroxylation over TS-1 Synthesized by Hydrothermal and Microwave Heating Method: Solvent Dependence (수열 합성법과 마이크로파 가열법으로 제조한 TS-1 촉매에 의한 페놀 수산화 반응: 용매의 영향)

  • Kwon, Song-Yi;Yoon, Song-Hun;Lee, Jong-Min;Chang, Jong-San;Lee, Chul-Wee
    • Korean Chemical Engineering Research
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    • v.49 no.2
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    • pp.151-154
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    • 2011
  • Catalytic activity such as conversion and selectivity on the phenol hydroxylation over TS-1 prepared by hydrothermal method and microwave heating method, respectively, was compared and discussed for understanding the dependence of solvent such as water, methanol, acetone, respectively, during phenol hydroxylation, with hydrogen peroxide. Basic physical properties such as XRD, EDS, SEM and $N_{2}$ adsorption/desorption were determined and compared. The relationship between catalytic activity and physical properties of TS-1 was explained.

Performance of Pilot-Scale Biodiesel Production System (파일럿 규모의 바이오디젤 생산공정의 실증연구)

  • Jeong, Gwi-Taek;Park, Jae-Hee;Park, Seok-Hwan;Park, Don-Hee
    • KSBB Journal
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    • v.24 no.1
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    • pp.89-95
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    • 2009
  • Biodiesel (fatty acid alkyl esters), which is produced from sustainable resources such as vegetable oil, animal fat and waste oils, have used to as substitutes for petro-diesel. In this study, we investigate the performance of 30 L and 300 L pilot-scale biodiesel production system using alkali-catalyst transesterification from soybean oil and rapeseed oil produced at Jeju island in Korea. The 30 L-scale biodiesel production was performed to in the condition of reaction temperature $65^{\circ}C$, catalyst amount 1% (w/w) and oil to methanol molar ratio 1 : 8. At that reaction condition, the fatty acid methyl ester contents of product are above 98% within reaction time 30 min. Also, the conversion yield of over 98% was obtained in 300 L-scale biodiesel production system using rapeseed oil and soybean oil. The quality of biodiesel produced from reaction system was satisfied to recommended quality standard of Korea. Our results may provide useful information with regard to the scale-up of more economic and efficient biodiesel production process.

Syngas and Hydrogen Production from $CeO_2/ZrO_2$ coated Foam Devices under Simulated Solar Radiation (다공성 폼에 코팅된 $CeO_2/ZrO_2$ 를 이용한 고온 태양열 합성가스 및 수소 생산 연구)

  • Jang, Jong-Tak;Yoon, Ki-June;Han, Gui-Young
    • 한국태양에너지학회:학술대회논문집
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    • 2012.03a
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    • pp.260-266
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    • 2012
  • Syngas and hydrogen from the $CeO_2/ZrO_2$ coated foam devices were investigated under simulated solar radiation. The $CeO_2/ZrO_2$ coated SiC, Ni and Cu foam device were prepared using drop-coating method. Syngas production step was performed at $900^{\circ}C$, and hydrogen production process was performed for ten repeated cycles to compare the CeO2 conversion in syngas production step, $H_2$ yield in hydrogen production step and cycle reproducibility. The produced syngas had the $H_2$/CO ratio of 2, which was suitable for methanol synthesis or Fischer-Tropsch synthesis process. In addition, syngas and hydrogen production process is one of the promising chemical pathway for storage and transportation of solar heat by converting solar energy to chemical energy. After ten cycles of redox reaction, the $CeO_2/ZrO_2$ was analyzed using XRD pattern and SEM image in order to characterize the physical and chemical change of metal oxide at the high temperature.

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Electron Donor Determination and Comparisons of Reaction Rates for Bioremediation of Nitrate Contaminated Groundwater (질산성 질소로 오염된 지하수의 생물복원을 위한 적정 전자공여체의 결정 및 반응속도 비교 연구)

  • Oa, Seongwook;Lee, Yoonhee;Kim, Geonha;Kim, Young
    • Journal of Korean Society on Water Environment
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    • v.21 no.6
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    • pp.630-636
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    • 2005
  • Groundwater contamination by nitrate exceeding water quality criteria (10 mg $NO_3{^-}-N/L$) occurs frequently. Fumarate, acetate, formate, lactate, propionate, ethanol, methane and hydrogen gas were evaluated for their nitrate removal efficiencies and removal rates for in situ bioremediation of nitrate contaminated groundwater. Denitrification rate for each substrate was in the order of: fumarate > hydrogen > formate/lactate > ethanol > propionate > methanol > acetate. Microcosm studies were performed with fumarate and acetate. When fumarate was used as a substrate, nitrate was removed 100 percent with rate of 0.66 mmol/day while conversion rate from nitrate to nitrogen gas or another by-product was 87 percent. 42 mg of fumarate was needed to remove 30 mg $NO_3{^-}-N/L$. When using acetate as carbon source, 31 percent of nitrate was removed during initial adjustment period. Among removed fraction, however, 83 percent of nitrate removed by cell growth. Overall nitrate removal rate was 0.37 mmol/day. Acetate showed longer lag time in consumption compared to that of nitrate, which implying that acetate would be better carbon source compared to fumarate as more amount was utilized for nitrate removal than cell growth.

Anthracene-Sensitized Photolysis of Onium Tetrakis(Pentafluorophenyl) Borate Cationic Photoinitiators

  • Yasumasa Toba;Midori Saito
    • Journal of Photoscience
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    • v.5 no.3
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    • pp.111-120
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    • 1998
  • Sensitized photolysis of two onium borates (diphenyliodoium and dimethylphenacylsulfonium tetrakis(pentafluorophenyl)borate, 1a and 2a , respectively) and cationic photopolymerization of an epoxy monomer by the photolysis were investigate. The onium borates were sensitized by the excited singlet of the athracenes(non-substituted, 9-methyl-and 9, 10-dimethylanthracene) and generated acid by decomposing teemselves. The quantum yields of photobleaching of the anthracenes($\Phi$-AH) and acid generatiion (øacid) by the onium borates were the same order as those of the corresponding onium salts in aerated solutions (methanol and acetoitrile) and in argon(Ar) saturated acetonitrile. However, in the photolysis of the iodonium borates 1a in Ar saturated MeOH , øacid was much higher than the corresponding ø-AH. The acid generated by the photolysis of the onium borates initiated cationic polymerization of an epoxy monomer. The values of both rate of polymerization (Rp) and degree of conversion on the photopolymerization for the iodonium borated 1a were higher than those of the sulfoium borate 2a. In the photopolymerization for the iodonium borate 1a, both the Rp value and the degree of conversinio increased upon the addition of glycerol as a hydrogen donor. It is suggested that the increase of both values may be caused with the increase of øacid by addition of glycerol.

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Bifunctional Fe-SBA-15-SO3H Mesoporous Catalysts with Different Si/Fe Molar Ratios: Synthesis, Characterization and Catalytic Activity

  • Erdem, Sezer;Erdem, Beyhan;Oksuzoglu, Ramis Mustafa;Citak, Alime
    • Bulletin of the Korean Chemical Society
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    • v.34 no.5
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    • pp.1481-1486
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    • 2013
  • Bifunctional Fe-SBA-15-$SO_3H$ mesoporous materials with different Si/Fe molar ratios (3, 5, and 7) have been synthesized via a simple direct hydrothermal method and characterized by XRD, $N_2$-adsorption/desorption, TG/DTG and FT-IR techniques, and used as solid acid catalysts in the esterification of lactic acid with methanol. XRD and $N_2$ sorption characterizations show successful iron doping within the mesoporous channels of SBA-15-$SO_3H$. The FT-IR and TG/DTG characterizations also reveal the presence of iron. With the incorporation of Fe ions into the SBA-15-$SO_3H$, the acid sites substantially increased because of the self-separated acidity of the hydrolysis of $Fe^{3+}$ solutions. However, in the Si/Fe = 3 molar ratio, the catalytic conversion decreased which is caused by the reduced cooperation effect between the acid pairs due to the weakened hydrogen bonds and collapse of the pore structure. This further suggests that the mesoporous structure decreases with the decrease in Si/Fe ratio.

The Preparation of High $J_c$ YBCO Films by DCA-MOD Method (DCA-MOD 법에 의한 High $J_c$ YBCO 박막의 제조)

  • Kim, Byeong-Joo;Kim, Hye-Jin;Yi, Keum-Young;Lee, Jong-Beum;Kim, Ho-Jin;Lee, Hee-Gyoun;Hong, Gye-Won
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2006.12a
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    • pp.107-108
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    • 2006
  • High $J_c$ $YBa_2Cu_3O_x$, superconducting films were fabricated by MOD method using fluorine-free dichloroacetic acid(DCA) as chelating solvent for preparing precursor solution. DCA-MOD precursor solution was coated on a single crystal (001) $LaAlO_3$(LAO) substrate by a dip coating method with a speed of 25 mm/min. Coated films were calcined at lower temperature up to $500^{\circ}C$ and Conversion heat treatment was performed at various temperatures of $780{\sim}810^{\circ}C$. SEM observations showed that films have very dense microstructures for the films prepared at the temperature higher than $800^{\circ}C$ regardless of diluting solvent; methanol or 2-methoxyethanol. A High critical current density ($J_c$) of 1.28 $MA/cm^2$ (@77 K and self-field) was obtained for the YBCO film prepared using 2-methoxyethanol as a solvent.

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Adsorption and Catalytic Characteristics of Acid-Treated Clinoptilolite Zeolite (산처리한 Clinoptilolite Zeolite 의 흡착 및 촉매특성)

  • Chon Hakze;Seo Gon
    • Journal of the Korean Chemical Society
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    • v.20 no.6
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    • pp.469-478
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    • 1976
  • Clinoptilolite zeolite samples were treated with hydrochloric acid, sulfuric acid and phosphoric acid of different strength and the adsorption characteristics and crystal structures of the original and acid-treated clinoptilolites were studied. By treating with hydrochloric acid, the adsorbed amount increased to 5-fold for nitrogen, to 3-fold for benzene, but for methanol no significant change was observed. As acid strength increased further, there were declines both in adsorption capacity and crystallinity. The results showed that the increase of adsorbed amount was caused by the rearrangement of the pore entrance and cation exchange. A method for determination of clinoptilolite content in natural mineral based on benzene adsorption on acid-treated sample is proposed. By this method, the original sample used in this study was found to contain approximately 40% of clinoptilolite. Using pulse technique in micro-catalytic reactor system, the catalytic activities of hydrochloric acid-treated clinoptilolites in cumene cracking and toluene disproportionation reactions were measured. For cumene cracking reaction, the maximum conversion was observed for the 0.5 N hydrochloric acid-treated sample. It is instructive to note that the maximum benzene adsorption was also observed for the sample treated with 0.5 N HCl. This suggest that the conversion rate was determined mainly by the rate of transport of reactants and the products through the pore structure. In the toluene disproportionation reaction, the same trend was observed. But the rate of deactivation was high for samples with strong acid sites. Since catalyst having higher activity was deactivated more easily, the conversion maximum was shifted to the sample treated with higher concentration of acid, -1N. The catalytic activity of $Ca^{2+} and La^{3+} ion exchanged samples for the toluene disproportion was much lower than that of acid-treated samples. Introduction of Ca^{2+} and La^{3+}$ into the pore structure apparently decreases the effective pore diameter of acid-treated clinoptilolite thus limiting the diffusion of reactants and products.

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Esterification Reaction of Animal Fat for Bio-diesel Production (바이오디젤 생산을 위한 동물성 오일의 에스테르화 반응)

  • Kim, Sung-Min;Kim, Deog-Keun;Lee, Jin-Suk;Park, Soon-Chul;Rhee, Young-Woo
    • Clean Technology
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    • v.18 no.1
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    • pp.102-110
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    • 2012
  • In this study, the production of bio-diesel from animal oil by esterification and trans-esterification was investigated. There were three different extraction methods for oil extraction from raw animal fat. Heterogeneous catalysts such as Amberlyst-15 and Amberlyst BD-20 and a homogeneous catalyst such as sulfuric acid were used for esterification. Among three catalysts, the removal efficiency of Free Fatty Acid (FFA) was the highest in sulfuric acid. Response surface method was carried out to find the optimal esterification condition of sulfuric acid and methanol. After the esterification under the optimal condition, this animal fat was used for the trans-esterification. Animal oil used for trans-esterification was below 1% of FFA content and 0.09% of water content. The catalysts for trans-esterification were KOH, NaOH and $NaOCH_3$. To investigate the effects of catalyst type and amount on trans-esterification, The amount of catalyst were changed with 0.3, 0.6 and 0.9 wt%. The molar ratio of methanol/oil was changed with 4, 6, 9 and 12. The amount of catalyst was fixed to 0.8 wt%. The KOH catalyst showed the highest FAME conversion for trans- esterification, and the optimal methanol/oil weight ratio was 6. In the experiments of various catalysts and methanol molar ratios, the highest content of FAME is 96%. However, this FAME content was below Korean bio-diesel standard which is 96.5% of FAME content. After distillation, FAME content increased to 98%.

The Esterification of Oleic Acid Using Acidic Ionic Liquid Catalysts Immobilized on Silica Gel (실리카겔에 고정화된 산성 이온성 액체 촉매를 이용한 올레산의 에스터화 반응연구)

  • Choi, Jae-Hyung;Park, Yong-Beom;Lee, Suk-Hee;Cheon, Jae-Kee;Woo, Hee-Chul
    • 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.