• Title/Summary/Keyword: Methanol Synthesis

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Dynamic Optimization of a Reactive Distillation Column Producing Methyl Acetate (메틸 아세테이트 생산을 위한 반응증류 공정의 동적 최적화)

  • Kim, Jiyong;Kim, Junghwan;Moon, Il
    • Korean Chemical Engineering Research
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    • v.46 no.4
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    • pp.739-746
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    • 2008
  • The aim of this study is finding the optimal design parameters and the optimal operation variables of a reactive distillation column. Different from steady state optimization, dynamic optimization makes it possible considering operation ability as well as design problems at process design step. For performing dynamic optimization, dynamic simulation should be done first. If dynamic simulation is already finished, dynamic optimization can be performed with less effort than that of dynamic simulation.Reactive distillation systems involving reaction and separation in a single unit have the potential to reduce capital and operating costs, particularly when reaction have conversion constraint or when azeotropes exist making conventional separation difficult and expensive. This study here present work on the continuous distillation process, the homogeneous catalyzed esterification of methanol and acetic acid, the synthesis of methyl acetate. Based on an equilibrium stage model of a reactive distillation column a dynamic optimization problem was formulated and solved. And the results were verified by performing dynamic simulation and showing the variation of conversion and purity as the variation of the operation variables. As the results of dynamic optimization, this study found optimal feed ratio, reflux ratio and reboiler duty of this system. And as this study applied it to dynamic simulations the dynamic characteristics of a reactive distillation column are showed under optimal operating condition.

Synthesis, Characterization and ESR Studies of New Copper(II) Complexes of Vicinal Oxime Ligands (Vicinal Oxime 리간드의 새로운 구리(II) 착물에 대한 합성, 특성 및 ESR 연구)

  • El-Tabl, Abdou S.;Shakdofa, Mohamad M.E.;El-Seidy, Ahmed M.A.
    • Journal of the Korean Chemical Society
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    • v.55 no.4
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    • pp.603-611
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    • 2011
  • Ethoxylacetyl oxime ligands [HL, (1) and $H_2L^1$, (3)] react with copper(II) acetate monohydrate yield octahedral and square planar complexes, respectively. The complexes have been postulated due to elemental analyses, IR, UVVis. spectra, magnetic susceptibility, conductivity and ESR spectra. Molar conductance of the complexes in DMF indicates a non-ionic character. The ESR spectra of [$(L)_2Cu(H_2O)_2$], (2) complex at room temperature and 77K are characteristic of an axial symmetry ($d_{x2-y2}$) with covalent bond character and have a large line width typical of dipolar interactions. However, [$(L^1)Cu$], (4) complex in the solid state showed spectra of marked broadening and loss of hyperfine splitting confirming spinexchange interactions between the copper(II) sites. The spectrum of the doped copper(II) complex at room temperature showed super-hyperfine splitting from coordinated nitrogen atoms and it has an axial type ($d_{x2-y2}$) with covalent bond character and an essentially square-planar arrangement around the copper(II) ion. The spectrum of [$(L^1)Cu$], (4) in frozen methanol at 77K was characteristic of the triplet state of a dimer species and the distance found between the two copper(II) centers was calculated and is equal to 4.8 ${\AA}$.

Synthesis and Characterization of Hybrid Nanocomposites of Pd Nanoparticles Containing POSS(Pd-POSS) and Poly(acrylic acid) via Ionic Interactions (실세스키옥세인을 포함한 팔라듐 나노입자와 폴리아크릴산과의 이온결합에 의한 나노복합체 제조 및 특성평가)

  • Jeon, Jong-Hwan;Lim, Jung-Hyurk;Chujo, Yoshiki;Kim, Kyung-Min
    • Polymer(Korea)
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    • v.33 no.6
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    • pp.615-619
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    • 2009
  • Pd-POSS nanoparticles were produced from the reaction of palladium (II) acetate and octa(3-aminopropyl)octasilsesquioxane octahydrochloride (POSS-${NH_3}^+$) in methanol at room temperature. Pd-POSS nanoparticles with a mean diameter of 60-80 nm were the highly ordered spherical aggregates. In contrast, Pd nanoparticles with a size of 4.0 nm were obtained when POSS-${NH_3}^+$ was not introduced. Pd-POSS/PAA nanocomposites of Pd-POSS nanoparticles and poly(acrylic acid) (PAA) were fabricated by utilizing ionic interactions between positively charged Pd-POSS nanoparticles and negatively charged carboxylate groups of PAA. PAA was used as a cross-linker for the preparation of hybrid nanocomposites with the controlled organized structures of Pd-POSS nanoparticles. That is, the self-organization of Pd-POSS nanoparticles was formed into the shape of continuous lines by using PAA as a cross-linker. The composition, structure, surface morphology, and thermal stability of the Pd-POSS/PAA nanocomposites were studied by FE-SEM, AFM, TEM, FT-IR, and TGA.

The Effects of Polymerization Catalyst Systems on the Synthesis of Poly(2,6-dimethyl-1,4-phenylene ether) (중합촉매 시스템이 폴리페닐렌에테르의 합성에 미치는 영향)

  • Lee, Chang-Jae;Kim, Yong-Tae;Kim, Jin-Kyu;Kim, Ji-Heung;Nam, Sung-Woo;Jeon, Boong-Soo;Kim, Young-Jun
    • Polymer(Korea)
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    • v.36 no.1
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    • pp.98-103
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    • 2012
  • Poly(2,6-dimethyl-1,4-phenylene ether) (PPE) was synthesized using $Cu(NO_2)_2{\cdot}3H_2O$ or CuCl catalyst with various amounts of ligand and base in several different solvent systems. CuCl/1-methylimidazole/ammonium hydroxide was found to be an effective catalyst system which showed the highest polymer yield and molecular weight. The effects of catalyst/monomer ratio, different amine ligands, and the content of mono-functional reagent 2,4,6-trimethylphenol (TMP) additive on the polymer yield and molecular weight were investigated. Among the co-solvent systems used in this polymerization, chloroform/methanol 9/1(v/v) gave the highest polymer yield and molecular weight ($\overline{M_n}$ 55 K, $\overline{M_w}$ 92 K, PDI 1.7). The catalytic activity between CuCl and CuI was compared by oxygen-uptake experiments and the formation of sideproduct, 5,5'-tetramethyl-4,4'-diphenoquinone (DPQ), was analyzed by ultraviolet spectroscopy.

Antioxidant and whitening effects of loquat (Eriobotrya japonica) fruit extracts (비파(Eriobotrya japonica) 열매 추출물의 산화방지능과 미백 효과)

  • Yun, Min-Kyu;Park, Gi-Cheol;Cho, Youn-Sup;Kim, Dae-Ok
    • Korean Journal of Food Science and Technology
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    • v.54 no.3
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    • pp.280-287
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    • 2022
  • The loquat (Eriobotrya japonica) is a fruit tree belonging to the Rosaceae family. Loquat fruit extracts from three cultivars (Tanaka, Mogi, and Jinwang) were prepared using absolute methanol and homogenization and ultrasound sonication procedures. We measured the total phenolic and flavonoid content of the fruit extracts and their antioxidant capacities. In addition, we evaluated tyrosinase activity and anti-melanogenic effects in B16F1 melanoma cells. The fruit extract from cv. Tanaka had the highest total phenolic content and showed the highest antioxidant capacity in the ABTS assay. The loquat fruit extract from cv. Jinwang had the highest total flavonoid content and showed the highest antioxidant capacity in the DPPH assay. Loquat fruit extracts from the Tanaka and Jinwang cultivars effectively inhibited mushroom tyrosinase activity. The loquat fruit extracts reduced intracellular oxidative stress in B16F1 melanoma cells. Treating B16F1 melanoma cells with loquat fruit extract from cv. Tanaka at a concentration of 125 ㎍/mL effectively inhibited melanin synthesis. However, treating the B16F1 melanoma cells with loquat fruit extracts from the Jinwang and Mogi cultivars did not. These results suggest that loquat fruit extracts from the Tanaka cultivar may serve as potential sources of antioxidants and act as a skin-whitening agent.

Characterization of a Psychrophilic Metagenome Esterase EM2L8 and Production of a Chiral Intermediate for Hyperlipemia Drug (메타게놈유래의 저온성 에스터라제 EM2L8의 효소적 특성과 이를 활용한 고지혈증 치료제 키랄소재의 생산)

  • Jung, Ji-Hye;Choi, Yun-Hee;Lee, Jung-Hyun;Kim, Hyung-Kwoun
    • Microbiology and Biotechnology Letters
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    • v.37 no.2
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    • pp.118-124
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    • 2009
  • Esterase EM2L8 gene isolated from deep sea sediment was expressed in Escherichia coli BL21 (DE3) and the esterase activity of the cell-free extract was assayed using p-nitrophenyl butyrate-spectrophotometric method. Its optimum temperature was $40-45^{\circ}C$ and 45% activity of the maximum activity was retained at $15^{\circ}C$. The activation energy at $15-45^{\circ}C$ was calculated to be 4.9 kcal/mol showing that esterase EM2L8 was a typical cold-adapted enzyme. Enzyme activity was maintained for 6 h and 4 weeks at $30^{\circ}C$ and $4^{\circ}C$, respectively. When each ethanol, methanol, and acetone was added to the reaction mixture to 15% concentration, enzyme activity was maintained. In the case of DMSO, enzyme activity was kept up to 40% concentration. (S)-4-Chloro-3-hydroxy butyric acid is a chiral intermediate for the synthesis of Atorvastatin, a hyperlipemia drug. When esterase EM2L8 (40 U) was added to buffer solution (1.2 mL, pH 9.0) containing ethyl-(R,S)-4-chloro-3-hydroxybutyrate (38 mM), it was hydrolyzed into 4-chloro-3-hydroxy butyric acid with a rate of $6.8\;{\mu}mole/h$. The enzyme hydrolyzed (S)-substrate more rapidly than (R)-substrate. When conversion yield was 80%, e.e.s value was 40%. When DMSO was added, hydrolysis rate increased to $10.4\;{\mu}mole/h$. The plots of conversion yield vs e.e.s in the presence or absence of DMSO were almost same, implying that the reaction enantioselectivity was not changed by the addition of DMSO. Taken together, esterase EM2L8 had high activity and stability at low temperatures as well as in various organic solvents/aqueous solutions. These properties suggested that it could be used as a biocatalyst in the synthesis of useful pharmaceuticals.

Antioxidant and Tyrosinase Inhibitory Effects of Brassica oleracea L. Fractions (적채 분획물의 항산화 및 Tyrosinase 억제 효과)

  • 윤경아;박윤자;배송자
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.33 no.1
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    • pp.7-15
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    • 2004
  • This research was designed to investigate the antioxidant activity of red cabbage (Brassica oleracea L., BO) fractions on the liposomes consisted of L-$\alpha$-dilinoleoylphosphatidylcholine (DLPC-liposome) and the tyrosinase activity of BO fractions. The methanol extract of BO (BOM) was fractionated into five different partition layers: hexane (BOMH), ethylether (BOMEE), ethylacetate (BOMEA), butanol (BOMB) and aqueous (BOMA) layers. The antioxidant activities of BOM fractions toward oxidized DLPC-liposome were examined by spectrophotometry measuring oxidized conjugated dines. The antioxidant activities of BOMEE and BOMEA fractions toward oxidized DLPC-liposomes were similar to the antioxidant activities of $\alpha$-tocopherol and weaker than that of BHT. The synergy effects of antioxidation of BOMEE and BOMEA fractions added with vitamin C and $\alpha$-tocopherol had even stronger antioxidant activities than the fractions without vitamin C and $\alpha$-tocopherol. These results showed that the fractions of BOMEE and BOMEA could be developed as a potent antioxidant. Out of five different partition layers of BOM fractions, BOMEA exhibited the strongest tyrosinase activity of 94% at a concentration of 40 $\mu\textrm{g}$/mL. This result suggests BOMEA fractions inhibit the foramation of melanin and therefore can be used as the inhibitor of melanin synthesis. Results of antioxidant activity and tyrosinase inhibition indicate that useful bioactive substances exist in BOMEE and BOMEA fractions. Both fractions from BO (red cabbage) have the potential of being developed into health related products.

Studies on the Ginseng Plants(III) -Radioactive Sodium $Acetate-U-C^{14}$ Feeding Experiments- (인삼식물(人參植物)에 관한 연구(III) -동위원소화합물(洞位元素化合物) Sodium $Acetate-U-C^{14}$을 투여한 실험-)

  • Kim, Jung-Yun;Staba, E. John
    • Korean Journal of Pharmacognosy
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    • v.5 no.2
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    • pp.111-124
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    • 1974
  • The radioactive compound sodium $acetate-U-C^{14}\;(C^{14}-acetate)$ was administered to two- and four-year-old July and September American ginseng (Araliaceae, Panax quinquefolium L.) plants and cuttings. The $C^{14}-acetate$ uptake was approximately 99%. The autoradiochromatograms suggest that the saponins isolated by preparative thin-layer chromatography contained impurities, especially those isolated from the leaf and stem extracts. The root and fruit methanol extracts yielded relatively pure saponins. The large amounts of panaquilin B and its proximity to panaquilin C on preparative thin-layer plates resulted in some admixing. The average concentration (% plant dry weight) of semi-purified saponins were high in the leaves (13.8%), as compared to fruits (9.8%), stems (7.9%) and roots (6.3%). The average percentage of $C^{14}-acetate$ incorporation into panaquilins was 4.8%. The average percentage of $C^{14}-acetate$ incorporation into panaquilins B and C was higher (1.40% and 1.13%, respectively) than that into panaquilins C, (d), G-1 and G-2 (0.75%, 0.65%, 0.13% and 0.53%, respectively). Panaquilin synthesis may be depending upon the part, collection period and age of the plant. The average percentage of $C^{14}-acetate$ incorporation into panaquilin B is high in roots (0.58%) and stems (0.48%); that into panaquilins C and (d) high in leaves (0.40% and 0.45%, respectively); and that into panaquilin E high in roots and leaves (0.55% and 0.50%, respectively). Panaquilin G-2 was synthesized in all parts of plants. The panaquilins appear to be biosynthesized more actively in July than September (exception-panaquilin G-1). Panaquilins B, C and G-1 may be biosynthesized more actively in four-year-old plants and panaquilins (d) and E more actively in two-year-old plants. The results from expectance with cuttings suggest that the panaquilins are synthesized de novo in the above-ground parts of ginseng plants, and that panaquilin G-1 may be synthesized de novo in the leaf. It is known from the tissue culture studies that panaquilins are produced by leaf, stem and root callus tissues and cailus-root cultures of American and Korean ginseng plants. Panaquilins may actively be synthesized de novo in most any cell or organ of the ginseng plants. It was verified that $C^{14}-acetate$ was incorporated into the panaxadiol portions of the panaquilins of two-year-old plants (sp. act. 0.56 mmcCi/mg) and four-year-old plants $(sp.\;act.\;0.54\;m{\mu}Ci/mg)$.

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Enzymatic Interesterification and Melting Characteristic for Asymmetric 1,2-Distearoyl-3-Oleoyl-rac-Glycerol Triacylglycerol Enriched Product (효소적 반응을 이용한 비대칭형 1,2-Distearoyl-3-Oleoyl-rac-Glycerol 혼합물의 생성 및 융점 특성)

  • Kim, Jin Young;Lee, Ki Teak
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.43 no.1
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    • pp.93-101
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    • 2014
  • Asymmetric 1,2-distearoyl-3-oleoyl-rac-glycerol (SSO) triacylglycerol (TAG) is used as a cocoa butter replacer (CBR). In this study, it was produced by lipase-catalyzed interesterification of fully hydrogenated soybean oil (FHSBO) and oleic ethyl ester (OEE) in a batch type reactor at $75^{\circ}C$, 250 rpm. Different molar ratios (FHSBO : OEE=1:1, 1:2 and 1:3, w/w) and various reaction times (1, 2, 3, 4, and 5 hr) were also tested. The optimized condition for SSO was a FHSBO : OEE molar ratio of =1:1 at reaction times of 2, 3, 4, and 5 hr. Enzymatic synthesis generated SSO/SOS, as well as the other TAGs (e.g., PSO/POS, SOO/OSO, SSS), ethyl esters, monoacylglycerol (MAG), and diacylglycerol (DAG). After scale-up, fractionation by solvent (methanol and acetone) fractionation and column chromatography was applied. To reduce ethyl esters, high-melting TAGs (e.g., SSS), and SOO/OSO in reactants, solvent fractionation was applied. Using a silica gel column (sample : silica gel=2:1, wt%), MAG and DAG were removed at $25^{\circ}C$. The major fatty acid composition of the final products (with a high SSO/SOS content) was palmitic acid (C16:0, 10.9~12.9 area%), stearic acid (C18:0, 52.2~54.9 area%), and oleic acid (C18:1, 34.2~35.5 area%). In reversed-phase HPLC analysis, the major TAG species of the final product (FHSBO : OEE=1:1, 2 hr) were SSO/SOS (82.31 area%) and PSO/POS (14.51 area%). Based on the $[SS]^+$ : $[SO]^+$ ratio obtained by RP-HPLC/APCI-MS, the final product had a higher SSO (AAB type TAG) content than cocoa butter (CB). The solid fat index (SFI) of CB and the final product obtained were similar with a narrow melting point range around ~32 to $35^{\circ}C$.

New Whitening Agent : Selina-4(14), 7(11)-dien-8-one (신규 미백제 : Selina-4(14), 7(11)-dien-8-one)

  • Kim, Cheong-Taek;Chang, Yun-Hee;Lee, Sang-Hwa;Kang, Sang-Jin;Cho, Wan-Goo
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.31 no.1 s.49
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    • pp.17-23
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    • 2005
  • We had previously reported that Selina (selina-4(14), 7(11)-dien-8-one) was isolated from methanol extract of Afractylodes rhizome and has strong whitening activity in B16 melanoma cells. In this report, we demonstrated its action mechanism in melan-a cells, non-tumorigenic melanocytes. We also investigated the clinical efficacy of cosmetic preparation containing Selina. Selina reduced the melanin synthesis of Melan-a cells by $50\%$ at a concentration of $10 {\mu}g/mL$ without any apparent cytotoxicity. We also found that the treatment of cells with Selina decreased tyrosinase activity by $60\%$ at a concentration of $10 {\mu}g/mL$ but Selina was not a direct inhibitor of tyrosinase activities. To elucidate the action mechanism of Selina, we investigated the changes in mRNA and protein level of tyrosinase, TRP-1 and TRP-2 using RT-PCR and western blotting, respectively. As a result, the mRNA and protein level of tyrosinase were markedly reduced at $10 {\mu}g/mL$ of Selina without any effect on TRP-1 and TRP-2. These results suggest that Selina exerts its whitening effect mainly through regulating expression of tyrosinase. A 7 week-clinical trial using formulation containing $0.2\%$ selina-4(14), 7(11)-dien-8-one with 20 volunteers resulted in statistically significant whitening effect (p < 0.05), without any adverse effect. Based on these results, Selina (selina-4(14), 7(11)-dien-8-one) can be s useful and safe ingredient for the cleanness and brightness of skin.