• Title/Summary/Keyword: disproportionation reaction

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The Physical and Catalytic Properties of Kuryongpo Natural Zeolite (九龍浦産 天然제올라이트의 物性 및 觸媒特性)

  • Chong Sik Chung;Gon Seo;Hakze Chon;Hoagy Kim
    • Journal of the Korean Chemical Society
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    • v.21 no.3
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    • pp.204-209
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    • 1977
  • The properties of the natural zeolite produced in Kuryongpo, Kyungsang-Bukdo, were investigated by X-ray diffraction analysis, chemical composition analysis, and nitrogen adsorption experiment. The quality of the acid treated natural zeolite as the catalyst for the disproportionation reaction of toluene was examined experimentally by observing the conversion in a microcatalytic reactor. The quantitative analysis and X-ray diffraction spectrum showed that the zeolite ore of Kuryongpo contained approximately 30 to 40 percent of mordenite structure. The surface area of the zeolite ore was $75m^2$/gm and increased to a maximum value of $320m^2$/gm after treatment with 2 N HCl solution. The catalytic activity for the toluene disproportionation reaction was maximum when the zeolite treated with 2 N HCl solution was used. The selectivity of xylene to benzene decreased with increasing degree of acid treatment.

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Improving Reproducibility of Coercivity of HDDR-treated Nd-Fe-B-type Material by Controlling Hydrogen Decrepitation (수소파쇄 제어를 통한 HDDR 처리한 Nd-Fe-B계 재료의 보자력 재현성 향상)

  • Kim, Kyung Min;Kim, Ja Young;Kwon, Hae-Woong;Lee, Jeong Gu;Yu, Ji Hun
    • Journal of the Korean Magnetics Society
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    • v.25 no.4
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    • pp.111-116
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    • 2015
  • Practical difficulty in the HDDR (hydrogenation - disproportionation - desorption - recombination) processing of Nd-Fe-B-type alloy is a poor reproducibility of coercivity of the HDDR-treated material. In an attempt to improve the reproducibility of coercivity of the HDDR-treated $Nd_{12.5}Fe_{80.6}B_{6.4}Ga_{0.3}Nb_{0.2}$ alloy, the hydrogen decrepitation was carefully controlled so as to induce more extensive micro-cracks in the particle. Prior to the hydrogenation and disproportionation reaction of HDDR processing, an additional hydrogen degassing was carried out at an elevated temperature of $600^{\circ}C$ under vacuum for the previously hydrogen decrepitated particle. During the additional hydrogen degassing the lattice of hydrogen absorbed $Nd_2Fe_{14}B$ phase was further shrunken, hence more microcracks were introduced in the particle due to its brittle nature. Particles with more micro-cracks had more homogeneous hydrogen absorption and desorption reaction during the HDDR-treatment. The improved reproducibility of coercivity of the HDDR-treated material was attributed to the improved homogeneity of the HDDR reactions due to the presence of more micro-cracks.

Physical and Rheological Properties of Thermoplasticized Crosslinked-Polyethylene Foam in Supercritical Methanol

  • Cho, Hang-Kyu;Hong, Soon-Man;Baek, Kyung-Yeol;Koo, Chong-Min;Lee, Hong-Shik;Lee, Youn-Woo
    • Macromolecular Research
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    • v.17 no.12
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    • pp.950-955
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    • 2009
  • The physical and rheological properties of thermoplasticized irradiation-crosslinked polyethylene foam using supercritical methanol treatment were investigated by GPC, FTIR, DSC, WAXS, DMTA and UDS. The polyethylene foam was selectively decrosslinked into thermoplasticized polyethylene in an appropriate supercritical methanol condition without any undesirable side reactions such as oxidation and disproportionation. The thermoplasticization was promoted with increasing reaction temperature to reach completion above $380^{\circ}C$. The supercritical reaction condition affected the crystallization behavior, and mechanical and rheological properties of the decrosslinked polyethylene foam, but not its crystallographic structure or crystallinity.

Attempts on the Preparation of Lithium Trialkoxyborohydrides. Stability and Stereoselective Reduction of Cyclic Ketones

  • Cha, Jin-Soon;Kim, Jin-Euog;Lee, Jae-Cheol;Yoon, Mal-Sook
    • Bulletin of the Korean Chemical Society
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    • v.7 no.1
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    • pp.66-69
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    • 1986
  • The reaction of potassium trialkoxyborohydrides of varying steric requirements with lithium chloride in tetrahydrofuran(THF) was examined in detail to establish the generality of this synthesis of the corresponding lithium trialkoxyborohydrides. The metal ion exchange reaction between potassium triisopropoxyborohydride and lithium chloride in THF proceeded instantly at room temperature and the corresponding lithium salt was very stable toward disproportionation. However, for R = s-Bu, t-Bu and 2-methylcyclohexyl, with increasing steric requirement, the lithium derivatives were unstable and thus dissociated into $(RO)BH_3^-\;and\; (RO)_4B^-$. The stereoselectivity of lithium triisopropoxyborohydride(LIPBH) in the reduction of representative cyclic ketones was examined and compared with that of the potassium derivative.

Shape Selective Catalysis of Cation-Exchanged Pentasil Zeolites (양이온 교환된 펜타실 제올라이트의 형상 선택적 촉매작용)

  • Byoung Joon Ahn;Byung Woo Hwang;Hakze Chon
    • Journal of the Korean Chemical Society
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    • v.28 no.1
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    • pp.62-69
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    • 1984
  • The reaction of toluene with ethanol was studied over various cation-exchanged pentasil zeolite catalysts. The toluene disproportionation reaction to produce xylenes increased with increasing reaction temperature and the activity of alkylation of toluene with ethanol showed maximum at around $400^{\circ}C$. Only Cs-ZSM-5 catalyst showed pronounced p-ethyltoluene selectivity increasing to 96% with increasing degree of Cs-exchange. The sorption rate of m-xylene was lower for Cs-exchanged ZSM-5 than H-ZSM-5 catalyst. These phenomena were interpreted in terms of shape selectivity arising from the partial blocking of channel intersections by large cesium ions.

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Electronic state calculation of ceramics by $DV-X\;{\alpha}$ cluster method

  • Adachi, Hirohiko
    • Proceedings of the Materials Research Society of Korea Conference
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    • 1994.11a
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    • pp.1-1
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    • 1994
  • ;The electronic state calculations for various types of ceramic materials have beell performed by the use of $DV-X\;{\alpha}$ cluster method. The molecular orbital levels and wave functions for model clusters have been computed to study the electronic properties ami chemical bonding of the ceramics. For ${\beta}-sialon(Si_{6-z}Al_zO_zN_{8-z})$ which is a high temperature structural material based on ${\beta}-Si_3N_4$, we have made model cluster calculations to estimate the strength of chemical bonding between atoms by the Mulliken population analysis. It is found that the covalent bonding between Si and N atoms is very strong in pure ${\beta}-Si_3N_4$, but the covalency around solute atom is considerably weakened when Si atom is substituted by AI. This tendency is enhanced by an additional substitution of oxygen atom for N. The result calculated can well explain the experimental data of changes in mechanical properties such as the reductions of Young's modulus and Vickers hardness with increment of z-value in ${\beta}-sialon$. Various model clusters for transition metal oxides which show many interesting physical and chemical properties have also been calculated. High-valent perovskite-type iron oxides EMFe0_3E(M=Ca and Sr) possess very interesting magnetic and chemical properties. In these oxides, iron exists as $Fe^{4+}$ state, but the experimental measurement of Mossba~er effect suggests that disproportionation $2Fe^{4+}=Fe^{3+}+Fe^{5+}$ takes place for $CaFe0_3$ at low temperatures. The model cluster calculations for these compounds indicated the existence of considerably strong covalent bonding of Fe-O. The calculations of hyperfine interaction at iron neucleus show very good agreement with the experimental Mossbauer measurements. The result calculated also implies that the disproportionation reaction is strongly possible by assuming the quenching of breathing phonon mode at low temperatures.tures.

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Purification and Characterization of Cycloinulooligosaccharide Fructanotransferase from Bacillus macerans CFC1

  • Kim, Hwa-Young;Choi, Yong-Jin
    • Journal of Microbiology and Biotechnology
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    • v.8 no.3
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    • pp.251-257
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    • 1998
  • Cycloinulooligosaccharide fructanotransferase (CFTase) which produces cyclofructan from inulin was purified 332-fold from a culture broth of Bacillus macerans CFCl. The molecular mass of the CFTase was estimated to be 110 kDa by SDS-polyacrylamide gel electrophoresis and gel filtration, indicating that the enzyme has a monomer structure. The maximal level of enzyme activity was observed at pH 7.5 and $45^{\circ}C$. The enzyme was stable in the pH range 6.0 to 9.5, and at temperatures up to $45^{\circ}C$ for 1 h. The enzyme activity was completely inhibited in the presence of 0.5 mM $Ag^+\;or\;Cu^2+$ ion. None of sucrose (GF), l-kestose (GF2), or nystose (GF3) were found to be substrates for the CFTase, but inulooligosaccharides larger than nystose were attacked by the enzyme. The CFTase catalyzes not only the cyclization as the major reaction, but also disproportionation and coupling reactions involving intermolecular transfructosylation in the same manner as cyclodextrin glucanotransferase (CGTase) (EC 2.4.1.19).

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XPS Studies of CO Adsorption on Polycrystalline Nickel Surface

  • Boo, Jin-Hyo;Ahn, Woon-Sun
    • Bulletin of the Korean Chemical Society
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    • v.9 no.6
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    • pp.388-393
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    • 1988
  • The chemisorption of CO molecules on polycrystalline nickel surface has been studied by investigating the resulting chemisorbed species with the X-ray photoelectron spectroscopy at temperatures between 300K through 433K. It is found that the adsorbed CO molecules are dissociated by the simple C-O bond cleavage as well as by the disproportionation reaction at temperatures above 373K. The former type dissociation is more favored at low coverages and at elevated temperatures. The isotherms of CO chemisorption are obtained from the xps intensities of C 1s peaks, and then the activation energy of the dissociative adsorption is estimated as a function of the CO exposure. These activation energies are extrapolated to zero coverage to obtain the activation energy of chemisorption in which thermal C-O bond cleavage takes place. The value obtained is 38.1 kJ/mol.

Reactions of Thianthrene Cation Radical Perchlorate with N-(p-Methoxyphenyl)benzene- and Methanesulphonamides

  • Sung Hoon Kim;Jung Hyu Shin;Kyongtae Kim
    • Bulletin of the Korean Chemical Society
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    • v.10 no.6
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    • pp.509-514
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    • 1989
  • Reactions of thianthrene cation radical perchlorate (1) with N-(p-methoxyphenyl)benzenesulphonamide (14) in acetonitrile at room temperature afforded various products : thianthrene (3), N-(p-hydroxyphenyl)benzenesulphonamide (16), benzenesulphonamide (18), hydroquinone (20); 5-(5-benzenesulphonamido-2-methoxyphenyl)-thia nthrenium perchlorate(21), 2-benzenesulphonamido-2'-hydroxy-5,5'-dimethoxy biphenyl(24), 2-benzenesulphonamido-2',5'-dihydroxy-5-methoxy -biphenyl(25), and a traceable amount of p-quinone(23). The formations of part of (3) and (21) can be explained by either disproportionation or half-regeneration mechanism but those of the remainders by diverse reactions of sulphonamidyl radical (27) derived from (14) (through single electron transfer, followed by deprotonation processes). Similar results were observed from the reaction with N-(p-methoxyphenyl)methanesulphonamide (15).

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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