• Title/Summary/Keyword: catalytic acid - sites

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Synthesis of Hβ (core)/SAPO-11 (shell) Composite Molecular Sieve and its Catalytic Performances in the Methylation of Naphthalene with Methanol

  • Wang, Xiaoxiao;Guo, Shaoqing;Zhao, Liangfu
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3829-3834
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    • 2013
  • $H{\beta}$ (core)/SAPO-11 (shell) composite molecular sieve was synthesized by the hydrothermal method in order to combine the advantages of $H{\beta}$ and SAPO-11 for the methylation of naphthalene with methanol. For comparison, the mechanical mixture was prepared through the blending of $H{\beta}$ and SAPO-11. The physicochemical properties of $H{\beta}$, SAPO-11, the composite and the mechanical mixture were characterized by various characterization methods. The characterization results indicated that $H{\beta}$/SAPO-11 composite molecular sieve exhibited a core-shell structure, with the $H{\beta}$ phase as the core and the SAPO-11 phase as the shell. The pore diameter of the composite was between that of $H{\beta}$ and SAPO-11. The composite had fewer acid sites than $H{\beta}$ and mechanical mixture while more acid sites than SAPO-11. The experimental results indicated that the composite exhibited high catalytic performances for the methylation of naphthalene with methanol.

Preparation of High-Temperature catalytic Support from Gibbsite II. Properties of Amophous Alumina as Precursor of Catalyst Support (깁사이트를 원료로 한 고온촉매용 담체의 제조 II, 비정질 알루미나의 담체 전구체로서의 특성)

  • 김성연;김연식
    • Journal of the Korean Ceramic Society
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    • v.33 no.1
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    • pp.92-100
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    • 1996
  • Amorphous alumina(AA) the precursor of ${\gamma}$-alumina for catalyst support was made in the newly designed ball filled heating column. Some properties of AA as precursor were investigated. In observation of microstruc-ture and pore structure of AA and its derivatives scanning electronic microscope(SEM) and transmission electronic microscope(TEM) were used. It was found that the width of one particle in AA was 45~60$\AA$ and the average distance among the particles ranged 9~12 $\AA$ which suggested a micropore structure. When AA was reacted with water the shape of the surface was found to be altered and acicular bioehmite was formed inside AA which contributed inproved formability. Pore distribution was evaluated for the three samples of AA ground and granulated lump and La2O3 coated alumina. Acid sites were quantitatively determined by ammonia TPD method and the effect of impurity of Na on acid sites was discussed. Water adsorption capacity was evaluated in terms of a desiccant.

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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.

Acidic Properties of Tungsten Oxide Supported on Zirconia and Catalytic Activities for Acid Catalysis (Zirconia에 담지된 산화텅스텐 촉매의 산 성질과 산 촉매활성)

  • Sohn, Jong Rack;Park, Man Young
    • Applied Chemistry for Engineering
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    • v.10 no.2
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    • pp.247-251
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    • 1999
  • Tungsten oxide supported on zirconia was prepared by drying powdered $Zr(OH)_4$ with ammonium metatungstate aqueous solution, followed by calcining in air at high temperature. Upon the addition of only small amount of tungsten oxide (1 wt % $WO_3$) to $ZrO_2$, both the acidity and acid strength of catalyst increased remarkably, showing the presence of $Br{\ddot{o}}nsted$ and Lewis acid sites on the surface of $WO_3$/$ZrO_2$. The high acid strength and large amount of acid sites on $WO_3$/$ZrO_2$ were due to the presence of the W=O bond nature of complex formed by the interaction between $WO_3$ and $ZrO_2$. The catalyst containing 20 wt % $WO_3$, calcined at 973 K, showed the highest catalytic activity for the 2-propanol dehydration, while the catalyst containing 15 wt % $WO_3$, calcined at 1023 K, exhibited the highest catalytic activity for the cumene dealkylation. For the 2-propanol dehydration the catalytic activities of $WO_3$/$ZrO_2$ catalysts were roughly correlated with their acidities.

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Mitogen-activated $p70^{s6k}$ signalling pathway

  • Han, Jeung-Whan
    • Proceedings of the Korean Society of Applied Pharmacology
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    • 1996.11a
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    • pp.135-139
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    • 1996
  • $p70^{s6k}$ lies on a $p21^{ras}$-independent signalling pathway and plays an important role in mitogenesis. Activation is associated with phosphorylation at multiple sites, four of which lie in an autoinhibitory region. The immunosuppressant rapamycin induces $p70^{s6k}$ inactivation through dephosphorylation of a second set of mitogen-induced sites. Here we identify these sites as $T_{229}$, $T_{389}$, and $S_{404}$. $T_{229}$ resides in the "T loop" of the catalytic domain, an essential phosphorylation site in other kinases. However, $p70^{s6k}$ inactivation by rapamycin most closely parallels $T_{389}$ dephosphorylation. Mutation of $T_{389}$ to alanine ablates kinase activity, whereas mutation to glutamic acid confers constitutive kinase activity and rapamycin resistance. indicating an essential role for phosphorylation at this site. $T_{389}$ resides in an unusual hydrophobic motif, not previously noted, between the catalytic and autoinhibitory domains. The importance of this site, and surrounding motif, is emphasized by its conservation in other kinases including homologues of $p70^{s6k}$ derived from such distantly related organisms as yeast and plant.

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Effect of Aluminium Addition to MCM-41 on Catalytic Cracking of an LDPE-LLDPE-EVA Copolymer Mixture (MCM-41을 이용한 LDPE-LLDPE-EVA 공중합체 혼합물의 접촉 열분해 반응에 미치는 Aluminium 첨가 효과)

  • Kim, Min Ji;Jeon, Jong-Ki;Park, Young-Kwon;Ko, Young Soo;Sohn, Jung Min
    • Korean Chemical Engineering Research
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    • v.45 no.2
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    • pp.117-123
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    • 2007
  • The effect of aluminium addition to MCM-41 on product yield and carbon number distribution was investigated in the catalytic cracking of a polymer mixture, LDPE, LLDPE, and EVA copolymer, with a composition similar to that found in real agricultural film wastes. Al-MCM-41 catalyst synthesized by post-synthetic grafting method (Al-MCM-41-P) as well as Al-MCM-41 catalyst synthesized by direct sol-gel (Al-MCM-41-D). The catalytic cracking of polymer mixture was carried out in vapor phase contact as well as in liquid phase contact. The amount of acid sites increased with aluminium addition by post method as well as direct method, which was seemed to be due to Lewis acid sites. In liquid phase catalytic cracking, the yield of light hydrocarbon fraction increased with aluminium addition. The effect of aluminium addition on production of $C_5-C_{12}$ hydrocarbons over Al-MCM-41-P catalysts was greater than that over Al-MCM-41-D catalysts. In the case of vapor phase catalytic cracking, the effect of aluminium addition was smaller than that of liquid phase catalytic cracking. The selectivity to $C_{13}-C_{32}$ hydrocarbons was smaller in vapor phase catalytic cracking.

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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Synthesis of Butenes through Butanol Dehydration over Catalyst Prepared from Water Treatment Sludge (정수 슬러지로부터 제조된 촉매 상에서 부탄올 탈수반응을 통한 부텐 제조)

  • Kim, Goun;Bae, Junghyun;Choi, Hyeonhee;Lee, Choul-Ho;Jeon, Jong-Ki
    • Korean Chemical Engineering Research
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    • v.53 no.1
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    • pp.121-126
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    • 2015
  • The objective of this study is to evaluate the catalytic potential of the porous material prepared from water treatment sludge. The textural properties of the catalyst were studied using $N_2$ adsorption and desorption isotherms, scanning electron microscope, and X-ray diffraction. The pellet-type catalyst prepared using water treatment sludge is determined to be a material that contains mesopores as well as micropores. The specific surface area of the catalyst is $157m^2/g$. Acidic characteristics of the catalyst are analyzed by temperature-programmed desorption of ammonia and infrared spectroscopy of adsorbed pyridine. 2-Butanol dehydration reaction was carried out in a fixed bed catalytic reactor. Yields of 1-butene, trans-2-butene, and cis-2-butene at $350^{\circ}C$ were 25.6 wt%, 19.2 wt%, and 29.9 wt%, respectively. This catalytic activity of the catalyst based on water treatment sludge in 2-butanol dehydration is due to the acid sites composed of Bronsted acid sites and Lewis acid sites. It was confirmed that the catalyst based on water treatment sludge can be utilized to produce $C_4$ olefin through butanol dehydration.

Effect of V2O5 Modification in V2O5/TiO2-ZrO2 Catalysts on Their Surface Properties and Catalytic Activities for Acid Catalysis

  • Sohn, Jong-Rack;Lee, Cheul-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2459-2465
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    • 2007
  • V2O5/TiO2-ZrO2 catalyst modified with V2O5 was prepared by adding Ti(OH)4-Zr(OH)4 powder into an aqueous solution of ammonium metavanadate followed by drying and calcining at high temperatures. The characterization of prepared catalysts was performed using XRD, DSC, solid-state 51V NMR, and FTIR. In the case of calcination temperature of 500 oC, for the catalysts containing low loading V2O5 below 25 wt % vanadium oxide was in a highly dispersed state, while for catalysts containing high loading V2O5 equal to or above 25 wt % vanadium oxide was well crystallized due to the V2O5 loading exceeding the formation of monolayer on the surface of TiO2-ZrO2. The strong acid sites were formed through the bonding between dispersed V2O5 and TiO2-ZrO2. The larger the dispersed V2O5 amount, the higher both the acidity and catalytic activities for acid catalysis.

Spectroscopic Studies on ZrO2 Modified with MoO3 and Activity for Acid Catalysis

  • Sohn, Jong-Rack;Chun, Eun-Woo;Pae, Young-Il
    • Bulletin of the Korean Chemical Society
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    • v.24 no.12
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    • pp.1785-1792
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    • 2003
  • Zirconia modified with $MoO_3$ was prepared by impregnation of powdered $Zr(OH)_4$ with ammonium heptamolybdate aqueous solution followed by calcining in air at high temperature. Spectroscopic studies on prepared catalysts were performed by using FTIR, Raman, XRD, and DSC and by measuring surface area. Upon the addition of molybdenum oxide to zirconia up to 15 wt%, the specific surface area increased in proportion to the molybdate oxide content, while acidity measured by irreversible chemisorption of ammonia exhibited a maximum value at 3 wt% of $MoO_3$. Since the $ZrO_2$ stabilizes the molybdenum oxide species, for the samples equal to or less than 30 wt%, molybdenum oxide was well dispersed on the surface of zirconia and no phase of crystalline $MoO_3$ was observed at any calcination temperature above $400^{\circ}C$. The catalytic activities for cumene dealkylation were roughly correlated with the acidity of catalysts measured by ammonia chemisorption method, while the catalytic activities for 2-propanol dehydration were not correlated with the acidity because weak acid sites are necessary for the reaction.