• Title/Summary/Keyword: Catalytic Dehydration

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Catalytic Dehydration of Methanol to Dimethyl Ether (DME) over Solid-Acid Catalysts

  • Jun, Ki-Won;Lee, Hye-Soon;Rho, Hyun-Seog;Park, Sang-Eon
    • Bulletin of the Korean Chemical Society
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    • v.23 no.6
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    • pp.803-807
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    • 2002
  • The conversion of dimethyl ether(DME) has been carried out over $\gamma-alumina$, silica-alumina, and modified $\gamma-aluminal$ catalysts. Especially, the water effect has been investigated on purpose to develop a suitable catalyst for one-step synthesis of DME from $CO_2$ hydrgenation, The $\gamma-Al_2O_3$ modified with 1 wt% silica is more active and less deactivated by water than unmodified one. $CO_2has$ no effect on catalytic dehydration of methanol to DME.

Catalytic and Acidic Properties of TiO2-SiO2 Unmodified and Modified with H2SO4 (TiO2-SiO2 및 H2SO4으로 개질된 TiO2-SiO2의 촉매특성과 산 성질)

  • Sohn, Jong-Rack;Jang, Hyang-Ja
    • Applied Chemistry for Engineering
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    • v.1 no.1
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    • pp.35-43
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    • 1990
  • A series of $TiO_2-SiO_2$catalysts were prepared by coprecipitation from the mixed solution of titanium tetrachloride and sodium silicate. Some of the samples were treated with 1N $H_2SO_4$ and used as modified catalysts. The catalytic activities of modified catalysts were higher than those of unmodified catalysts, and the effect of modification on the catalytic activity was higher for 2 - propanol dehydration than for cumene dealkylation. The catalytic activity of unmodified catalysts was correlated with their acid amount for the above two reactions. As $TiO_2-SiO_2$ catalysts had relatively large amount of weak acid sites and small amount of strong acid sites, the catalytic activity for 2 - propanol dehydration was higher than that for cumene dealkylation. The effect of modification on catalytic activity increased with increasing $TiO_2$content of the catalysts. Actually, $92-TiO_2-SiO_2/SO_4{^2}$had the highest increment in catalytic activity and $10-TiO_2-SiO_2/SO_4{^2}$had the lowest increment for the 2 - propanol dehydration.

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Gas-phase Dehydration of Glycerol over Supported Silicotungstic Acids Catalysts

  • Kim, Yong-Tae;Jung, Kwang-Deog;Park, Eun-Duck
    • Bulletin of the Korean Chemical Society
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    • v.31 no.11
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    • pp.3283-3290
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    • 2010
  • The gas-phase dehydration of glycerol to acrolein was carried out over 10 wt % HSiW catalysts supported on different supports, viz. $\gamma-Al_2O_3$, $SiO_2-Al_2O_3$, $TiO_2$, $ZrO_2$, $SiO_2$, AC, $CeO_2$ and MgO. The same reaction was also conducted over each support without HSiW for comparison. Several characterization techniques, $N_2$-physisorption, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), the temperature-programmed desorption of ammonia ($NH_3$-TPD), temperature-programmed oxidation (TPO) with mass spectroscopy and CHNS analysis were employed to characterize the catalysts. The glycerol conversion generally increased with increasing amount of acid sites. Ceria showed the highest 1-hydroxyacetone selectivity at $315^{\circ}C$ among the various metal oxides. The supported HSiW catalyst showed superior catalytic activity to that of the corresponding support. Among the supported HSiW catalysts, HSiW/$ZrO_2$ and HSiW/$SiO_2-Al_2O_3$ showed the highest acrolein selectivity. In the case of HSiW/$ZrO_2$, the initial catalytic activity was recovered after the removal of the accumulated carbon species at $550^{\circ}C$ in the presence of oxygen.

Phosphoric Acid Modified Nb2O5: A Selective and Reusable Catalyst for Dehydration of Sorbitol to Isosorbide

  • Tang, Zhen-Chen;Yu, Ding-Hua;Sun, Peng;Li, Heng;Huang, He
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3679-3683
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    • 2010
  • Niobium oxide ($Nb_2O_5$) and phosphated $Nb_2O_5$ were synthesized and used as catalysts for sorbitol dehydration to isosorbide. The characterization results of $N_2$ adsorption, XRD and $NH_3$-TPD revealed that the phosphoric acid modification could well prevent the crystallization of $Nb_2O_5$. And the amorphous phosphated $Nb_2O_5$ catalysts kept the relatively large surface area and stable acidity at high calcination temperature. The catalytic results showed that the selectivity to isosorbide could be dramatically enhanced over phosphated $Nb_2O_5$. The excellent catalytic performance with 100.0% sorbitol conversion and 62.5% isosorbide selectivity were obtained over the 0.8P/NBO-400 catalyst. Comparing with $Nb_2O_5$ catalysts, phosphated $Nb_2O_5$ catalysts regenerated through a simple calcination process showed no significant activity loss after recycling three runs.

Characterization of Zirconium Sulfate Supported on Zirconia and Activity for Acid Catalysis

  • Son, Jong Rak;Gwon, Tae Dong;Kim, Sang Bok
    • Bulletin of the Korean Chemical Society
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    • v.22 no.12
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    • pp.1309-1315
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    • 2001
  • Zirconium sulfate supported on zirconia catalysts were prepared by impregnation of powdered $Zr(OH)_4$ with zirconium sulfate aqueous solution followed by calcining in air at high temperature. The characterization of prepared catalysts was performed using Fourier transform infrared (FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and by the measurement of surface area. The addition of zirconium sulfate to zirconia increased the phase transition temperature of $ZrO_2$ from amorphous to tetragonal due to the interaction between zirconium sulfate and zirconia, and the specific surface area and acidity of catalysts increased in proportion to the zirconium sulfate content up to 10 wt% of $Zr(SO_4)_2$. Infrared spectra of ammonia adsorbed on $Zr(SO_4)2}ZrO_2$ showed the presence of Bronsted and Lewis acid sites on the surface. $10-Zr(SO_4)_2}ZrO_2$ calcined at $600^{\circ}C$ exhibited maximum catalytic activities for 2-propanol dehydration and cumene dealkylation. The catalytic activities for both reactions were correlated with the acidity of catalysts measured by ammonia chemisorption method.

Acidic Properties and Catalytic Activity of Titanium Sulfate Supported on TiO2

  • Sohn, Jong-Rack;Lee, Si-Hoon;Cheon, Park-Won;Kim, Hea-Won
    • Bulletin of the Korean Chemical Society
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    • v.25 no.5
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    • pp.657-664
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    • 2004
  • Titanium sulfate supported on $TiO_2$was prepared by impregnation of powdered $TiO_2$with an aqueous solution of titanium sulfate followed by calcining in air at high temperature. For Ti$(SO_4)_2/TiO_2$ samples calcined at 300 $^{\circ}C$, no diffraction lines of titanium sulfate are observed at $Ti(SO_4)_2$loading up to 30 wt%, indicating good dispersion of $Ti(SO_4)_2$ on the surface of $TiO_2$. The acidity of the catalysts increased in proportion to the titanium sulfate content up to 20 wt% of $Ti(SO_4)_2$. 20 wt% $Ti(SO_4)_2/TiO_2$ calcined at 300 $^{\circ}C$ exhibited maximum catalytic activities for 2-propanol dehydration and cumene dealkylation. The catalytic activities for these reactions, were correlated with the acidity of catalysts measured by ammonia chemisorption method.

Preparation and Characterization of Al-Zr Mixed Oxide Catalysts (Al-Zr 혼합산화물 촉매의 제조 및 특성분석)

  • Park, Jung-Hyun;Youn, Hyun Ki;Shin, Chae-Ho
    • Clean Technology
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    • v.22 no.1
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    • pp.9-15
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    • 2016
  • xAl-yZr mixed oxide catalysts with different molar ratios of Al/(Al+Zr) were prepared by a co-precipitation method and its catalytic performance was compared in the iso-propanol dehydration as a model reaction. The catalysts were characterized by X-ray diffraction (XRD), differential thermal analysis (DTA), N2 adsorprion-desorption, NH3 temperature programmed desorption (NH3-TPD), and iso-propanol TPD analyses. The addition of Al into ZrO2 promoted the formation of relatively small particles with large surface areas and retarded the transformation of teragonal phase to monoclnic phase. NH3-TPD results revealed that the relative acidity of the catalysts increased along with the increase of Al molar ratio. The catalytic activity for the dehydration of iso-propanol to propylene was also increased with the same tendency. The catalytic activity could be correlated with high surface area, acidity and easy desorption of iso-propanol.

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.

Acidic and Catalytic Properties of Modified Silica Catalyst with Benzenesulfo Groups

  • Sohn, Jong-Rack;Ryu, Sam-Gon;Pae, Young-Il;Choi, Sang-June
    • Bulletin of the Korean Chemical Society
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    • v.11 no.5
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    • pp.403-406
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    • 1990
  • Two types of new silica catalysts modified with benzenesulfonic acid derivatives were prepared by esterification or phenylation followed by sulfonation. Both catalysts thus prepared were tested as acid catalysts for 2-propanol dehydration and cumene dealkylation reactions. B catalyst () were more active than A catalyst (). Highter catalytic activity for B catalyst may be accounted for by higher resistance to water, higher acid strength, more acidity, and better thermal stability as compared with A catalyst.

Dehydration of Methanol to Dimethyl ether, Ethylene and Propylene over Silica-Doped Sulfated Zirconia

  • Hussain, Syed T.;Mazhar, M.;Gul, Sheraz;Chuang, Karl T;Sanger, Alan R.
    • Bulletin of the Korean Chemical Society
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    • v.27 no.11
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    • pp.1844-1850
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    • 2006
  • Two types of catalyst samples were prepared, one sulfated zirconia and the other silica doped sulfated zirconia. The acidity tests indicate that sulfated zirconia doped with silica has higher concentration and strength of acidic catalyst sites than undoped sulfated zirconia. The acidic surface sites have been characterized using FTIR, NMR, pyridine adsorption, TPD, XRD and nitrogen adsorption. Doping with silica increased the concentration of surface Lewis and Brfnsted acid sites and resulted in generation of proximate acid sites.The activity test indicates that doping sulfated zirconia with silica increases both the acidity and catalytic activity for liquid phase dehydration of methanol at 413-453 K. Methanol is sequentially dehydrated to dimethyl ether and ethylene over both catalysts. Significant amounts of propylene are also formed over the silica-doped catalyst, but not over the undoped catalyst.