• Title/Summary/Keyword: Catalytic Dehydration

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Preparation and Reactivity of Cu-Zn-Al Based Hybrid Catalysts for Direct Synthesis of Dimethyl Ether by Physical Mixing and Precipitation Methods (물리혼합 및 침전법에 의한 DME 직접 합성용 Cu-Zn-Al계 혼성촉매의 제조 및 반응특성)

  • Bang, Byoung Man;Park, No-Kuk;Han, Gi Bo;Yoon, Suk Hoon;Lee, Tae Jin
    • Korean Chemical Engineering Research
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    • v.45 no.6
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    • pp.566-572
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    • 2007
  • Two hybrid catalysts for the direct synthesis of DME were prepared and the catalytic activity of these catalysts were investigated. The hybrid catalyst for the direct synthesis of DME was composed as the catalytic active components of methanol synthesis and dehydration. The methanol synthesis catalyst was formed from the precursor contained Cu and Zn, the methanol dehydration catalyst was used ${\gamma}-Al_2O_3$. As PM-CZ+D and CP-CZA/D, Two hybrid catalysts were prepared by physical mixing method (PM-CZ+D) and precipitation method (CP-CZA/D), respectively. PM-CZ+D was prepared by physically mixing methanol synthesis catalyst and methanol dehydration catalyst, CP-CZA/D was prepared by depositing Cu-Zn or Cu-Zn-Al components on ${\gamma}-Al_2O_3$. The crystallinity and the surface morphology of synthesized catalyst were analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM) to investigate the physical property of prepared catalyst. And BET surface area by $N_2$ adsorption and the surface area of Cu by $N_2O$ chemisorption were investigated about the hybrid catalysts. In addition, catalytic activity of these hybrid catalysts was examined with varying reaction conditions. At that time, the reaction temperature of $250{\sim}290^{\circ}C$, the reaction pressure of 50~70 atm, the $[H_2]/[CO]$ mole ratio of 0.5~2.0 and the space velocity of $1,500{\sim}6,000h^{-1}$ were investigated the catalytic activity. From these results, it was confirmed that the reactivity of CP-CZA/D was higher than that of PM-CZ+D. When the conditions of reaction temperature, pressure, $[H_2]/[CO]$ ratio and space velocity were $260^{\circ}C$, 50 atm and 1.0, $3,000h^{-1}$ respectively, CO conversion using CP-CZA/D hybrid catalyst was 72% and the CO conversion of CP-CZA/D was more than 20% compared with the CO conversion of PM-CZ+D. It was known that Cu surface area of CP-CZA/D hybrid catalyst was higher than that of hybrid PM-CZ+D catalyst using $N_2O$ chemisorption. It was assumed that the catalytic activity was improved because Cu particle of hybrid catalyst prepared by precipitation method was well dispersed.

Dehydration of D-xylose into Furfural Using Sulfonic Acid Modified ${\gamma}-Al_2O_3$ (황산기가 도입된 감마 알루미나를 이용한 자일로즈 탈수화 반응을 통한 푸르푸랄의 생성)

  • Kim, Eun-Gyu;Kim, Saet-Byul;Park, Eun-Duck;Kim, Sang-Wook
    • Clean Technology
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    • v.17 no.1
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    • pp.31-36
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    • 2011
  • All types of ${\gamma}-Al_2O_3$ such as acidic, neutral and basic forms were chemically modified with (3-mercaptopropyl) trimethoxysilane (3-MPTMS) and oxidized by 30 wt% $H_2O_2$ solution. As a result, sulfonic acid modified ${\gamma}-Al_2O_3$ catalysts were obtained. Their formation was achieved more easily by treating 1M HCl solution. Their catalytic performance was tested by dehydration reaction of D-xylose to furfural. The sulfonic acid modified ${\gamma}-Al_2O_3$ catalysts showed high conversion (>90%) of D-xylose, and the selectivity to furfural was increased with the amount of sulfonic acid anchored on the catalyst.

Dehydration of D-Xylose into Furfural Using Propylsulfonic Acid Modified Mesoporous Silica (황산 표면개질 메조다공 실리카를 이용한 푸르푸랄 제조에 관한 연구)

  • Kim, Eun-Gyu;Kim, Saet-Byul;Park, Eun-Duck;Kim, Sang-Wook
    • Clean Technology
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    • v.16 no.2
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    • pp.95-102
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    • 2010
  • Sulfonic acid (-SO3H) functionalized mesoporous silica containing HMS, SBA 15(S15), MCM 41(M41) were synthesized by post-synthesis and co-condensation method. Their catalytic performance is tested by dehydration reaction of D-xylose to furfural. As a result, good conversion and selectivity was obtained using water as an environmentally friendly solvent. Additionally, increased amounts of sulfuric acid in catalysts resulted in improved conversion of D-xylose. All of the acid-functionalized mesoporous silica showed higher selectivity than other solid acids such as ${\gamma}-Al_{2}O_{3}$ and zeolite.

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.

Effect of Dispersed MoO3 Amount on Catalytic Activity of NiO-ZrO2 Modified with MoO3 for Acid Catalysis

  • Sohn, Jong-Rack;Lee, Sung-Gyu;Shin, Dong-Cheol
    • Bulletin of the Korean Chemical Society
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    • v.27 no.10
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    • pp.1623-1632
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    • 2006
  • NiO supported on zirconia modified with $MoO_3$ for acid catalysis was prepared by drying powdered $Ni(OH)_2-Zr(OH)_4$ with ammonium heptamolybdate aqueous solution, followed by calcining in air at high temperature. The characterization of prepared catalysts was performed using FTIR, Raman, XRD, and DSC. $MoO_3$ equal to or less than 15 wt% was dispersed on the surface of catalyst as two-dimensional polymolybdate or monomolybdate, while for $MoO_3$ above 15 wt%, crystalline orthorhombic phase of $MoO_3$ was formed, showing that the critical dispersion capacity of $MoO_3$ on the surface of catalyst is 0.18 g/g NiO-$ZrO_2$ on the basis of XRD analysis. Acidity and catalytic activities for acid catalysis increased with the amount of dispersed $MoO_3$. The high acid strength and acidity was responsible for the Mo=O bond nature of the complex formed by the interaction between $MoO_3$ and $ZrO_2$. The catalytic activity for acid catalysis was correlated with the acidity of the catalysts measured by the ammonia chemisorption method.

Catalytic Reactions of Ethanol and Acetaldehyde Over $TiO_2$-supported Gold Catalysts

  • Kim, Jeong-Jin;Kim, Yu-Gwon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.264-264
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    • 2012
  • As an environment-friendly alternative energy resource, ethanol may be used to obtain hydrogen, a clean energy source. Thus, studies on catalytic reactions involving ethanol have been studied to understand the underlying principles in the reaction mechanism using various oxide-supported catalysts. Among them, Au-based catalysts have shown a superior activity in producing hydrogen gas. In the present study, Au/$TiO_2$ catalysts were prepared by deposition-precipitation method to understand their catalytic activities toward ethanol and acetaldehyde with increasing gold loading, especially at the very low Au loading regime. A commercially available $TiO_2$ (Degussa P-25) was employed and the Au loading was varied to 0, 0.1, 0.5, and 1.0 wt% respectively. The catalysts showed characteristic x-ray diffraction (XRD) features at $2{\theta}=78.5^{\circ}$ that could be assigned to the presence of gold nanoparticles. Its reactivity measurements were performed under a constant flow of ethanol and acetaldehyde at a flow rate of ${\sim}0.6{\mu}mol/sec$ and the substrate temperature was slowly raised at a rate of 0.2 K/sec. We observed that the overall reactivity of the catalysts increased with increasing Au loading along with selectivity favoring dehydrogenation to product hydrogen gas. In addition, we disclosed various reaction channels involving competitive reaction paths such as dehydrogenation, dehydration, and condensation. In addition, subsequent reactions of acetaldehyde obtained from dehydrogenation of ethanol, were found to occur and produce butene, crotonaldehyde, furan, and benzene. Based on the results, we proposed overall reaction pathways of such reaction channels.

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Enhancement of High-Temperature Catalytic Reactions Using Membranes (분리막을 이용한 고온 촉매 반응 효율 향상)

  • Eun-Young Kim;Myeong-Hun Hyeon;Su-Young Moon
    • Membrane Journal
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    • v.33 no.6
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    • pp.305-314
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    • 2023
  • Various methods for removing by-products from chemical reactions are being studied to improve yield of catalytic reaction. Since the water is predominantly generated as a by-product in industrially significant reactions, it is necessary to develop the technology that can reliably remove water over a wide range of temperatures. Although several strategies using absorbents and additional dehydration reactions, have been proposed, they have limitations due to the issues such as additional energy and time consuming steps and sustainability of conversion. Membrane technology, which offers advantages such as easy operation, installation, and low maintenance costs, proves to be a promising approach for enhancing the efficiency of catalysts in various catalytic reactions. Therefore, this review discusses the removal of by-products using membranes and the associated benefits in this context.

Influence of Ionic Liquid as a Template on Preparation of Porous η-Al2O3 to DME Synthesis from Methanol

  • Yoo, Kye-Sang;Lee, Se-Hee
    • Bulletin of the Korean Chemical Society
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    • v.31 no.6
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    • pp.1628-1632
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    • 2010
  • Porous ${\eta}-Al_2O_3$ was synthesized by modified sol-gel method using ionic liquid as a templating material. The addition of ionic liquid assisted to increase the surface area of alumina. However, the acidity of aluminas prepared with ionic liquids was hardly affected regardless the change of its structural properties. Among the ionic liquids used in this study, 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][$PF_6$]) was the most effective ionic liquid to produce porous ${\eta}-Al_2O_3$ particles. The catalytic performance of these aluminas has been investigated in dehydration of methanol to produce dimethyl ether. The alumina prepared with [Bmim][$PF_6$] outperformed the other aluminas except ${\eta}-Al_2O_3$ without modification in this reaction.

Acid Structure of MgO-SiO₂Binary Oxide Catalyst and Activity for Acid Catalysis

  • 손종락;박은희;김하원
    • Bulletin of the Korean Chemical Society
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    • v.18 no.2
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    • pp.203-208
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    • 1997
  • A series of MgO-SiO2 catalysts were prepared by coprecipitation from the mixed solution of magnesium chloride and sodium silicate. Some of the sample were modified with 1 N H2SO4 and used as modified catalysts. The addition of MgO to SiO2 caused the increase of acidity and the shift of O-H and Si-O stretching bands of the silanol group to a lower frequency in proportion to the MgO content. The acid structure of MgO-SiO2 agreed with that proposed by Tanabe et al.. Catalytic activity for 2-propanol dehydration increased in relation to the increase of acidity and band shift to a lower frequency.

Acidic Properties of Mg-Al Mixed Oxides in the Dehydration of iso-Propanol (이소프로판올의 탈수반응에 있어서 Mg-Al 혼합 산화물의 산점 특성)

  • Youn, Hyunki;Ahn, Ji-Hye;Park, Jung-Hyun;Shin, Chae-Ho
    • Clean Technology
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    • v.20 no.3
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    • pp.330-336
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    • 2014
  • Mg-Al mixed oxides with molar ratio of Mg/Al = 1-3 were prepared by co-precipitation and characterized by using X-ray diffraction, scanning electron microscopy, BET surface area and pore volume measured by $N_2$ sorption analysis, and temperature programmed desorption of iso-propanol. As Al content in Mg-Al mixed oxide increased, the acidity and BET surface area proportionally increased. This increase of acidity directly influenced the catalytic activity of iso-propanol conversion and selectivity to propylene.