• Title/Summary/Keyword: palladium catalyst

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Removal Characteristics of 1,4-dioxane with O3/H2O2 and O3/Catalyst Advanced Oxidation Process (O3/H2O2와 O3/Catalyst 고급산화공정에서 1,4-dioxane의 제거 특성)

  • Park, Jin-Do;Suh, Jung-Ho;Lee, Hak-Sung
    • Journal of Environmental Science International
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    • v.15 no.3
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    • pp.193-201
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    • 2006
  • Advanced oxidation processes involving $O_3/H_2O_2$ and $O_3/catalyst$ were used to compare the degradability and the effect of pH on the oxidation of 1,4-dioxane, Oxidation processes were carried out in a bubble column reactor under different pH. Initial hydrogen peroxide concentration was 3.52 mM in $O_3/H_2O_2$ process and 115 g/L (0.65 wt.%) of activated carbon impregnated with palladium was packed in $O_3/catalyst$ column. 1,4-dioxane concentration was reduced steadily with reaction time in $O_3/H_2O_2$ oxidation process, however, in case of $O_3/catalyst$ process, about $50{\sim}75%$ of 1,4-dioxane was degraded only in 5 minutes after reaction. Overall reaction efficiency of $O_3/catalyst$ was also higher than that of $O_3/H_2O_2$ process. TOC and $COD_{cr}$ were analyzed in order to examine the oxidation characteristics with $O_3/H_2O_2\;and\;O_3/catalyst$ process. The results of $COD_{cr}$ removal efficiency and ${\Delta}TOC/{\Delta}ThOC$ ratio in $O_3/catalyst$ process gave that this process could more proceed the oxidation reaction than $O_3/H_2O_2$ oxidation process. Therefore, it was considered that $O_3/catalyst$ advanced oxidation process could be used as a effective oxidation process for removing non-degradable toxic organic materials.

Hydropurification of Crude Terephthalic Acid over PdRu/Carbon Composite Catalyst (PdRu/Carbon Composite 촉매를 이용한 테레프탈산의 수소화 정제)

  • Jhung, Sung-Hwa;Park, Youn-Seok
    • Journal of the Korean Chemical Society
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    • v.46 no.1
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    • pp.57-63
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    • 2002
  • The hydropurification reaction of CTA (crude terephthalic acid) was carried out with hydrogen over PdRu/CCM (carbon-carbonaceous composite material) catalyst in a batch reactor at high temperature. The first order kinetics of hydropurification is confirmed with the linear dependence of ln(4-CBA; 4-carboxybenzaldehyde) with reaction time. The reaction condition studied is thought to represent the hydropurification well because of the linear dependence of catalytic activity on the catalyst weight. The p-toluic acid (p-tol) in solid and liquid increases with the conversion of reaction or the decrease of 4-CBA. However, the benzoic acid (BA) concentration does not depend much on the conversion. The AT (alkali transmittance) does not depend on the 4-CBA when the concentration is higher than about 0.2% which shows the 4-CBA, in itself, does not cause the coloring effect. The AT of PTA depends inversely with the concentration of 4-CBA when the 4-CBA is less than about 0.15%. This may show the coloring materials are removed in parallel with the hydrogenation of 4-CBA. The (0.3%Pd-0.2%Ru)/CCM shows larger residual catalytic activity than a commercial catalyst, 0.5%Pd/C, after using in a commercial reactor even though the former has smaller fresh activity than the latter. The palladium and ruthenium in PdRu/CCM show the synergetic effect in activity when the ruthenium concentration is about $0.2{\sim}0.35$ wt%. It may be supposed that the PdRu/CCM catalyst can be a promising candidate to replace the commercial Pd/C catalyst.

The Effect of Fuel Sulfer on Particulate Matter of Diesel Engine Equipped with Oxidation Catalyst (경유 중 황이 산화촉매 장착 디젤엔진의 입자상 물질에 미치는 영향)

  • 조강래;신영조;류정호;김희강
    • Journal of Korean Society for Atmospheric Environment
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    • v.13 no.6
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    • pp.487-495
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    • 1997
  • The most desirable diesel oxidation catalyst (DOC) should have the properties of oxidizing CO, HC and SOF effectively at low exhaust gas temperature while minimizing the formation of sulfate at high exhaust gas temperature. Precious metals such as platinum and palladium have been known to be sufficiently active for oxidizing SOF and also to have high activity for the oxidation of sulfur dioxide $(SO_2)$ to sulfur trioxide $(SO_3)$. There is a need to develop a highly selective catalyst which can promote the oxidation SOF efficiently, on the other hand, suppress the oxidation of $SO_2$. In this study, a Pt-V catalyst was prepared by impregnating platinum and vanadium onto a Ti-Si wash coated ceramic monolith substrate. A prepared Pt-V catalytic converter was installed on a heavy duty diesel engine and the effect of fuel sulfur on particulate matter (PM) of heavy duty diesel engine was measured. The effect of fuel sulfur on PM of Pt-V was also compared with that of a commercialized Pt catalyst currently being used in some of the heavy duty diesel engines in advanced countries. Only 1 $\sim$ 3% of sulfur in the diesel fuel was converted to sulfate in PM for the engine without catalyst, but almost 100% of sulfur conversion was achieved for the engine with Pt catalyst at maximum loading condition. In the case of Pt-V catalyst, there was no big difference in conversion with the base engine even at maximum loading condition. The reason of SOF increase according to the increase of suflate emission was identified as the washing off effect of bound water in sulfate.

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Ligand Effect in Recycled CNT-Pd Heterogeneous Catalyst for Decarboxylative Coupling Reactions

  • Kim, Ji Dang;Pyo, Ayoung;Park, Kyungho;Kim, Gwui Cheol;Lee, Sunwoo;Choi, Hyun Chul
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2099-2104
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    • 2013
  • We present here an efficient and simple method for preparation of highly active Pd heterogeneous catalyst (CNT-Pd), specifically by reaction of dichlorobis(triphenylphosphine)palladium ($Pd(PPh_3)_2Cl_2$) with thiolated carbon nanotubes (CNTs). The as-prepared CNT-Pd catalysts demonstrated an excellent catalytic activity for the carbon-carbon (C-C) cross-coupling reactions (i.e. Suzuki, Stille, and decarboxylative coupling reactions) under mild conditions. The CNT-Pd catalyst could easily be removed from the reaction mixture; additionally, in the decarboxylative coupling of iodobenzene and phenylpropiolic acid, it showed a six-times recyclability, with no loss of activity. Moreover, once its activity had decreased by repeated recycling, it could easily be reactivated by the addition of phosphine ligands. The remarkable recyclability of the decarboxylative coupling reaction is attributable to the high degree of dispersion of Pd catalysts in CNTs. Aggregation of the Pd catalysts is inhibited by their strong adhesion to the thiolated CNTs during the chemical reactions, thereby permitting their recycling.

Palladium-Catalyzed Carbonylative Homocoupling Reaction of Vinylmercuric Chlorides with Carbon Monoxide (팔라듐 촉매를 이용한 Vinylmercuric-chlorides 의 CO 첨가 호모커플링반응)

  • KimJin-Il 김진일;Kwang-Hyek Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.657-661
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    • 1989
  • Symmetrical divinyl ketone or divinyl ${\alpha}$-diketone was synthesized in moderately good yields through palladium catalyzed carbonylative homocoupling reaction of vinylmercuric chlorides with carbon monoxide. In order to find out optimum synthetic reaction conditions, we examined the effect of catalysts, bases, solvents and reaction temperature when (E)-styrylmercuric chloride was used as a typical starting material. The best yield of divinyl ${\alpha}$-diketone was obtained in the reaction using 10 mol% of dichlorobis(triphenyl phosphine)palladium (II) as a catalyst, an equivalent of pyridine as a base, 10 mol% of iodine and acetonitrile at 50${\circ}$C under 10 atmospheric pressure of carbon monoxide. The yield of divinyl ${\alpha}$-diketone was decreased under atmospheric pressure of carbon monoxide.

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Palladium Catalyzed New Synthesis of Divinyl Ketones and Divinyl ${\alpha}$-Diketones (팔라듐 촉매를 이용한 디비닐케톤과 디비닐 ${\alpha}$-디케톤의 새로운 합성)

  • Jin Il Kim;Kwang Hyek Lee;Seung Jae Im
    • Journal of the Korean Chemical Society
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    • v.33 no.5
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    • pp.522-529
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    • 1989
  • Symmetrical divinyl ketones and divinyl ${\alpha}$-diketones were synthesized in moderately good yields through palladium catalyzed carbonylative homocoupling reaction of vinylic halides. Divinyl ${\alpha}$-diketones were obtained in the highest yield in the presence of 10 atm of carbon monoxide, using 2 mol% ligand added to palladium(II) acetate as catalyst and three equivalents of tributylamine as base in polar solvent at $100^{\circ}C$. Divinyl ketones were synthesized mainly under atmospheric pressure of carbon monoxide. The reaction was also proceeded to several other vinylic halides under the above reaction condition. Thus, divinyl ketones and divinyl ${\alpha}$-diketones were synthesized selectively as expected.

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A Research on Direct Formic Acid Fuel Cell (DFAFC) using Palladium Catalyst Synthesized by Polyol Method (폴리올 방법으로 합성된 팔라듐 촉매를 이용한 직접개미산연료전지에 대한 연구)

  • YANG, JONGWON;KIM, EUI HYUN;CHOI, MIHWA;KWON, YONGCHAI
    • Transactions of the Korean hydrogen and new energy society
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    • v.26 no.3
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    • pp.227-233
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    • 2015
  • In this study, we evaluate catalytic activity of Pd/C catalyst that is synthesized by modified polyol method. With such formed Pd/C is used as anodic catalyst for direct formic acid fuel cell (DFAFC) and performances of the DFAFC are measured to verify whether the new catalyst is effective for enhancing DFAFC performance and to determine optimal loadings of the Pd/C needed for obtaining best DFAFC performance. Pd particle distribution of the Pd/C catalyst is analyzed by TEM, while its catalytic activity is estimated by using cyclic voltammogram (CV) as measuring formic acid oxidation reaction and active surface area. As a result of that, the Pd/C catalyst synthesized by modified polyol shows better catalytic activity and DFAFC performance with small loading amount of Pd/C. When loading amount of Pd/C is $1.5mgcm^{-2}$, maximum power density of DFAFC adopting the catalyst is $122mWcm^{-2}$.

Composition Survey and Analysis of Non-Pt Oxygen Reduction Catalysts for Proton Exchange Membrane Fuel Cells (고체 고분자 연료전지용 비백금계 산소환원촉매 조성 조사 및 분석)

  • Kwon, Kyung-Jung
    • Journal of the Korean Electrochemical Society
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    • v.15 no.1
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    • pp.12-18
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    • 2012
  • The prohibitively high cost of Pt catalyst might be the biggest barrier for the commercialization of proton exchange membrane fuel cells (PEMFC) of which wide application is expected. Worldwide research efforts for the development of alternative to Pt oxygen reduction reaction (ORR) catalyst are made recently. One of the important considerations in the catalyst development is durability issue as well as economic aspect. From this point of view, platinum group metals (PGM) except Pt can be a candidate for replacing Pt catalyst because the material properties and the catalytic activity of PGM are expected to be similar to Pt. In contrast to Ir, Rh and Os to which not so much attention has been paid as an ORR catalyst, Pd that is most similar to Pt in terms of material properties and catalytic activity and Ru that is in the form of chalcogenide have been studied intensively. Activity comparison between non-Pt and Pt oxygen reduction catalysts by half cell test using RDE (rotating disk electrode) or PEMFC MEA (membrane electrode assembly) operation indicates that Pd-based catalysts show the most similar activity to Pt. In this paper we analyze the composition of PGM ORR catalyst in literature to promote the development of non-Pt ORR catalyst.

Effect of Acetate Promotor on the Pd-Au/SiO2-catalyzed Synthesis of Vinyl Acetate from the Reaction of Ethylene with Acetic Acid (Pd-Au/SiO2 촉매에 의한 에틸렌과 아세트산으로부터 비닐 아세트산염의 생성반응에 대한 아세트산염의 촉진 효과)

  • Atashi, Hossein;Motahari, Kazem;Tabrizi, Farshad Farshchi;Sarkari, Majid;Fazlollahi, Farhad
    • Journal of the Korean Chemical Society
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    • v.55 no.1
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    • pp.92-97
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    • 2011
  • The effect of Group I alkali acetate promoters on vinyl acetate (VA) synthesis was evaluated. Catalyst product selectivity and ethylene conversion are compared to the unpromoted catalyst in the fixed-bed reactor with oxidation reaction of ethylene and acetic acid in gaseous phase over Pd-Au/$SiO_2$ catalyst. It was found that: a) the promoters were stabilized on the catalyst surface, b) common effect for the alkali promoted Pd-Au catalysts increaseed in product selectivity and ethylene conversion compared to unpromoted catalyst (these effects increase from top to the bottom of Group I). These promoting effect is due to the common-ion effect of acetate, present in the reaction, resulting in an increase in the activity of the catalyst. In addition a complementary theory for the effect of Au in the structure of the catalyst is proposed the imposition of distribution of palladium particles through decreasing the particle's diameter.