• Title/Summary/Keyword: Hydrogenation catalyst

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Palladium Nanoparticles Suspended in an Ionic Liquid as Reusable Catalyst for Alkyne Semihydrogenation

  • Lee, Jin-Kyu;Kim, Dae-Won;Cheong, Min-Serk;Lee, Hyun-Joo;Cho, Byung-Won;Kim, Hoon-Sik;Mukherjee, DebKumar
    • Bulletin of the Korean Chemical Society
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    • v.31 no.8
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    • pp.2195-2200
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    • 2010
  • The reaction of $PdCl_2$ dispersed in tetra-n-butylammonium bromide with tributyl amine at $120^{\circ}C$ under argon leads to stable isolable nanometric particles. X-ray diffraction analysis of the material indicated that it is constituted of Pd(0). Transmission electron microscopy analysis of the particles dispersed in acetone shows the mean particle size distribution ($4{\pm}1\;nm$). The isolated palladium nanoparticles can be dispersed in an ionic liquid or in methanol or used in solventless condition for selective hydrogenation of 2-hexyne under mild reaction conditions(0.2 MPa and $20^{\circ}C$). The commercial variety of the Lindlar catalyst was also studied for comparative investigations.

The effect of the modification methods on the catalytic performance of activated carbon supported CuO-ZnO catalysts

  • Duan, Huamei;Yang, Yunxia;Patel, Jim;Burke, Nick;Zhai, Yuchun;Webley, Paul A.;Chen, Dengfu;Long, Mujun
    • Carbon letters
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    • v.25
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    • pp.33-42
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    • 2018
  • Activated carbon (AC) was modified by ammonium persulphate or nitric acid, respectively. AC and the modified materials were used as catalyst supports. The oxygen groups were introduced in the supports during the modifications. All the supports were characterized by $N_2$-physisorption, Raman, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and thermogravimetric analysis. Methanol synthesis catalysts were prepared through wet impregnation of copper nitrate and zinc nitrate on the supports followed by thermal decomposition. These catalysts were measured by the means of $N_2$-physisorption, X-ray diffraction, XPS, temperature programmed reduction and TEM tests. The catalytic performances of the prepared catalysts were compared with a commercial catalyst (CZA) in this work. The results showed that the methanol production rate of AC-CZ ($23mmol-CH_3OH/(g-Cu{\cdot}h)$) was higher, on Cu loading basis, than that of CZA ($9mmol-CH_3OH/(g-Cu{\cdot}h)$). We also found that the modification methods produced strong metal-support interactions leading to poor catalytic performance. AC without any modification can prompt the catalytic performance of the resulted catalyst.

Selectivity Changes in CO Hydrogenation over Potassium Added Titania-supported Cobalt Catalysts (티타니아 담지 코발트 촉매를 이용한 일산화탄소 수소화 반응에서 칼륨첨가에 의한 선택성 변화)

  • Lee, Dong-Keun;Ahn, Jou-Hyeon
    • Applied Chemistry for Engineering
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    • v.1 no.1
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    • pp.100-105
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    • 1990
  • Small amounts of potassium were added to the titania - supported cobalt catalysts in order to produce higher and olefinic hydrocarbons in CO hydrogenation. Titania and potassium played important roles not only for the enhancement of the production of higher and olefinic hydrocarbons, but also for the prevention of the catalyst deactivation by carbon deposits. Titania support induced the so - called SMSI, and potassium seemed to act as an electronic modifier, giving rise to an electron enrichment of the metallic phase.

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Syntheses and Reactions of Iridium Complexes Containing Mixed Phosphine-Olefin Ligand: (3-(Diphenylphosphino)propyl)(3-butenyl)phenylphosphine

  • Young-ae W. Park;Devon W. Meek
    • Bulletin of the Korean Chemical Society
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    • v.16 no.6
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    • pp.524-528
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    • 1995
  • The reaction of [IrCl(cod)]2 with ppol ligand, Ph2PCH2CH2CH2P(Ph)CH2CH2CH=CH2, in ethanol gives an iridium complex, whose structure is converted from an ionic form, [Ir(cod)(ppol)]Cl·2C2H5OH (1),in polar solvents (ethanol, methanol and acetonitrile), to a molecular form, [IrCl(cod)(ppol)], in non-polar solvents (benzene and toluene). The cationic complexes, [Ir(cod)(ppol)]AsF6·1/2C2H5OH and [Ir(cod)(ppol)]PF6·1/2CH3CN, were prepared to compare with the ionic form by 31P NMR spectroscopy. When carbon monoxide is introduced to 1, cod is replaced by CO to give the 5-coordinated complex, [IrCl(CO)(ppol)]. Hydrogenation of 1-octene was not successful in the presence of 1. In order to verify the reason for 1 not behaving as a good catalyst for hydrogenation, electrophilic reactions with HCl, I2 and HBF4·etherate were performed, which yielded the oxidative addition product, [IrHCl2(ppol)], the substitution product, [IrI(cod)(ppol)], and another cationic product, [Ir(cod)(ppol)]BF4, respectively. Thus, the iridium complex is not sufficiently basic to activate hydrogen atoms or the olefin of the ppol ligand.

Material Life Cycle Assessment on Mg2NiHx-CaF2 Composites (Mg2NiHx-CaF2 수소 저장 복합체의 물질 전과정 평가)

  • HWANG, JUNE-HYEON;SHIN, HYO-WON;HONG, TAE-WHAN
    • Transactions of the Korean hydrogen and new energy society
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    • v.33 no.2
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    • pp.148-157
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    • 2022
  • Research on hydrogen storage is active to properly deal with hydrogen, which is considered a next-generation energy medium. In particular, research on metal hydride with excellent safety and energy efficiency has attracted attention, and among them, magnesium-based hydrogen storage alloys have been studied for a long time due to their high storage density, low cost, and abundance. However, Mg-based alloys require high temperature conditions due to strong binding enthalpy, and have many difficulties due to slow hydrogenation kinetics and reduction in hydrogen storage capacity due to oxidation, and various strategies have been proposed for this. This research manufactured Mg2Ni to improve hydrogenation kinetics and synthesize about 5, 10, 20 wt% of CaF2 as a catalyst for controlling oxidation. Mg2NiHx-CaF2 produced by hydrogen induced mechanical alloying analyzed hydrogenation kinetics through an automatic PCT measurement system under conditions of 423 K, 523 K, and 623 K. In addition, material life cycle assessment was conducted through Gabi software and CML 2001 and Eco-Indicator 99' methodology, and the environmental impact characteristics of the manufacturing process of the composites were analyzed. In conclusion, it was found that the effects of resource depletion (ARD) and fossil fuels had a higher burden than other impact categories.

Changes in the Physicochemical Characteristics and Trans Acid of Cottonseed Oil during Selective Hydrogenation (선택적 수소첨가 면실유의 이화학적 특성변화 및 트란스산 생성)

  • Kim, Hyean-Wee;Kim, Jong-Soo;Shim, Joong-Hwan;Park, Seong-Joon;Ahn, Tae-Hoe;Park, Ki-Moon;Choi, Chun-Un
    • Korean Journal of Food Science and Technology
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    • v.22 no.6
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    • pp.681-685
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    • 1990
  • Changes in the physicochemical characteristics and trans acid of cottonseed oil under the condition of selective hydrogenation, temperature$210^{\circ}C,\;H_2\;pressure\;0.3\;kg/cm^2$ Ni catalyst amount 0.12% (in oil), agitation speed 280 rpm, were investigated. The saturated fatty acid such as palmitic acid and stearic acid did not show any difference, while linoleic acid($50.03%{\rightarrow}9.38%$) were transformed to oleic acid ($20.65%{\rightarrow}60.35%$) during hydrogenation. In linoleic acid isomers, cc form were reduced significantly, but ct, tc, tt form showed little change, respectively. In oleic acid isomer, t form increased markedly, whereas there was no significant difference in c form. Meanwhile, melting point(MP) and solid fat content (SFC) were linearly increased, but iodine value(IV) linearly decreased as hydrogenation proceeded. From these results, linear regression equations were obtained as follows. MP & IV : Y= 1.59-2.36X(r=-0.96, p<0.05), SFC($at\;20^{\circ}C$) & MP : Y=2.81+2.01X(r=0.96, p<0.05), SFC($at\;20^{\circ}C$) & IV : Y=9.40-5.16X(r=-0.99, p<0.01), SFC($at\;20^{\circ}C$) & 18 : 1t : Y=6.25+8.48X(r=0.97, p<0.05)

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The Effect of Promotor and Reaction Condition for FT Oil Synthesis over 12wt% Co-based Catalyst (12wt% Co 담지 촉매에서 합성오일 제조시 조촉매 효과 및 반응조건 영향 분석)

  • Park, Yonhee;Lee, Jiyoon;Jung, Jongtae;Lee, Jongyeol;Cho, Wonjun;Baek, Youngsoon
    • Transactions of the Korean hydrogen and new energy society
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    • v.25 no.3
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    • pp.247-254
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    • 2014
  • The synthesis of Fischer-Tropsch oil is the catalytic hydrogenation of CO to give a range of products, which can be used for the production of high-quality diesel fuel, gasoline and linear chemicals. Our cobalt based catalyst was prepared Co/alumina, silica and titania by the incipient wet impregnation of the nitrates of cobalt and promoter with supports. Cobalt catalysts was calcined at $350^{\circ}C$ before being loaded into the FT reactors. After the reduction of catalyst has been carried out under $450^{\circ}C$ for 24hrs, FT reaction of the catalyst has been carried out at GHSV of 4,000/hr under $200^{\circ}C$ and 20atm. From these test results, we have obtained the results as following ; in case of 12wt% Co-supported $Al_2O_3$, $SiO_2$ and $TiO_2$ catalysts, maximum activities of the catalysts were appeared at the promoters of Mn, Mo and Ce respectively. The activity of 12wt% $Co/Al_2O_3$ added a Mn promoter was about 3 times as high as that of 12wt% $Co/Al_2O_3$ catalyst without promoters. When it has been the experiment at the range of reaction temperature of $200{\sim}220^{\circ}C$ and GHSV of 1,546~5,000/hr, the results have shown generally increasing the activities with the increase of reaction temperature and GHSV.

Recovery of Palladium (Pd) from Spent Catalyst by Dry and Wet Method and Re-preparation of Pd/C Catalyst from Recovered Pd (폐촉매로부터 Pd회수 및 이를 이용한 Pd/C 촉매 재제조 기술 개발)

  • Kim, Ji Sun;Kwon, Ji Soo;Baek, Jae Ho;Lee, Man sig
    • Applied Chemistry for Engineering
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    • v.29 no.4
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    • pp.376-381
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    • 2018
  • The purpose of this study is to investigate and optimize an effectiveness process for the recovery of Pd from the spent Pd/C catalyst by the process of hydrogenation of maleic anhydride over Pd/C. Pd solution recovered from Pd/C catalyst was used to prepare Pd/C catalysts. Their characteristics were compared to those of Pd/C catalyst prepared by using a reagent grade precursor solution. Pd in the spent catalyst was leached by the modified process with dry and wet methods to obtain the high recovery ratio of Pd. The burn-out of carbon in the spent Pd/C catalyst was carried out in the rage of $600-900^{\circ}C$. Pd content of carbonized catalyst was confirmed by XRF and ICP. Pd was extracted from carbonized spent catalysts with acid solutions of 1,2 and 4 M HCl at a leaching temperature of $90^{\circ}C$ for 2 h. The high recovery ratio of Pd was shown as 92.4% that leached in 4 M HCl. Also Pd/C catalysts were prepared by using the leached solution and the reagent grade of $H_2PdCl_4$ as a precursor solution and the characteristics were analyzed by XRD, CO-chemisorption and FE-TEM. As a result, the dispersion of the catalyst prepared by using the leached solution was 34.6%, which was found to be equal to or more than that of the Pd/C catalyst prepared by the reagent grade precursor solution.

Synthesis of Indoline tri-isopropyl benzene sulfonamide as a potential new asymmetric catalyst (새로운 술폰아미드계의 촉매의 합성)

  • Yun, In-Gwon;Kim, Hwan-Cheol
    • The Journal of Natural Sciences
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    • v.7
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    • pp.47-51
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    • 1995
  • In order to develope new asymmetric catalyst, we synthesized the following new sulfonamide derivatives start from S-Indoline-2-Carboxylic Acid via the following 5 steps. Hydroxy methyl derivative(1) was thus treated with methane sulfonyl chloride in the presence of triethylamine as base to give mesylated derivative(2) in 85% of isolated yield. The mesylate compound (2) was treated with excess sodium azide to give Azido derivative (4) in 95% isolated yield. Azido compound (3) was then reduced to the corresponding amino derivative in near quntitative yield by the hydrogenation under hydrogen atmospere in the presence of catalytic amount of Pd-C. The amino derivative (4) was converted to its sulfonamide derivatives by the treatment of compound(4) with triisopropyl benzene sulfonyl chloride in the presence of triethyl amine as base. Finally t-BOC group of the compound(5) was removed by the treatement of excess Trifluoro-acetic acid in near quantitative yield to give the target sulfonamide derivative (7) .in this paper we prepared compound(6) in 49% overall yield via the 5 steps of synthesis starting from t-Boc- 2-hydroxy methyl indoline(1) which cab be easily prepared from commercial available S-indoline-2-carboxylic acid by known methods. we plan to apply this new catalyst for the asymmetric reduction , diels-alder reaction, aldolcondensation reaction in due courses.

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Formation of Al2O2 supported Ni2P based 3D catalyst for atmospheric deoxygenation of rubberwood sawdust

  • Pranshu Shrivastava
    • Advances in Energy Research
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    • v.8 no.4
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    • pp.223-231
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    • 2022
  • An ex-situ gravitational fixed bed pyrolysis reactor was used over Al2O3 supported Ni2P based catalyst with various Ni/P molar ratios (0.5-2.0) and constant nickel loading of 5.37 mmol/g Al2O3 to determine the hydrodeoxygenation of rubberwood sawdust (RWS) at atmospheric pressure. The 3D catalysts formed were characterized structurally as well as acidic properties were determined by hydrogen-temperature programmed reduction (TPR). The Ni2P phase formed completely on Al2O3 for 1.5 Ni/P ratio, although lesser crystallite sizes of Ni2P were seen at Ni/P ratios less than 1.5. Additionally, it was shown that when nickel loading level increased, acidity increased and specific surface area dropped, probably because nickel phosphate is not easily converted to Ni2P. When Ni/P ratio was 1.5, Ni2P phase fully formed on Al2O3. The catalytic activity was explained in terms of impacts of reaction temperature and Ni/P molar ratio. At relatively high temperature of 450℃, the high-value deoxygenated produce was predominantly composed of n-alkanes. Based on the findings, it was suggested that hydrogenolysis, hydrodeoxygenation, dehydration, decarbonylation, and hydrogenation are all part of mechanism underlying hydrotreatment of RWS. In conclusion, the synthesized Ni2P/ Al2O3 catalyst was capable of deoxygenating RWS with ease at atmospheric pressure, primarily resulting in long chained (C9-C24) hydrocarbons and acetic acid.