F:Flammable;
110-82-7Relevant articles and documents
-
Janz
, p. 751 (1954)
-
Carra,Ragaini
, p. 1079 (1967)
-
Ipatieff,Corson,Kurbatov
, (1940)
-
Subtle factors are important: Radical formation and transmetallation in reactions of butyl cuprates with cyclohexyl iodide
Bertz, Steven H.,Human, Jason,Ogle, Craig A.,Seagle, Paul
, p. 392 - 394 (2005)
The reactions of Bu2CuLi·LiI and Bu2CuLi LiCN with cyclohexyl iodide are critically dependent upon subtle factors such as the surface properties of the reaction vessel, nature of the solvent still and lot of 'ultrapure' copper salt i
Doping effects of B in ZrO2 on structural and catalytic properties of Ru/B-ZrO2 catalysts for benzene partial hydrogenation
Zhou, Gongbing,Pei, Yan,Jiang, Zheng,Fan, Kangnian,Qiao, Minghua,Sun, Bin,Zong, Baoning
, p. 393 - 403 (2014)
The B-doped ZrO2 (B-ZrO2) samples with different B/Zr ratios were synthesized using zirconium oxychloride and boric acid as the precursors. Their crystallographic phase retained as tetragonal ZrO2 after the doping of B; however, the amount of the Lewis acid sites increased from 46.1 μmolNH3 g-1 on ZrO2 to 100.6 μmolNH3 g-1 on B-ZrO2(1/10) with the nominal B/Zr molar ratio of 1/10. The Ru/B-ZrO2 catalysts were then prepared by chemical reduction, and their electronic and structural properties were systematically characterized by spectroscopic techniques. It is identified that the Ru nanoparticles (NPs) supported on these B-ZrO2 samples exhibited similar size, chemical state, and microstructure. In the partial hydrogenation of benzene, the turnover frequency of benzene was linearly proportional to the amount of the acid sites on the supports, whereas the selectivity toward cyclohexene displayed a volcanic evolution passing through a maximum of 88% on the Ru/B-ZrO2(1/15) catalyst. Kinetic analysis indicated that the acid sites improved the rate constants of the benzene to cyclohexene step (k1) and the cyclohexene to cyclohexane step (k 2) to different degrees. The resulting k1/k2 ratio increased from 3.7 × 10-2 l mol-1 (Ru/ZrO 2) to 4.8 × 10-2 l mol-1 (Ru/B-ZrO 2(1/15)), and then declined to 4.1 × 10-2 l mol -1 (Ru/B-ZrO2(1/10)), which explained the volcanic evolution of the selectivity toward cyclohexene with respect to the acid amount.
Effect of the thermal treatment temperature of RuNi bimetallic nanocatalysts on their catalytic performance for benzene hydrogenation
Zhu, Lihua,Zheng, Jinbao,Yu, Changlin,Zhang, Nuowei,Shu, Qing,Zhou, Hua,Li, Yunhua,Chen, Bing H.
, p. 13110 - 13119 (2016)
The thermal treatment temperature of bimetallic nanocatalysts plays an important role in determining their catalytic performance. In this study, the synthesis of RuNi bimetallic nanoparticles (BNPs) supported on carbon black catalysts (denoted as RuNi BNS
Bimolecular Hydrogen Transfer over Zeolites and SAPOs having the Faujasite Structure
Dwyer, John,Karim, Khalid,Ojo, Adeola F.
, p. 783 - 786 (1991)
Silica-rich Y zeolites prepared by primary or secondary synthesis and samples of SAPO-37 have been synthesized and characterized.These materials are then evaluated as catalysts for the transformation of cyclohexene.From product distribution at low conversion the relative rates of isomerization and bimolecular hydrogen tranfer are measured and discussed in terms of active site density.
Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts
Wang, Hongliang,Wang, Huamin,Kuhn, Eric,Tucker, Melvin P.,Yang, Bin
, p. 285 - 291 (2018)
Super Lewis acids containing the triflate anion [e.g., Hf(OTf)4, Ln(OTf)3, In(OTf)3, Al(OTf)3] and noble metal catalysts (e.g., Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids.
HYDROGENATION OF BENZENE ON TECHNETIUM CATALYSTS
Pokrovskaya, O. V.,Voronin, Yu. V.,Pirogova, G. N.
, (1986)
-
Ru–Zn/ZrO2 Nanocomposite Catalysts Fabricated by Galvanic Replacement for Benzene Partial Hydrogenation
Zhou, Gongbing,Wang, Hao,Tian, Jing,Pei, Yan,Fan, Kangnian,Qiao, Minghua,Sun, Bin,Zong, Baoning
, p. 1184 - 1191 (2018)
A strategy based on galvanic replacement between metallic Zn and Ru salt followed by acid treatment was developed to fabricate supported Ru–Zn/ZrO2 nanocomposite catalysts with controlled contents of Zn for the benzene partial hydrogenation to cyclohexene. The catalysts were systematically characterized by techniques such as extended X-ray absorption fine structure, X-ray photoelectron spectroscopy, and transmission electron microscopy. In benzene partial hydrogenation, with the decrease in the content of Zn, the turnover frequency (TOF) of benzene increased monotonically, whereas the selectivity to cyclohexene evolved in a volcanic trend, passing through a maximum of 72 %. Kinetic analysis indicated that with the depletion of Zn, the rate constant for benzene hydrogenation to cyclohexene and that for cyclohexene hydrogenation to cyclohexane increased simultaneously, but the extents of the increments were at variance. It was identified that the ratios of the rate constants were in parallel with the change in the selectivity to cyclohexene, which is attributed to the electronic effect of metallic Zn that modifies the interactions of Ru with benzene and cyclohexene.
Catalytic ring expansion, contraction, and metathesis-polymerization of cycloalkanes
Ahuja, Ritu,Kundu, Sabuj,Goldman, Alan S.,Brookhart, Maurice,Vicente, Brian C.,Scott, Susannah L.
, p. 253 - 255 (2008)
Tandem dehydrogenation-olefin-metathesis catalyst systems, comprising a pincer-ligated iridium-based alkane dehydrogenation catalyst and a molybdenum-based olefin-metathesis catalyst, are reported to effect the metathesis-cyclooligomerization of cyclooctane and cyclodecane to give cycloalkanes with various carbon numbers, predominantly multiples of the substrate carbon number, and polymers. The Royal Society of Chemistry.
-
Sternberg et al.
, p. 4191 (1969)
-
Murphy,Prager
, p. 463 (1976)
NOVEL APPLICATIONS OF ZIEGLER-TYPE CATALYSTS, AROMATIZATION OF TETRALIN AND DISPROPORTIONATION OF CYCLIC OLEFINS
Costa, J. L.,Noels, A. F.,Hubert, A. J.,Teyssie, Ph.
, p. 649 - 650 (1984)
Ziegler catalysts based on Co and Ni efficiently promote the aromatization of tetralin as well as the disproportionation of cyclohexadiene and cyclohexene into benzene and cyclohexane.
Influence of Support on the Availability of Nickel in Supported Catalysts for Hydrogen Chemisorption and Hydrogenation of Benzene
Narayanan, Sankarasubbier,Sreekanth, Gutala
, p. 3785 - 3796 (1989)
Oxides such as SiO2, γ-Al2O3, TiO2 (anatase and rutile), ZrO2 and MgO with different properties have been used as supports for loading nickel by the pore volume impregnation method.Catalysts were calcined in air at 723 K for 6 h before reduction at the sa
-
Dewey,van Tamelen
, p. 3729 (1961)
-
Supported organoactinide complexes as heterogeneous catalysts. A kinetic and mechanistic study of facile arene hydrogenation
Eisen, Moris S.,Marks, Tobin J.
, p. 10358 - 10368 (1992)
This contribution reports a kinetic and mechanistic study of arene hydrogenation by the supported organoactinide complexes Cp′Th(benzyl)3/DA (1/DA), Th(1,3,5-CH2C6H3Me2)4/DA (2/DA), and Th(
Natural zeolite supported Ni catalysts for hydrodeoxygenation of anisole
Kennedy, Eric,Stockenhuber, Michael,Yan, Penghui
, p. 4673 - 4684 (2021)
Natural and synthetic (BEA, MOR) zeolite-supported nickel (～5 wt%) catalysts were prepared and employed for the hydrogenation of toluene and hydrodeoxygenation of anisole in a continuous-flow reactor. Ni/BEA and Ni/MOR display a higher level of metal dispersion and stronger metal-support interaction compared to the Ni/NZ and Ni/Escott catalysts, resulting in a higher concentration of charge-compensating Ni species and a larger high-temperature reduction peak. The Ni/BEA and Ni/MOR also present a significant mass of low-temperature desorbed H2(centred at 150 °C) based on H2-TPD, suggesting the H species are weakly adsorbed on small Ni clusters. In contrast, the H species were strongly adsorbed by the bulk Ni crystal over Ni/Escott and Ni/NZ, which were desorbed at maxima between 211 and 222 °C. We propose that the strongly adsorbed H species play a crucial role in the hydrogenation of toluene, leading to a significantly higher yield of methylcyclohexane over Ni/Escott and Ni/NZ compared to Ni/BEA and Ni/MOR. Both metal and acid sites are required in the hydrodeoxygenation of anisole. The strong Br?nsted acid sites and numerous smaller Ni species over Ni/BEA facilitated the transalkylation of anisole to phenol and methylanisole and subsequently hydrogenolysis of phenol to benzene, followed by the hydrogenation of benzene to cyclohexane.
TRANSFORMATION OF PHENOL AND ITS ETHERS IN CONDITIONS OF HYDROGENATION ON BIFUNCTIONAL ZEOLITE CATALYSTS
Marchenko, L. S.,Levin, D. Z.,Plakhotnik, V. A.,Mortikov, E. S.
, p. 81 - 84 (1986)
-
ON THE MECHANISM OF THE Co2(CO)8 CATALYZED HYDROFORMYLATION OF OLEFINS IN HYDROCARBON SOLVENTS. A HIGH PRESSURE UV AND IR STUDY
Mirbach, Marlis F.
, p. 205 - 214 (1984)
High pressure IR and UV spectroscopic experiments confirm the Heck and Breslow mechanism of the hydroformylation of 1-octene and cyclohexene with Co2(CO)8 as the starting catalyst.The major repeating unit is HCo(CO)4, which is formed via the reaction of acylcobalt tetracarbonyl with H2.The rates are 6.7 x 10-4 mol l-1 min-1 and 8.8 x 10-5 mol l-1 min-1 for 1-octene and cyclohexene, respectively at 80 deg C and 95 bar CO/H2 = 1 in methylcyclohexane.The alternative reaction of RCOCo(CO)4 with HCo(CO)4 is only a minor pathway, with rates of 1.8 x 10-5 mol l-1 min-1 and 1.1 x 10-5 mol l-1 min-1 for 1-octene and cyclohexene, respectively.It represents an exit from the catalytic cycle.The activation of the catalyst precursor Co2(CO)8 is the slowest step of the reaction.
-
Ichikawa et al.
, p. 928 (1972)
-
Ruthenium-catalyzed selective hydrogenation of benzene to cyclohexene in the presence of an ionic liquid
Schwab, Frederick,Lucas, Martin,Claus, Peter
, p. 10453 - 10456 (2011)
Reducing circumstances: The hydrogenation of benzene in organic phase leads rapidly to cyclohexane. A very simple catalyst system comprising only supported ruthenium in water with the addition of the ionic liquid 1 (R=Me) in the ppm range catalyzes the extremely difficult selective hydrogenation of benzene to cyclohexene. It is not necessary to add large amounts of salt (ZnSO4) or other metals, which is otherwise done to control selectivity. Copyright
Mechanism of Tritium-Atom-Promoted Isotope Exchange in the Benzene Ring: Application to Tritium Labeling of Biologically Important Aryl Compounds
Powell, M. F.,Morimoto, H.,Erwin, W. R.,Gordon, B. E.,Lemmon, R. M.
, p. 6266 - 6271 (1984)
Reaction of thermal tritium atoms, generated by microwave activation os T2 gas, with benzene and biphenyl was studies at ca.-50 and -196 deg C.The saturation reactions (i.e.,benzene->cyclohexane-t6)predominated over isotope exchange (i.e.,benzene->benzene-t( at -196 deg C.However, significant exchange labeling occurred at ca.-50 deg C, with a concomitant reduction in the yields of saturated products.This reversal in labeled product yields at the different temperatures is due, in part, to the faster rate of H expulsion from the intermediate cyclohexadienyl radical at -50 deg C and to the increased mobility of the warmer matrix that retards multiple T- reactions with the same aryl molecule by covering up singly tritiated intermediates.The less volatile aryl compound, biphenyl, was labeled in a diffusionally active matrix of either benezene or cyclohexane, whereas it could not be labeled otherwise.
Palladium hydrogenation catalyst based on a porous carbon material obtained upon the dehydrochlorination of a chloro polymer
Mironenko,Belskaya,Solodovnichenko,Gulyaeva,Kryazhev, Yu. G.,Likholobov
, p. 229 - 233 (2016)
The applicability of a porous carbon material obtained as a result of the “chemical” dehydrochlorination of chlorinated polyvinyl chloride as a support for palladium hydrogenation catalysts was demonstrated. The efficiency of the catalyst was evaluated in the liquid-phase reactions of nitrobenzene hydrogenation and chlorobenzene hydrodechlorination. Although the specific activity of the catalyst was lower by a factor of 3–4 than that of the samples based on Sibunit and carbon nanotubes, the complete conversion of the initial compounds with the selective formation of end products under mild conditions was achieved at a relatively low palladium content (1.5%).
-
Hubert,A.J.
, p. 2149 - 2152 (1967)
-
Synergies of surface-interface multiple active sites over Al-Zr oxide solid solution supported nickel catalysts for enhancing the hydrodeoxygenation of anisole
Fan, Guoli,Li, Feng,Lin, Yanjun,Yang, Lan,Zhang, Yaowen
, (2022/01/19)
Currently, the catalytic hydrodeoxygenation (HDO) of oxygen-containing compounds derived from biomass to highly valuable chemicals or hydrocarbon bio-fuels is attracting more and more attention. Concerning the design and synthesis of high-performance supported metal catalysts for HDO, the efficient deposition/immobilization of active metal species on supports, as well as the construction of the favorable properties of supports, is quite necessary. In this work, we fabricated series of aluminum-zirconium oxide solid solution supported Ni-based catalysts by a simple surfactant-assisted homogeneous coprecipitation and applied them in the HDO of anisole. Various structural characterizations showed that surface-interface properties of Ni-based catalysts (i.e., surface acidity, defective structures, and metal-support interactions) could be finely tuned by adjusting the amount of Al introduced into Al-Zr oxide solid solutions, thus profoundly governing their catalytic HDO activities. It was demonstrated that the introduction of an appropriate amount of Al could not only enhance surface acidity and promote the formation of defective Zr-Ov-Al structures (Ov: oxygen vacancy) but also facilitate the generation of interfacial Niδ+ species bound to the support. Over the Ni-based catalyst bearing an Al2O3:ZrO2 mass ratio of 5:2, a high cyclohexane yield of ～77.4% was attained at 230 °C and 1.0 MPa initial hydrogen pressure. The high catalytic HDO efficiency was revealed to be correlated with the catalytic synergy between Ni0 and adjacent interfacial Niδ+ species, together with the promotion of neighboring defective oxygen vacancies and acidic sites, which contributed to the enhanced activation of the methoxy group in anisole and reaction intermediate and thus greatly improved HDO activity. The present findings offer a new and promising guidance for constructing high-performance metal-based catalysts via a rational surface-interface engineering.
One-step conversion of lignin-derived alkylphenols to light arenes by co-breaking of C-O and C-C bonds
Di, Yali,Li, Guangyu,Li, Zhiqin,Liu, Weiwei,Qiu, Zegang,Ren, Xiaoxiong,Wang, Ying
, p. 2710 - 2721 (2022/02/21)
The conversion of lignin-derived alkylphenols to light arenes by a one-step reaction is still a challenge. A 'shortcut' route to transform alkylphenols via the co-breaking of C-O and C-C bonds is presented in this paper. The catalytic transformation of 4-ethylphenol in the presence of H2 was used to test the breaking of C-O and C-C bonds. It was found that the conversion of 4-ethylphenol was nearly 100%, and the main products were light arenes (benzene and toluene) and ethylbenzene under the catalysis of Cr2O3/Al2O3. The conversion of 4-ethylphenol and the selectivity of the products were significantly influenced by the reaction temperature. The selectivity for light arenes reached 55.7% and the selectivity for overall arenes was as high as 84.0% under suitable reaction conditions. Such results confirmed that the co-breaking of the C-O and C-C bonds of 4-ethylphenol on a single catalyst by one step was achieved with high efficiency. The adsorption configuration of the 4-ethylphenol molecule on the catalyst played an important role in the breaking of the C-O and C-C bonds. Two special adsorption configurations of 4-ethylphenol, including a parallel adsorption and a vertical adsorption, might exist in the reaction process, as revealed by DFT calculations. They were related to the breaking of C-O and C-C bonds, respectively. A path for the hydrogenation reaction of 4-ethylphenol on Cr2O3/Al2O3 was proposed. Furthermore, the co-breaking of the C-O and C-C bonds was also achieved in the hydrogenation reactions of several alkylphenols. This journal is
Hydrodeoxygenation of lignin and its model compounds to hydrocarbon fuels over a bifunctional Ga-doped HZSM-5 supported metal Ru catalyst
Cao, Jing-Pei,Jiang, Wei,Xie, Jin-Xuan,Yang, Zhen,Zhang, Chuang,Zhang, Jian-Li,Zhao, Liang,Zhao, Xiao-Yan,Zhao, Yun-Peng,Zhu, Chen
, (2022/02/14)
Hydrodeoxygenation (HDO) of lignin to value-added biofuels and chemicals has a great significance for the advanced utilization of renewable lignocelluloses and the future biobased economy but is always a big challenge. Herein, a Ga-doped HZSM-5 supported metal Ru catalyst (bifunctional Ru/Ga-HZSM-5) exhibited the excellent HDO performance for converting diphenyl ether (DPE) to produce the only product, i.e., cyclohexane, under extremely mild conditions (180 °C, 1 MPa H2 and 2 h). The oxygen-containing group in DPE was mainly removed through the cleavage of the C-O ether bond, followed by metal- and acid-catalyzed comprehensive hydrogenation and deoxygenation. Further characterization results confirmed that the doping of Ga remarkably enhanced the interaction between the metal Ru and the support. For the depolymerization of real lignin, Ru/Ga-HZSM-5 could not only significantly improve the total liquid yield of lignin, but also convert the oxygen-containing species into the aliphatic hydrocarbons.
