1013-08-7Relevant articles and documents
Mesoporous zeolite-supported metal sulfide catalysts with high activities in the deep hydrogenation of phenanthrene
Fu, Wenqian,Zhang, Lei,Wu, Dongfang,Xiang, Mei,Zhuo, Qian,Huang, Kai,Tao, Zhongdong,Tang, Tiandi
, p. 423 - 433 (2015)
Developing highly active hydrogenation catalysts for deep aromatics saturation is of great importance in the production of ultraclean diesel fuel at a low cost. Toward this goal, we synthesized a mesoporous zeolite ZSM-5 (MZSM-5) that was cost-effective and available on a large scale, and used it as a support for the preparation of highly efficient metal sulfide catalysts (NiMoS/MZSM-5 and CoMoS/MZSM-5) for the deep hydrogenation of phenanthrene. The intrinsic activity of the NiMoS/MZSM-5 catalyst (7.4 × 10-4 mol kg-1 s-1) was much higher than that of the alumina-supported NiMo catalyst (NiMoS/γ-Al2O3, 4.8 × 10-4 mol kg-1 s-1), and the selectivity of the deep hydrogenation products over NiMoS/MZSM-5 (20.9%) was higher than for NiMoS/γ-Al2O3 (15.2%). Compared with γ-Al2O3, the relatively weak metal-support interaction could facilitate the formation of polymolybdates on MZSM-5. After sulfidation, the more multistacked MoS2 active phases were formed on the MZSM-5, enhancing the hydrogenation activity of the NiMoS/MZSM-5 catalyst.
Acid-Catalyzed Skeletal Rearrangements in Arenes: Aryl versus Alkyl Ring Pirouettes in Anthracene and Phenanthrene
Skraba-Joiner, Sarah L.,Brulet, Jeffrey W.,Song, Min K.,Johnson, Richard P.
, p. 13076 - 13083 (2017)
In 1 M triflic acid/dichloroethane, anthracene is protonated at C9, and the resulting 9-anthracenium ion is easily observed by NMR at ambient temperature. When heated as a dilute solution in triflic acid/dichloroethane, anthracene undergoes conversion to phenanthrene as the major volatile product. Minor dihydro and tetrahydro products are also observed. MALDI analysis supports the simultaneous formation of oligomers, which represent 10-60% of the product. Phenanthrene is nearly inert to the same superacid conditions. DFT and CCSD(T)//DFT computational models were constructed for isomerization and automerization mechanisms. These reactions are believed to occur by cationic ring pirouettes which pass through spirocyclic intermediates. The direct aryl pirouette mechanism for anthracene has a predicted DFT barrier of 33.6 kcal/mol; this is too high to be consistent with experiment. The ensemble of experimental and computational models supports a multistep isomerization process, which proceeds by reduction to 1,2,3,4-tetrahydroanthracene, acid-catalyzed isomerization to 1,2,3,4-tetrahydrophenanthrene with a predicted DFT barrier of 19.7 kcal/mol, and then reoxidation to phenanthrene. By contrast, DFT computations support a direct pirouette mechanism for automerization of outer ring carbons in phenanthrene, a reaction demonstrated previously by Balaban through isotopic labeling.
Reductive hydrogenation of polycyclic aromatic hydrocarbons catalyzed by metalloporphyrins
Nelkenbaum, Elza,Dror, Ishai,Berkowitz, Brian
, p. 210 - 217 (2007)
The hydrogenation of polycyclic aromatic hydrocarbons (PAHs) (naphthalene, anthracene, and phenanthrene) catalyzed by metalloporphyrins based on cobalt, nickel or iron was studied in aqueous solutions at room temperature and ambient pressure. Nickel porphyrin (P1) activated by nanosized zero-valent iron (nano-ZVI) and cobalt porphyrins (P2) and (P4) activated by titanium(III) citrate as the electron donor were demonstrated to be promising catalysts for the reductive hydrogenation of PAHs. In particular, partially saturated di-, tetra-, and octahydrogenated products were obtained for anthracene or phenanthrene using a nickel porphyrin activated by nano-ZVI, while naphthalene was transformed to tetralin. Systems containing cobalt porphyrins activated by titanium(III) citrate exhibited a high selectivity and activity toward hydrogenation of anthracene, producing 9,10-dihydroanthracene. However, no formation of hydrogenated hydrocarbons was observed from naphthalene or phenanthrene using cobalt porphyrins.
Selective Homogeneous Catalytic Hydrogenation of Polynuclear Aromatics
Grey, Roger A.,Pez, Guido P.,Wallo, Andrea
, p. 5948 - 5949 (1980)
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Durland,Adkins
, (1939)
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Interaction between Aromatics and Zinc Chloride. III. The Dissociation of Triphenylmethane and 9,10-Dihydroanthracene into Ions.
Morita, Mikio,Hirosawa, Kunio,Sato, Toshio,Ouchi, Koji
, p. 540 - 544 (1981)
Triphenylmethane and 9,10-dihydroanthracene were found to produce colored complexes placed in contact with molten zinc chloride or with solid zinc chloride pulverized or supported on porous Vycor glass.The triphenylmethane complex gave the same electronic absorption spectrum as that of the triphenylmethyl cation generated by contact with silica-alumina and BF3 on silica.The 9,10-dihydroanthracene complex exhibited the same electronic absorption band as that of the 9-anthracenium ion produced by the reaction of anthracene with concd H2SO4.The reaction of the triphenylmethane complex with deuterium gas provided HD gas and (C6H5)3CD.Similarly, the 9,10-dihydroanthracene complex and deuterium gas produced HD gas and 9,10-dihydroanthracene-9-d.Furthemore, their colored complexes on the supported zinc chloride gave a very weak IR absorption band at about 1720 cm-1, which is interpreted as corresponding to the formation of a Zn-H bond.These observations led us to conclude that triphenylmethane and 9,10-dihydroanthracene dissociate into ions upon contact with zinc chloride: (C6H5)3CH+nZnCl2 (C6H5)3C+(ZnCl2)n-H + nZnCl2 =
Comparison of nickel boride and Raney nickel electrode activity in the electrocatalytic hydrogenation of phenanthrene
Mahdavi,Los,Lessard,Lessard
, p. 2268 - 2277 (1994)
The electrocatalytic activity of nickel boride in the electrocatalytic hydrogenation of phenanthrene in ethylene glycol-water at 80°C has been compared to that of Raney nickel and fractal nickel. It is shown that the intrinsic activity of the electrode material (real electrode activity) is the same for nickel boride and Raney nickel electrodes and is lower for fractal nickel electrodes. The apparent electrode activity of nickel boride pressed powder electrodes is less than that of codeposited Raney nickel electrodes and pressed powder fractal nickel/Raney nickel electrodes. The relation in terms of the Tafel and alternating current impedance parameters are also determined.
Aromatic compound hydrogenation and hydrodeoxygenation method and application thereof
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Paragraph 0094-0095; 0106-0113, (2021/05/29)
The invention belongs to the technical field of medicines, and discloses an aromatic compound hydrogenation and hydrodeoxygenation method under mild conditions and application of the method in hydrogenation and hydrodeoxygenation reactions of the aromatic compounds and related mixtures. Specifically, the method comprises the following steps: contacting the aromatic compound or a mixture containing the aromatic compound with a catalyst and hydrogen with proper pressure in a solvent under a proper temperature condition, and reacting the hydrogen, the solvent and the aromatic compound under the action of the catalyst to obtain a corresponding hydrogenation product or/and a hydrodeoxygenation product without an oxygen-containing substituent group. The invention also discloses specific implementation conditions of the method and an aromatic compound structure type applicable to the method. The hydrogenation and hydrodeoxygenation reaction method used in the invention has the advantages of mild reaction conditions, high hydrodeoxygenation efficiency, wide substrate applicability, convenient post-treatment, and good laboratory and industrial application prospects.
