534-22-5Relevant articles and documents
Bimetallic Fe-Ni/SiO2 catalysts for furfural hydrogenation: Identification of the interplay between Fe and Ni during deposition-precipitation and thermal treatments
Shi, Dichao,Yang, Qifeng,Peterson, Christi,Lamic-Humblot, Anne-Félicie,Girardon, Jean-Sébastien,Griboval-Constant, Anne,Stievano, Lorenzo,Sougrati, Moulay T.,Briois, Valérie,Bagot, Paul A.J.,Wojcieszak, Robert,Paul, Sébastien,Marceau, Eric
, p. 162 - 172 (2019)
Supported Fe-Ni catalysts have been reported for their activity and selectivity in the hydrogenation of unsaturated organic molecules. However, the control of the size and composition of the bimetallic nanoparticles remains a bottleneck when oxide-supported catalysts are prepared by impregnation, and alternative procedures should be investigated. Starting with Ni(II) and Fe(II) sulfates as precursor salts, deposition-precipitation with urea (DPU) on SiO2 in an inert atmosphere initially leads to the formation of an ill-crystallized Fe-containing Ni(II) 1:1 phyllosilicate, which reduces under hydrogen at 700 °C into bimetallic fcc Fe-Ni nanoparticles of 5.4 nm in average. Compared with the composition of the DPU solution (50 Fe at %, 50 Ni at %), an excess of Ni is detected on the catalyst (38 Fe at %, 62 Ni at %), due to the preferential reaction of Ni2+ ions with silica. In situ X-ray absorption spectroscopy and 57Fe M?ssbauer spectroscopy show that the reduction of Fe ions to the metallic state is triggered by the formation of reduced Ni centers above 350 °C, and, from then, proceeds progressively, resulting in an excess of Fe in the outer shells of the bimetallic particles. The composition of individual Fe-Ni particles evidences a standard deviation of 8%. The bimetallic Fe-Ni/SiO2 catalyst gives high yields in furfuryl alcohol in the hydrogenation of furfural, in contrast with an analog Ni/SiO2 catalyst that favours side-reactions of etherification, hydrogenolysis and hydrogenation of the furan ring.
Mechanistic insights into metal lewis acid-mediated catalytic transfer hydrogenation of furfural to 2-methylfuran
Gilkey, Matthew J.,Panagiotopoulou, Paraskevi,Mironenko, Alexander V.,Jenness, Glen R.,Vlachos, Dionisios G.,Xu, Bingjun
, p. 3988 - 3994 (2015)
Biomass conversion to fuels and chemicals provides sustainability, but the highly oxygenated nature of a large fraction of biomass-derived molecules requires removal of the excess oxygen and partial hydrogenation in the upgrade, typically met by hydrodeoxygenation processes. Catalytic transfer hydrogenation is a general approach in accomplishing this with renewable organic hydrogen donors, but mechanistic understanding is currently lacking. Here, we elucidate the molecular level reaction pathway of converting hemicellulose-derived furfural to 2-methylfuran on a bifunctional Ru/RuOx/C catalyst using isopropyl alcohol as the hydrogen donor via a combination of isotopic labeling and kinetic studies. Hydrogenation of the carbonyl group of furfural to furfuryl alcohol proceeds through a Lewis acid-mediated intermolecular hydride transfer and hydrogenolysis of furfuryl alcohol occurs mainly via ring-activation involving both metal and Lewis acid sites. Our results show that the bifunctional nature of the catalyst is critical in the efficient hydrodeoxygenation of furanics and provides insights toward the rational design of such catalysts.
Gas-Phase Heteroaromatic Substitution. 3. Electrophilic Methylation of Furan and Thiophene by CH3XCH3+ (X = F or Cl) Ions
Angelini, Giancarlo,Lilla, Gaetano,Speranza, Maurizio
, p. 7091 - 7098 (1982)
A previous radiolytic study on the gas-phase methylation of pyrrole and N-methylpyrrole by CH3XCH3+ (X = F or Cl) ions, from the γ radiolysis of CH3X, is extended to furan (3) and thiophene (4).The mechanism of the susbstitution and of the subsequent isomerization occuring via intramolecular 1,2 methyl-group shift is discussed and the substrate and positional selectivity of the selected electrophilic species evaluated.As for pyrroles, gas-phase CH3FCH3+ methylation of furan and thiophene is characterized by a scarce substrate discrimination (kS/kB = 1.2 (3), 0.8 (4), accompanied by an apprreciable positional selectivity toward those substrate positions with the highest negative net charge (O:α:β = 36percent:35percent:29percent for 3; S:α:β = 19percent:43percent:38percent for 4).On the contrary, CH3ClCH3+ confirm its inherent affinity toward n-type nucleophilic centers by attacking preferently the heteroatom of 3 and 4.In light of the previous results concerning CH3XCH3+ methylation of pyrroles, it is concluded that gas-phase attack of CH3XCH3+ on simple five-membered heteroaromatics is essentially regulated by the electrostatic interaction established within the encounter pair.A close correspondence does exist between this rationalization of the present gas-phase results and recent theoretical predictions.
Conversion of furfuryl alcohol into 2-methylfuran at room temperature using Pd/TiO2 catalyst
Iqbal, Sarwat,Liu, Xi,Aldosari, Obaid F.,Miedziak, Peter J.,Edwards, Jennifer K.,Brett, Gemma L.,Akram, Adeeba,King, Gavin M.,Davies, Thomas E.,Morgan, David J.,Knight, David K.,Hutchings, Graham J.
, p. 2280 - 2286 (2014)
The selective hydrogenation of furfuryl alcohol into 2-methylfuran was investigated at room temperature using palladium supported catalysts. We have shown that Pd-TiO2 catalysts can be very effective for the synthesis of 2-methylfuran at room t
Molybdenum carbide as a highly selective deoxygenation catalyst for converting furfural to 2-methylfuran
Xiong, Ke,Lee, Wen-Sheng,Bhan, Aditya,Chen, Jingguang G.
, p. 2146 - 2149 (2014)
Selectively cleaving the C = O bond outside the furan ring of furfural is crucial for converting this important biomass-derived molecule to value-added fuels such as 2-methylfuran. In this work, a combination of density functional theory (DFT) calculations, surface science studies, and reactor evaluation identified molybdenum carbide (Mo2C) as a highly selective deoxygenation catalyst for converting furfural to 2-methylfuran. These results indicate the potential application of Mo2C as an efficient catalyst for the selective deoxygenation of biomass-derived oxygenates including furanics and aromatics.
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Rice
, p. 3193 (1952)
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Promotion effect of Ce or Zn oxides for improving furfuryl alcohol yield in the furfural hydrogenation using inexpensive Cu-based catalysts
Jiménez-Gómez, Carmen P.,Cecilia, Juan A.,Franco-Duro, Francisco I.,Pozo, Manuel,Moreno-Tost, Ramón,Maireles-Torres, Pedro
, p. 121 - 131 (2018)
Kerolite/Mg-smectite mixed layer was used as inexpensive material to support metallic copper, with metal loadings (5–30 wt.%). These catalysts are active in gas-phase furfural hydrogenation, maintaining conversion values higher than 80 mol%, at 210 °C, after 5 h of time-on-stream, with high copper loading (15–30 wt.% Cu) catalysts, being furfuryl alcohol and 2-methylfuran the only detected products. The incorporation of Ce and Zn as promoters causes a decrease in the furfural conversion, although catalysts become much more selective toward furfuryl alcohol, reaching a maximum furfuryl alcohol yield above 80%, at 190 °C, after 5 h of TOS, after CeO2 addition.
Investigating hydrogenation and decarbonylation in vapor-phase furfural hydrotreating over Ni/SiO2 catalysts: Propylene production
Chen, Szu-Hua,Tseng, Ya-Chun,Yang, Sheng-Chiang,Lin, Shawn D.
, (2021/02/26)
Furfural can be mass-produced from lignocellulose biomass and can be a platform chemical for producing valuable chemicals. In this study, we examine Ni/SiO2 catalysts for the conversion of furfural under a hydrogen atmosphere. The reactivity an
Conversion of furfural to 2-methylfuran over CuNi catalysts supported on biobased carbon foams
Varila, Toni,M?kel?, Eveliina,Kupila, Riikka,Romar, Henrik,Hu, Tao,Karinen, Reetta,Puurunen, Riikka L.,Lassi, Ulla
, p. 16 - 27 (2020/12/28)
In this study, carbon foams prepared from the by-products of the Finnish forest industry, such as tannic acid and pine bark extracts, were examined as supports for 5/5% Cu/Ni catalysts in the hydrotreatment of furfural to 2-methylfuran (MF). Experiments were conducted in a batch reactor at 503 K and 40 bar H2. Prior to metal impregnation, the carbon foam from tannic acid was activated with steam (S1), and the carbon foam from pine bark extracts was activated with ZnCl2 (S2) and washed with acids (HNO3 or H2SO4). For comparison, a spruce-based activated carbon (AC) catalyst and two commercial AC catalysts as references were investigated. Compressive strength of the foam S2 was 30 times greater than that of S1. The highest MF selectivity of the foam-supported catalysts was 48 % (S2, washed with HNO3) at a conversion of 91 %. According to the results, carbon foams prepared from pine bark extracts can be applied as catalyst supports.
