25212-86-6Relevant articles and documents
Vapor phase hydrodeoxygenation of furfural to 2-methylfuran on molybdenum carbide catalysts
Lee, Wen-Sheng,Wang, Zhenshu,Zheng, Weiqing,Vlachos, Dionisios G.,Bhan, Aditya
, p. 2340 - 2352 (2014)
Vapor phase hydrodeoxygenation (HDO) of furfural over Mo2C catalysts at low temperatures (423 K) and ambient pressure showed high/low selectivity to CO bond/C-C bond cleavage, resulting in selectivity to 2-methylfuran (2MF) and furan of ~50-60% and 2 for deoxygenation, instead of unwanted sequential hydrogenation, was evidenced by the low selectivity to 2-methyltetrahydrofuran. The apparent activation energy and H2 order for 2MF production rates were both found to be invariant with furfural conversion caused by catalyst deactivation, suggesting that (1) the measured reaction kinetics are not influenced by the products of furfural HDO and (2) the loss of active sites, presumably by formation of carbonaceous species observed by TEM analysis, is the reason for the observed catalyst deactivation. The observed half order dependence of 2MF production rates on H2 pressure at different furfural pressures (~0.12-0.96 kPa) and the 0-0.3 order dependence in furfural pressure support the idea of two distinct sites required for vapor phase furfural HDO reactions on Mo2C catalysts. The invariance of 2MF production rates normalized by the number of catalytic centers assessed via ex situ CO chemisorption suggests that metal-like sites on Mo2C catalysts are involved in selective HDO reactions.
Ruthenium on phosphorous-modified alumina as an effective and stable catalyst for catalytic transfer hydrogenation of furfural
Campisi, Sebastiano,Ferri, Davide,Fovanna, Thibault,Kambolis, Anastasios,Kr?cher, Oliver,Nachtegaal, Maarten,Peng, Gael,Rentsch, Daniel,Villa, Alberto
, p. 11507 - 11516 (2020)
Supported ruthenium was used in the liquid phase catalytic transfer hydrogenation of furfural. To improve the stability of Ru against leaching, phosphorous was introduced on a Ru/Al2O3 based catalyst upon impregnation with ammonium hypophosphite followed by either reduction or calcination to study the effect of phosphorous on the physico-chemical properties of the active phase. Characterization using X-ray diffraction, solid state 31P nuclear magnetic resonance spectroscopy, X-ray absorption spectroscopy, temperature programmed reduction with H2, infrared spectroscopy of pyridine adsorption from the liquid phase and transmission electron microscopy indicated that phosphorous induces a high dispersion of Ru, promotes Ru reducibility and is responsible for the formation of acid species of Br?nsted character. As a result, the phosphorous-based catalyst obtained after reduction was more active for catalytic transfer hydrogenation of furfural and more stable against Ru leaching under these conditions than a benchmark Ru catalyst supported on activated carbon.
Highly dispersed Cu nanoparticles as an efficient catalyst for the synthesis of the biofuel 2-methylfuran
Dong, Fang,Ding, Guoqiang,Zheng, Hongyan,Xiang, Xiaoming,Chen, Linfeng,Zhu, Yulei,Li, Yongwang
, p. 767 - 779 (2016)
Cu/SiO2 catalysts were synthesized by different methods, which greatly influenced their texture and the catalytic performance. The AE-Cu/SiO2 catalyst was prepared via the ammonia evaporation method and showed a 95.5% yield for 2-methylfuran (a promising fuel additive) because of the cooperative effects of surface Cu0, Cu+ species and acid sites, which respectively stemmed from the reduction of highly dispersed CuO species, copper species that fiercely interacted with the support SiO2, and the special structure. The ammonia evaporation method favored the formation of a copper phyllosilicate phase with a lamellar structure, which could provide a large number of Cu nanoparticles and acid sites and further improve the activity and selectivity. Crucially, the stability of the AE-Cu/SiO2 catalyst (>210 h) was also significantly improved due to the enhanced copper-silicon interactions, which could immobilize copper particles and resist the fast transmigration (aggregation and loss) of copper particles in the thermal treatment process. In contrast, the CP-Cu/SiO2 catalyst was synthesized via the conventional precipitation method and presented poor activity and stability toward 2-methylfuran because of large copper particles, severe aggregation and a loss of copper species during reaction. Compared with the conventional CP-Cu/SiO2 catalyst, the use of the AE-Cu/SiO2 catalyst in the synthesis of the biofuel 2-methylfuran could not only improve the yield of the desired product, but also decrease by at least 20 °C the reaction temperature which is propitious for prolonging the lifetime of the Cu/SiO2 catalyst.
Cyclodextrins as growth controlling agents for enhancing the catalytic activity of PVP-stabilized Ru(0) nanoparticles
Herbois, Rudy,Noel, Sebastien,Leger, Bastien,Bai, Lei,Roucoux, Alain,Monflier, Eric,Ponchel, Anne
, p. 3451 - 3453 (2012)
Cyclodextrins act as growth controllers in the synthesis of PVP-stabilized Ru(0) nanoparticles, leading to enhancement of the catalytic activity in the hydrogenation of furfural.
Fe/FeOx embedded in LDH catalyzing C-C bond forming reactions of furfural with alcohols in the absence of a homogeneous base
Wang, Lijun,Zhong, Yang,Zhou, Bo
, (2020)
Fe/FeOx embedded in LDH was prepared by reducing the pre-synthesized [Fe(C2O4)3]3? anions intercalated LDH and used as a multi-functional catalyst for synthesis of C7-C9 compound via transfer hydrogenation between furfural (C5) and short-chain alcohols (C2-C4) and a subsequent aldol reaction of furfural with intermediate short-chain aldehydes in the absence of a homogeneous base with furfuryl alcohol as a byproduct. Screening reaction conditions, evaluation and improvement of the cyclic catalytic performance, and determination of catalytically active components were performed, and the results demonstrated that both high conversion and high selectivity to the C[sbnd]C bond forming product can be obtained under a non-oxidizing atmosphere of Ar or H2/Ar mixed gas, a reaction temperature of 140 °C and a reaction time of 4 h; the catalyst was easily deactivated during the cycle experiments, however, its catalytic stability can be effectively improved by depositing Ni with weak reducibility on the surface of Fe nanoparticles at the cost of reducing partial catalytic activity. Fe/FeOx together with LDH as a whole proved to be effective in catalyzing the transfer hydrogenation reaction and the support LDH imparted basic catalytic function to the composite realizing the aldol reaction in the absence of a homogeneous base.
Properties of copper chromite catalysts in hydrogenation reactions
Rao,Dandekar,Baker,Vannice
, p. 406 - 419 (1997)
A pretreatment involving a 4-h reduction under H2 at 573 K, compared to either 473 or 673 K, gave the highest specific activity for furfural and crotonaldehyde hydrogenation over an unpromoted copper chromite catalyst. Both H2 and CO chemisorption declined monotonically with increasing reduction temperature, but turnover frequencies also showed a maximum after a pretreatment at 573 K. DRIFTS identified a band, associated with CO adsorbed on Cu+1 sites, which reached a maximum intensity after a 573 K pretreatment, while XRD patterns also provided evidence for a CuCrO2 phase and showed a continuous increase in Cu0 as temperature increased. Selectivity to furfuryl alcohol ranged from 35-80% and reaction orders on furfural and H2 were near unity. In contrast, crotonaldehyde hydrogenation gave primarily butyraldehyde with only around 3% crotyl alcohol and a near zero-order dependence on crotonaldehyde, although the H2 dependence was still near first order. IR spectra under reaction conditions revealed adsorbed crotonaldehyde, provided evidence for an unsaturated alkoxide intermediate and detected no butyraldehyde on the surface. A simple Langmuir-Hinshelwood sequence nicely explained both reactions, it was consistent with the DRIFTS results obtained during crotonaldehyde hydrogenation, and the resultant rate expression gave meaningful entropies and enthalpies of adsorption for H2 and crotonaldehyde.
Efficient catalytic transfer hydrogenation of biomass-based furfural to furfuryl alcohol with recycable Hf-phenylphosphonate nanohybrids
Li, Hu,Li, Yan,Fang, Zhen,Smith, Richard L.
, p. 84 - 92 (2019)
An acid-base bifunctional nanohybrid phenylphosphonic acid (PhP) - hafnium (1:1.5) was synthesized through assembly of PhP with HfCl4 for catalytic transfer hydrogenation of furfural (FUR) to furfuryl alcohol (FFA) using 2-propanol as both reaction solvent and hydrogen donor source. An FFA yield of 97.6 % with formation rate of 9760 μmol g?1 h?1 at 99.2 % FUR conversion was obtained with the reaction system at 120 °C for 2 h reaction time. Activation energy (Ea) was estimated to be 60.8 kJ/mol with respect to FUR concentration, which is comparable with or even lower than Ea values attained over metal catalysts. The pronounced catalytic activity of PhP-Hf (1:1.5) is attributed to its moderate acidity and relatively strong basicity. The PhP-Hf (1:1.5) catalyst was demonstrated to maintain its activity for five consecutive reuse cycles.
Transfer hydrogenation of furfural catalyzed by multi-centers collaborative Ni-based catalyst and kinetic research
Kong, Deyu,Liu, Junhua,Mao, Weizhong,Miao, Shiwen,Wang, Fang,Yin, Bingqian
, (2021)
We propose a simple preparation route that converting biomass-derived furfural (FUR) to furfuryl alcohol (FOL) over a series of Ni-Mg-Al catalysts (NMA-n) with different molar ratios. Yield of FOL can reach 96.8 % over NMA-2 catalyst under the mild reacti
A gas-phase coupling process for simultaneous production of γ-butyrolactone and furfuryl alcohol without external hydrogen over bifunctional base-metal heterogeneous catalysts
Hu, Qi,Fan, Guoli,Yang, Lan,Cao, Xinzhong,Zhang, Peng,Wang, Baoyi,Li, Feng
, p. 2317 - 2322 (2016)
A solvent-free gas-phase coupling process through hydrogen transfer without external hydrogen supply over novel bifunctional base-metal heterogeneous catalysts was developed for the simultaneous production of γ-butyrolactone and furfuryl alcohol with high yields of 95.0% from biomass-derived compounds. Such a practical, unparallely efficient and environmentally benign process makes it promising in terms of both green sustainable chemistry and industrial perspective.
A new synthesis of 2,3-dihydrofurans: Cycloisomerization of alkynyl alcohols to endocyclic enol ethers
McDonald,Connolly,Gleason,Towne,Treiber
, p. 6952 - 6953 (1993)
Molybdenum pentacarbonyl-trimethylamine promotes the cyclization of 1-alkyn-4-ols to the isomeric 2,3-dihydrofurans.
