13529-27-6Relevant articles and documents
Aqueous phase hydrogenation of furfural to tetrahydrofurfuryl alcohol over Pd/UiO-66
Kogan, Victor M.,Liu, Ying-Ya,Sun, Zhichao,Wang, Anjie,Wang, Chunhua,Wang, Yao,Yu, Zhiquan
, (2021)
A Pd/UiO-66 catalyst was synthesized with well-dispersed Pd nanoparticles. The obtained catalyst was tested in the hydrogenation of furfural to tetrahydrofurfuryl alcohol in various solvents, Water was found to be the most suitable solvent. Pd/UiO-66 exhibited much higher activity than Pd/SiO2 and Pd/γ-Al2O3, completely converting furfural to tetrahydrofurfuryl alcohol with 100% selectivity under mild conditions. The hydrogenation of C[dbnd]O moiety in tetrahydrofurfural was rate-determining step. Static adsorption measurement indicated that the adsorption of furfural on UiO-66 was significantly stronger than that on SiO2 or γ-Al2O3, suggesting that the adsorption play an important role in the gas-liquid-solid furfural hydrogenation reaction.
Hydrogenation and hydrogenolysis of furfural and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes
Gowda, Anitha S.,Parkin, Sean,Ladipo, Folami T.
, p. 86 - 93 (2012)
The catalytic activity of ruthenium(II) bis(diimine) complexes cis-[Ru(6,6′-Cl2bpy)2(OH2) 2](Z)2 (1, Z = CF3SO3; 2, Z = (3,5-(CF3)2C6H3)4B, i.e. BArF) and cis-[Ru(4,4′-Cl2bpy)2(OH2) 2](Z)2 (3, Z = CF3SO3; 4, Z = BArF) for the hydrogenation and/or the hydrogenolysis of furfural (FFR) and furfuryl alcohol (FFA) was investigated. The molecular structures of cis-[Ru(4,4′- Cl2bpy)2(CH3CN)2](CF 3SO3)2 (3′) and dimeric cis-[(Ru(4,4′-Cl2bpy)2Cl)2](BArF) 2 (5) were characterized by X-ray crystallography. The structures are consistent with the anticipated reduction in steric hindrance about the ruthenium centers in comparison with corresponding complexes containing 6,6′-Cl2bpy ligands. While compounds 1-4 are all active and highly selective catalysts for the hydrogenation of FFR to FFA under modest reaction conditions, 3 and 4 showed decreased activity. This is best explained in terms of reduced Lewis acidity of the Ru2+ centers and reduced steric hindrance about the metal centers of catalysts 3 and 4. cis-[Ru(6,6′-Cl2bpy)2(OH2) 2](BArF)2 (2) also displayed high catalytic efficiency for the hydrogenation of FFA to tetrahydrofurfuryl alcohol. Presumably, this is because coordination of C=C bonds of FFA to the ruthenium center is poorly inhibited by non-coordinating BArF counterions. Interestingly, cis-[Ru(6,6′-Cl2bpy)2(OH2) 2](CF3SO3)2 (1) showed some catalytic activity in ethanol for the hydrogenolysis of FFA to 2-methylfuran, albeit with fairly modest selectivity. Nonetheless, these results indicate that ruthenium(II) bis(diimine) complexes need to be further explored as catalysts for the hydrogenolysis of C-O bonds of FFR, FFA, and related compounds. Copyright
Furfural hydrogenation on nickel-promoted Cu-containing catalysts prepared from hydrotalcite-like precursors
Xu, Chenghua,Zheng, Liangke,Liu, Jianying,Huang, Zunyu
, p. 691 - 697 (2011)
The nickel-promoted Cu-containing catalysts (CuxNi y-MgAlO) for furfural (FFR) hydrogenation were prepared from the hydrotalcite-like precursors, and characterized by X-ray powder diffraction, inductively-coupled plasma atomic emission spectroscopy, N2 adsorption-desorption, UV-Vis diffuse reflectance spectra and temperature-programmed reduction with H2 in the present work. The obtained catalysts were observed to exhibit a better catalytic property than the corresponding Cu-MgAlO or Ni-MgAlO samples in FFR hydrogenation, and the CuNi-MgAlO catalyst with the actual Cu and Ni loadings of 12.5 wt% and 4.5 wt%, respectively, could give the highest FFR conversion (93.2%) and furfuryl alcohol selectivity (89.2%). At the same time, Cu0 species from the reduction of Cu2+ ions in spinel phases were deduced to be more active for FFR hydrogenation. The nickel-promoted Cu-containing catalysts were prepared from hydrotalcite-like precursors. Cu0 species from spinel phase was found to be the best active sites in furfural hydrogenation and the Ni2+ species in catalysts acted as the promoter.
Integrated catalytic process to directly convert furfural to levulinate ester with high selectivity
Chen, Bingfeng,Li, Fengbo,Huang, Zhijun,Lu, Tao,Yuan, Yin,Yuan, Guoqing
, p. 202 - 209 (2014)
Levulinic acid is an important platform molecule from biomass-based renewable resources. A sustainable manufacturing process for this chemical and its derivatives is the enabling factor to harness the renewable resource. An integrated catalytic process to directly convert furfural to levulinate ester was developed based on a bifunctional catalyst of Pt nanoparticles supported on a ZrNb binary phosphate solid acid. The hydrogenation of furfural and the following alcoholysis of furfuryl alcohol were performed over this catalyst in a one-pot conversion model. Mesoporous ZrNb binary phosphate was synthesized by a sol-gel method and had a high surface area of 170.1 m2g-1 and a large average pore size of around 8.0 nm. Pt nanoparticles remained in a monodisperse state on the support, and the reaction over Pt/ZrNbPO4 (Pt loading: 2.0 wt%; Zr/Nb, 1:1) gave a very high selectivity to levulinate derivatives (91 % in total). The sustainability of this conversion was greatly improved by the process intensification based on the new catalyst, mild reaction conditions, cost abatement in separation and purification, and utilization of green reagents and solvents.
The influence of metal selection on catalyst activity for the liquid phase hydrogenation of furfural to furfuryl alcohol
O'Driscoll,Leahy,Curtin
, p. 194 - 201 (2017)
In this work the replacement of toxic chromium containing catalysts for the selective hydrogenation of furfural to furfuryl alcohol was investigated. The initial focus was on the synthesis of monometallic catalysts by wet impregnation and concentrated on the employment of metals such as platinum, palladium, copper and nickel. Experiments were conducted using ethanol as the solvent which was found to have a negative effect on the selectivity to the desired product, furfuryl alcohol, with high quantities of 2-Furaldehyde diethyl acetal and difurfuryl ether formed. Consequently, toluene was selected as an alternative solvent facilitating selectivity to furfuryl alcohol only. It was found that platinum was the most promising metal of those studied as it displayed higher selectivity to furfuryl alcohol and was subsequently employed for the synthesis of bimetallic catalysts. The bimetallic catalysts were synthesised by surface reactions using a variety of promoter metals selected according on their electronegativity. It was found that, while the selectivity of all catalysts to furfuryl alcohol was close to 100%, the conversion was influenced significantly by the second metal and followed the order tin > molybdenum > manganese > barium > iron > nickel. The purpose of the research was to produce an active catalyst for the liquid phase hydrogenation under suitable industrial conditions with the results presented here conducted at 100 °C and 20 bar hydrogen pressure. Furfural conversion of 47% and close to 100% selectivity to furfuryl alcohol was achieved using a 0.6%Pt0.4%Sn/SiO2 catalyst.
A catalytic aldol condensation system enables one pot conversion of biomass saccharides to biofuel intermediates
Li, Huixiang,Xu, Zhanwei,Yan, Peifang,Zhang, Z. Conrad
, p. 1751 - 1756 (2017)
Producing bio-intermediates from lignocellulosic biomass with minimal process steps has a far-reaching impact on the biofuel industry. We studied the metal chloride catalyzed aldol condensation of furfural with acetone under conditions compatible with the upstream polysaccharide conversions to furfurals. In situ far infrared spectroscopy (FIR) was applied to guide the screening of aldol condensation catalysts based on the distinguishing characteristics of metal chlorides in their coordination chemistries with carbonyl-containing compounds. NiCl2, CoCl2, CrCl3, VCl3, FeCl3, and CuCl2 were selected as the potential catalysts in this study. The FIR results further helped to rationalize the excellent catalytic performance of VCl3 in furfural condensation with acetone, with 94.7% yield of biofuel intermediates (C8, C13) in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) solvent. Remarkably, addition of ethanol facilitated the acetal pathway of the condensation reaction, which dramatically increased the desired product selectivity over the furfural pathway. Most significantly, we demonstrate for the first time that VCl3 catalyzed aldol condensation in acidic medium is fully compatible with upstream polysaccharide hydrolysis to monosaccharide and the subsequent monosaccharide isomerization and dehydration to furfurals. Our preliminary results showed that a 44% yield of biofuel intermediates (C8, C13) can be obtained in one-pot conversion of xylose catalyzed by paired metal chlorides, CrCl2 and VCl3. A number of prior works have shown that the biofuel intermediates derived from the one-pot reaction of this work can be readily hydrogenated to biofuels.
A kinetic study of heteropolyacid-catalyzed furfural acetalization with methanol at room temperature via ultraviolet spectroscopy
Teixeira, Milena Galdino,Natalino, Ricardo,da Silva, Márcio José
, p. 143 - 149 (2020)
In this work, the ultraviolet spectroscopy was used as a tool to monitor the kinetics of acetalization reaction of furfural with alkyl alcohols. Among the Bronsted acids evaluated, Keggin heteropolyacids (e.g., H3PW12O40 and H3PMo12O40) were the more active and selective in the acetalization of furfural in reactions carried out at room temperature. The ultraviolet spectroscopy, a simple and inexpensive analytic technique was used to quantify the furfural and acetals during the reaction progress. The influence of main reaction parameters such as temperature, time, and catalyst load were assessed. The reaction scope was extended to the other alcohols. The activation energy of heteropolyacid-catalyzed reactions was determined.
Efficient hydrogenation of concentrated aqueous furfural solutions into furfuryl alcohol under ambient conditions in presence of PtCo bimetallic catalyst
Dohade,Dhepe
, p. 1144 - 1154 (2017)
Furfural (FAL), a major biomass-derived chemical, can be hydrogenated to yield the industrially important platform chemical, furfuryl alcohol (FOL). Although heterogeneous catalyst-based methods are known to yield FOL from dilute solutions of FAL, they mainly operate at high temperatures and/or high pressures of hydrogen and in the presence of organic solvents. In this work, we employ bimetallic PtCo/C catalysts with varying metal concentrations to achieve the maximum possible FOL yield (100%) at 35 °C under 0.1 MPa H2 in water. With concentrated FAL (40 wt%) at 50 °C and under 1 MPa H2 pressure, 86% yield of FOL was observed. Moreover, efficient catalyst recycling was observed over at least four runs with marginal loss in activity due to handling error and isolation of FOL in pure form confirmed by NMR and HPLC. Characterization of catalysts with several physico-chemical techniques (XRD, TEM, XPS, ICP, TPR) reveals the presence of electron-rich Pt and ionic Co species in proximity with each other and these work synergistically to facilitate maximum possible yield of FOL under ambient conditions and in water medium.
Practical acetalization and transacetalization of carbonyl compounds catalyzed by recyclable PVP-I
Cao, Fu-Rong,Lu, Guangying,Ren, Jiangmeng,Wang, Di,Zeng, Bu-Bing
, (2021/06/21)
A novel PVP-I catalyzed acetalizations/transacetalizations of carbonyl compounds has been developed processing with a mild and easy handling fashion. Different types of Acyclic and cyclic acetals were prepared from carbonyl compounds or their acetals successfully. Further applications of newly developed catalytic combination were testified. This protocol featured with simplicity of operation, mild reaction condition, short reaction time, recyclable of catalyst and broad substrates scope with excellent yields.
Production of Furfural-Diethyl-Acetal as Biofuel Additives for Gasoline by Metal Free Porphyrin Photocatalyst Under Visible Light
Bhagat, Pundlik Rambhau,Bhansali, Karan Jeevanlal
, (2021/10/14)
The protocol presents conversion of furfural (FFL) to furfural-diethyl-acetal (FDA), using ionic liquid tangled, sulphonic acid functionalized, porphyrin (ILSAFPc) as a photocatalyst under visible light at ambient conditions. The formation of FDA was achieved by reacting furfural and ethanol (1: 2.2) over ILSAFPc photocatalyst in a home-made photoreactor under 5?W LED light. The product was attained with 92% yield by photocatalytic acetalization in 18?h at room temperature and confirmed by 1H NMR and 13C NMR. The acetal was confirmed by the presence of CH singlet in 1H NMR, at (8.08) ppm and disappearance of CHO proton of the substrate at 18?h. In addition, FDA exhibited as an excellent fuel additive and results presented that both 15 and 20% blending by volume with the gasoline found comparable physicochemical properties including octane number and calorific value. Finally, ILSAFPc displayed reusability for six times under optimized conditions without significant change in the yield and structure. Graphic Abstract: [Figure not available: see fulltext.]
