3208-43-3Relevant articles and documents
Tailor-made biofuel 2-butyltetrahydrofuran from the continuous flow hydrogenation and deoxygenation of furfuralacetone
Strohmann, Marc,Bordet, Alexis,Vorholt, Andreas J.,Leitner, Walter
supporting information, p. 6299 - 6306 (2019/12/03)
In this work, we present the first continuous flow process to produce the tailored biofuel 2-butyltetrahydrofuran from renewable resources. In a two-step approach lignocellulose-derived furfuralacetone is first hydrogenated and then deoxygenated over commercial catalysts to form the desired product. Both reactions were studied independently in batch conditions. The transition to a continuous flow system was done and various parameters were tested in the miniplant. Both reactions were performed in a two-reactor-concept approach to yield the desired 2-butyltetrahydrofuran in a high yield directly from furfuralacetone.
Solvent effects in hydrodeoxygenation of furfural-acetone aldol condensation products over Pt/TiO2 catalyst
Ramos, Rubén,Ti?ler, Zdeněk,Kikhtyanin, Oleg,Kubi?ka, David
, p. 174 - 183 (2016/12/06)
The solvent effects on hydrodeoxygenation (HDO) of 4-(2-furyl)-3-buten-2-one (F-Ac) over Pt/TiO2 catalyst were investigated at T = 200 °C and P(H2) = 50 bar. The initial reactant is the main product of aldol condensation between furfural and acetone, which constitutes a promising route for the production of bio-based chemicals and fuels. A sequence of experiments was performed using a selection of polar solvents with different chemical natures: protic (methanol, ethanol, 1-propanol, 2-propanol, 1-pentanol) and aprotic (acetone, tetrahydrofuran (THF), n,n-dimethylformamide (DMF)). In case of protic solvents, a good correlation was found between the polarity parameters and conversion. Consequently, the highest hydrogenation rate was observed when 2-propanol was used as a solvent. In contrast, the hydrogenation activity in presence of aprotic solvents was related rather to solvent-catalyst interactions. Thus, the initial hydrogenation rate declined in order Acetone > THF > DMF, i.e. in accordance with the increase in the nucleophilic donor number and solvent desorption energy. Regarding the product distribution, a complex mixture of intermediates was obtained, owing to the successive hydrogenation (aliphatic C[dbnd]C, furanic C[dbnd]C and ketonic C[dbnd]O bonds), ring opening (via C[sbnd]O hydrogenolysis) and deoxygenation reactions. Based on the proposed reaction scheme for the conversion of F-Ac into octane, the influence of the studied solvents over the cascade catalytic conversion is discussed. A significant formation of cyclic saturated compounds such as 2-propyl-tetrahydropyran and 2-methyl-1,6-dioxaspiro[4,4]nonane took place via undesirable side reactions of cyclization and isomerization. The best catalytic performance was found when using acetone and 2-propanol as solvents, achieving significant yields of 4-(2-tetrahydrofuryl)-butan-2-ol (28.5–40.4%) and linear alcohols (6.3–10.4%). The better performance of these solvents may be associated with a lower activation energy barrier for key intermediate products, due to their moderate interaction with the reactant and the catalyst. In case of methanol and DMF, undesired reactions between the reactant and the solvent took place, leading to a lower selectivity towards the targeted hydrodeoxygenated products.
Enhancing the Catalytic Properties of Ruthenium Nanoparticle-SILP Catalysts by Dilution with Iron
Luska, Kylie L.,Bordet, Alexis,Tricard, Simon,Sinev, Ilya,Grünert, Wolfgang,Chaudret, Bruno,Leitner, Walter
, p. 3719 - 3726 (2016/07/06)
The partial replacement of ruthenium by iron ("dilution") provided enhanced catalytic activities and selectivities for bimetallic iron-ruthenium nanoparticles immobilized on a supported ionic liquid phase (FeRuNPs@SILP). An organometallic synthetic approach to the preparation of FeRuNPs@SILP allowed for a controlled and flexible incorporation of Fe into bimetallic FeRu NPs. The hydrogenation of substituted aromatic substrates using bimetallic FeRuNPs@SILP showed high catalytic activities and selectivities for the reduction of a variety of unsaturated moieties without saturation of the aromatic ring. The formation of a bimetallic phase not only leads to an enhanced differentiation of the hydrogenation selectivity, but even reversed the order of functional group hydrogenation in certain cases. In particular, bimetallic FeRuNPs@SILP (Fe:Ru = 25:75) were found to exhibit accelerated reaction rates for C=O hydrogenation within furan-based substrates which were >4 times faster than monometallic RuNPs@SILP. Thus, the controlled incorporation of the non-noble metal into the bimetallic phase provided novel catalytic properties that could not be obtained using either of the monometallic catalysts.
Towards understanding the hydrodeoxygenation pathways of furfural-acetone aldol condensation products over supported Pt catalysts
Ramos,Ti?ler,Kikhtyanin,Kubi?ka
, p. 1829 - 1841 (2016/04/05)
Aiming at the valorisation of furfural-derived compounds, the hydrodeoxygenation of furfural-acetone condensation products has been studied using supported platinum catalysts. The influence of the catalytic properties of different supports, such as SiO2, Al2O3, TiO2, hydrotalcite (HTC), Beta zeolite, Al-SBA-15 and WO3-ZrO2, was evaluated in a batch reactor for 480 min at 200 °C and 50 bar of H2. The used feed consisted of a mixture of furfural-acetone adducts (C8-C19), obtained in previous experiments using a continuous flow reactor and hydrotalcite as a catalyst. Except for Pt/SiO2, all catalysts showed high conversion of the reactants, especially due to the hydrogenation of all the aliphatic CC bonds. However, the extent of further hydrogenation (furan CC and ketone CO bonds) was limited, particularly when HTC and Al2O3 were used as supports. The higher accessibility of Pt/TiO2 and the smaller Pt particle size shown by Pt/Al-SBA-15, Pt/WO3-ZrO2 and Pt/Beta in comparison with the other catalysts led to an improvement in the hydrogenation of furanic and ketonic groups, likely due to lower adsorption constraints. The higher acid character of the latter group of catalysts promotes dehydration and ring opening steps, thus enhancing the selectivity towards linear alcohols. Likewise, a significant increase in the extent of aldol condensation reactions was also observed with these catalysts, yielding longer carbon chain compounds. Based on this study, a reaction scheme for the transformation of 4-(2-furyl)-3-buten-2-one (C8) into octane has been proposed in order to establish a valuable correlation between the main conversion pathways and the catalytic properties of the employed heterogeneous catalyst, thus contributing to further development of efficient deoxygenation catalysts.
Energy-efficient production of 1-octanol from biomass-derived furfural-acetone in water
Xia, Qineng,Xia, Yinjiang,Xi, Jinxu,Liu, Xiaohui,Wang, Yanqin
, p. 4411 - 4417 (2015/08/11)
An energy-efficient catalytic system for the one-pot production of 1-octanol from biomass-derived furfural-acetone (FFA) under mild conditions in water was developed, by sequential hydrogenation/hydrogenolysis over a hydrophilic Pd/NbOPO4 catalyst. A strategy of creating an intentional "phase problem" has been employed to prevent the over-hydrogenolysis of 1-octanol into n-octane and therefore increased the selectivity to 1-octanol. The effects of reaction conditions as well as a variety of noble-metal loaded bifunctional catalysts have been systematically investigated to maximize the yield of 1-octanol. Moreover, the addition of liquid acids to the catalytic system further enhanced the selectivity towards the formation of 1-octanol. There is a strong correlation between the acid strength of an acidic additive and the sum yield of 1-octanol and octane. With the addition of TfOH, the highest yield of 1-octanol (62.7%) was obtained from one-pot conversion of biomass-derived FFA over Pd/NbOPO4.
Pd/NbOPO4 multifunctional catalyst for the direct production of liquid alkanes from aldol adducts of furans
Xia, Qi-Neng,Cuan, Qian,Liu, Xiao-Hui,Gong, Xue-Qing,Lu, Guan-Zhong,Wang, Yan-Qin
supporting information, p. 9755 - 9760,6 (2015/01/16)
Great efforts have been made to convert renewable biomass into transportation fuels. Herein, we report the novel properties of NbO x-based catalysts in the hydrodeoxygenation of furan-derived adducts to liquid alkanes. Excellent activity and st
Effective production of octane from biomass derivatives under mild conditions
Xu, Wenjie,Xia, Qineng,Zhang, Yu,Guo, Yong,Wang, Yanqin,Lu, Guanzhong
experimental part, p. 1758 - 1761 (2012/03/27)
Cool cats dont feel pressure: Furfural is catalytically converted into octane in high yields at relatively low pressures and temperatures. In a three-step process, two bifunctional catalysts, Pt/Co2AlO4 and Pt/NbOPO4, play crucial roles in achieving C8-ols from 4-(2-furyl)-3-buten-2-one and transforming the C8-ols into octane, respectively.
Selective hydrogenation of biomass derived substrates using ionic liquid-stabilized ruthenium nanoparticles
Julis, Jennifer,Hoelscher, Markus,Leitner, Walter
experimental part, p. 1634 - 1639 (2010/12/24)
Ionic liquid-stabilized ruthenium nanoparticles with an average size between 2-3 nm are very active catalysts for the hydrogenation of biomass derived substrates. Their catalytic performance complements that of classic homogeneous and heterogeneous ruthenium catalysts.
A novel mesoporous Pd/cobalt aluminate bifunctional catalyst for aldol condensation and following hydrogenation
Xu, Wenjie,Liu, Xiaohui,Ren, Jiawen,Zhang, Peng,Wang, Yanqin,Guo, Yanglong,Guo, Yun,Lu, Guanzhong
experimental part, p. 721 - 726 (2010/07/06)
A novel mesoporous Pd/cobalt aluminate bifunctional catalyst has been synthesized by a facile co-precipitation process and used in aldol condensation of furfural with acetone and the following hydrogenation of condensation products. This kind of bifunctional catalyst has good activity and can be recycled and regenerated easily. Crown Copyright
