Biomass-derived Furfural Research Articles

Transfer Hydrogenation of Biomass-Derived Furfural to 2-Methylfuran over CuZnAl Catalysts

2-Methylfuran production through catalytic transfer hydrogenation (CTH) of furfural in liquid phase has been investigated over CuZnAl catalysts using alcohol as hydrogen donor. Results suggested that furfuryl alcohol was generated immediately and subsequently transformed into 2-methylfuran. The cleavage of C–O(H) was the rate-determining step and positively relied on the copper content. Prereduction of CuZnAl by H2 provided surface reduced Cu0 and Cu+ species with the preservation of the CuAl2O4 phase. By using the Cu2.5Zn–Al-600 catalyst with a Cu/Zn molar ratio of 2.5, we can achieve a 72% 2-methylfuran yield and a specific rate of 7.5 mmolMF/(gCat. h) under ordinary pressure in N2 at 180 °C, which is even superior to the reported noble metal catalysts. After six reaction cycles, the catalytic activity remained almost unchanged. The low cost and facile availability of the CuZnAl catalyst make it available for the potential use in industry.

Selective Synthesis of Furfuryl Alcohol from Biomass-Derived Furfural Using Immobilized Yeast Cells

Furfuryl alcohol (FA) is an important building block in polymer, food, and pharmaceutical industries. In this work, we reported the biocatalytic reduction of furfural, one of the top value-added bio-based platform chemicals, to FA by immobilized Meyerozyma guilliermondii SC1103 cells. The biocatalytic process was optimized, and the tolerance of this yeast strain toward toxic furfural was evaluated. It was found that furfural of 200 mM could be reduced smoothly to the desired product FA with the conversion of 98% and the selectivity of >98%, while the FA yield was only approximately 81%. The gap between the substrate conversion and the product yield might partially be attributed to the substantial adsorption of the immobilization material (calcium alginate) toward the desired product, but microbial metabolism of furans (as carbon sources) made a negligible contribution to it. In addition, FA of approximately 156 mM was produced within 7 h in a scale-up reaction, along with the formation of trace 2-furoic acid (1 mM) as the byproduct. The FA productivity was up to 2.9 g/L/h, the highest value ever reported in the biocatalytic synthesis of FA. The crude FA was simply separated from the reaction mixture by organic solvent extraction, with the recovery of 90% and the purity of 88%. FA as high as 266 mM was produced by using a fed-batch strategy within 15.5 h.

Liquid phase hydrogenation of furfural using 2-propanol over $$\hbox {ZrO}_{2}$$ ZrO 2

Hydrogenation of furfural is carried out efficiently by $$\hbox {ZrO}_{2}$$ using 2-propanol as a hydrogen source in liquid phase. Various characterizations like XRD, Pyridine-FTIR, $$\hbox {NH}_{3}$$ -TPD (acidity), $$\hbox {CO}_{2}$$ -TPD (basic property), and $$\hbox {N}_{2}$$ physisorption study for surface area analysis were used to understand the properties and to correlate with the activity results. These results revealed that zirconia calcined at low temperature (573 K) possesses amorphous phase, high surface area and large number of acid-base sites which are helpful in achieving higher activity. Synopsis. Transfer hydrogenation of biomass-derived Furfural to Furfuryl alcohol using 2-propanol acting as solvent and hydrogen donor over $$\hbox {ZrO}_{2}$$ in liquid phase conditions at atmospheric pressure is reported.

Novel preparation method of bimetallic Ni-In alloy catalysts supported on amorphous alumina for the highly selective hydrogenation of furfural

A novel preparation method for bimetallic nickel-indium alloy catalysts supported on amorphous alumina (Ni-In(x)/AA; x=Ni/In molar ratio) catalysts has been developed and evaluated for the highly selective hydrogenation of biomass-derived furfural. Ni-In(x)/AA catalysts were obtained via the hydrothermal treatment of Raney® nickel supported on aluminium hydroxide (R-Ni/AlOH) and an InCl2·H2O solution in an ethanol/H2O mixture at 423K for 2h, followed by reduction with H2 at 573–873K for 1.5h. The formation of Ni-In alloy phases such as Ni3In2, Ni3In, Ni2In, and NiIn in Ni-In(2.0)/AA was clearly observed after reduction with H2 at 873K for 1.5h. Ni-In(2.0)/AA contained a Ni2In alloy as the major phase, which exhibited the best catalytic performance for the selective hydrogenation of furfural into furfuryl alcohol and was stable for at least five consecutive reaction runs.

Highly Catalytic Performance of La2O3 in the Selective Transfer Hydrogenation of Biomass-derived Furfural

Highly catalytic performance of La2O3 in transfer hydrogenation reactions was achieved following pretreatment involving a sequence of heat treatments under different atmospheric gases. Furfural (FFR) was converted to furfuryl alcohol (FFA) in a very selective manner (98% conversion, with 96% selectivity) using La2O3 that had been calcined under air at 923 K and treated under H2 at 673 K. Strongly basic sites and weakly acidic sites were generated after heat pretreatment.

Effects of Reaction Conditions on Electroreduction of Biomass-Derived Furfural and Its Side Reactions in Acidic Electrolyte

Current investigations for electrochemical energy storage and generation systems help to dramatically decrease the demand for traditional fossil fuels. However, organic carbon resources, also, need to be replaced with alternatives to totally reduce their demands. In this respect, biomass is a promising sustainable resource for both alternative fuels and organic carbon-based materials [1]. Furfural (FF) is a lignocellulose-derived C­5 chemical platform that can be converted to furfuryl alcohol (FA) and 2-methyl furan (MF), which are an adhesive intermediate and a promising fuel candidate, respectively [2]. Traditionally, catalytic hydrogenation and hydrogenolysis (CH) is used for the conversion of FF to FA and MF, but it requires externally supplied hydrogen gas, high pressure and high temperature for the reaction[1, 2]. In contrast, electrochemical hydrogenation and hydrogenolysis (ECH) facilitates the conversion of FF at ambient conditions with no H2 gas. ECH of FF can use atomic hydrogen, supplied from the aqueous electrolyte. These advantages led to emerging studies for ECH of biomass, but it has not been broadly studied [3]. The relationships between electrochemical reaction conditions and results will greatly contribute to broadening the ECH of FF. In our previous study, FA and MF yield increased as a current density increased when the equivalent amount of charge was applied to the reaction in acidic solutions [4]. Also, we found that furanic compounds participate in homogeneous side reactions in pH ≤ 1 solution that can decrease mole balance and products yield as reaction time increase [4]. Another concurrent side reaction that undesirably consumes electrons is the hydrogen evolution reaction[5]. Here, we focus on the effects of applied potentials and Cu electrocatalysts, combined with rapid evaporation of MF, produced from ECH of FF. This is to investigate the product yield and electrochemical efficiency for products as well as side reactions at multiple applied potentials in 0.5 M sulfuric acid (pH 0). Also, rapid evaporation of MF with N2 gas flowing is used for avoiding its homogeneous side reactions at pH 0 [4]. Bare Cu foil and micro-sized Cu supported on Cu have been used as electrocatalysts. Rapid N2 gas flowing enhanced the mole balance and MF yield. FF conversion and MF yield increased when applied potential increased, but electrochemical efficiency for FA and MF production increased as applied potential decreased. Micro-sized Cu electrocatalysts had higher conversion of FF and yield of MF than bare Cu foil. [1] G.W. Huber, S. Iborra, A. Corma, Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering, Chemical Reviews, 106 (2006) 4044-4098. [2] Y. Nakagawa, M. Tamura, K. Tomishige, Catalytic reduction of biomass-derived furanic compounds with hydrogen, ACS Catalysis, 3 (2013) 2655-2668. [3] Y. Kwon, K.J.P. Schouten, J.C. van der Waal, E. de Jong, M.T.M. Koper, Electrocatalytic conversion of furanic compounds, ACS Catalysis, 6 (2016) 6704-6717. [4] S. Jung, E.J. Biddinger, Electrocatalytic hydrogenation and hydrogenolysis of furfural and the impact of homogeneous side reactions of furanic compounds in acidic electrolytes, ACS Sustainable Chemistry & Engineering, 4 (2016) 6500-6508. [5] R. Parsons, The rate of electrolytic hydrogen evolution and the heat of adsorption of hydrogen, Transactions of the Faraday Society, 54 (1958) 1053-1063.

Using benzene carboxylic acids to prepare zirconium-based catalysts for the conversion of biomass-derived furfural

Benzene carboxylic acid (BCAs) are common and useful chemical blocks, which can be derived from the abundant low rank coals (LRCs) via oxidative degradation. In this work, we proposed a novel strategy to utilize BCAs as raw materials to prepare catalysts with transition metal zirconium, and the prepared catalysts were applied into the conversion of the renewable biomass resources. Typical model BCAs in the oxidative products of LRCs, including pyromellitic acid, trimesic acid (TMSA), trimellitic acid, and benzoic acid, were used as the block to construct the Zr-BCAs catalysts. The chemoselective conversion of furfural into furfuryl alcohol (FAL), an important reaction in the biomass conversion chain, is chosen to evaluate the activity of the catalysts. The preparation conditions of the catalysts and experiment factors during the reaction were systematically investigated. The prepared catalysts were characterized by SEM, TEM, XRD and TG-DTG. The results showed that the prepared catalysts were efficient for the conversion of furfural into FAL, among which Zr-TMSA gave the highest activity. Zr-TMSA could be recycled for ten times without obvious deactivation, indicating an excellent stability. The strategy proposed in this work may be beneficial for the value-added utilization of both LRCs and biomass resources.Graphical Zr-BCAs catalysts prepared using benzene carboxylic acids and Zr are very efficient and stable for hydrogenation of biomass-derived furfural to furfuryl alcohol at mild conditions.

Hydrogenation of Biomass-Derived Furfural to Tetrahydrofurfuryl Alcohol over Hydroxyapatite-Supported Pd Catalyst under Mild Conditions

Tetrahydrofurfuryl alcohol (THFAL), as a green industrial solvent, can be obtained directly from biomass-derived furfural with 100% conversion and 100% yield over a hydroxyapatite-supported Pd catalyst (Pd-HAP) under relatively mild conditions (40 °C, 1 MPa H2, and 3 h) in 2-propanol. At room temperature and reacting for 8 h, the yield of THFAL was more than 99%. By capturing the intermediates, two pathways were proposed as follows: (1) Furfural was partially hydrogenated to furfuryl alcohol, and then, furfuryl alcohol was further hydrogenated to THFAL. (2) Furfural and 2-propanol first formed 2-(isopropoxymethyl)furan (2-IPMF) via etherification, and then, 2-IPMF was ultimately converted to THFAL. The Pd-HAP catalyst was characterized by various techniques including XRD, SEM, TEM, HAADF-STEM, XPS, and ICP-AAS. The results revealed that the outstanding catalytic performance of Pd-HAP was attributed to the quasicoordination effect between Pd and HAP, which not only contributed to highly dispersed and stabl...

Palladium-catalyzed hydrodehalogenation of butenolides: An efficient and sustainable access to β-arylbutenolides

Several α-unsubstituted β-arylbutenolides have been prepared in 69–92% yield by reductive dehalogenation of α-halo-β-arylbutenolides. The latter were assembled in a single-step from α,β-dihalobutenolides, which are accessible on a large-scale from biomass-derived furfural. Our dehalogenation protocol is illustrated by a new synthesis of the marine antibiotics rubrolide E and F, and 3″-bromorubrolide F.

Conversion of Furfural to 1,5-Pentanediol: Process Synthesis and Analysis

A new process for the production of 1,5-pentanediol (1,5-PDO) from biomass-derived furfural is studied. In this process, furfural is converted to 1,5-PDO in a high overall yield (80%) over inexpensive catalysts via multiple steps involving hydrogenation, dehydration, hydration, and hydrogenation subsequently. To effectively recycle H2 as well as recover 1,5-PDO, detailed separation subsystems have been designed and integrated with reaction subsystems. Furthermore, a pioneer plant analysis is performed to estimate the risk on the cost growth and plant performance shortfalls. The integrated process leads to a minimum selling price of $1973 ton–1 for 1,5-PDO, which suggests that it could be a promising approach for converting biomass into oxygenated commodity chemicals, which are difficult to produce from petroleum-derived feedstocks. The sensitivity analysis also identifies that the most important economic parameters for the process include the furfural feedstock price and plant size.

Efficiently Recyclable and Easily Separable Ni-Fe Alloy Catalysts for Chemoselective Hydrogenation of Biomass-derived Furfural

Efficient Ni-Fe alloy catalysts prepared by environmentally friendly method exhibited high selectivity in the hydrogenation of furfural (FFald) to give 95% yield of furfuryl alcohol (FFalc) under 1 MPa of H2 at 423 K using Ni-Fe(2-1) hydrogen treated at 673 K catalyst (denoted as Ni-Fe(2-1)HT-673) within 3 h. No significant loss of catalytic activity after 4 running cycles showed a high stability of the catalysts on furfural hydrogenation.

Highly Selective and Efficient Rearrangement of Biomass-Derived Furfural to Cyclopentanone over Interface-Active Ru/Carbon Nanotubes Catalyst in Water

Biomass-derived furfural was efficiently converted to valuable cyclopentanone over interface-active Ru/carbon nanotubes (CNTs) catalyst in water. The effect of reaction conditions, including furfural concentration, reaction temperature, hydrogen pressure, speed of stirring, and reaction time on the catalytic performance of Ru/CNTs has been studied in detail. The furfural conversion of 99% and cyclopentanone selectivity of 91% were efficiently achieved at very low concentration of Ru/CNTs catalyst (0.26 wt % Ru) under mild reaction conditions (1 MPa H2, 160 °C, 500 rpm). Possible reaction pathways of furfural transformation over Ru/CNTs nanoparticles in water are proposed.

Highly Selective Hydrogenation of Biomass-Derived Furfural into Furfuryl Alcohol Using a Novel Magnetic Nanoparticles Catalyst

Designing efficient and facile recoverable catalysts is desired for sustainable biomass valorization. This work reports the one-pot synthesis of a novel magnetic Fe(NiFe)O4–SiO2 nanocatalyst for hydrogenation of biomass-derived furfural into valuable furfuryl alcohol. Various techniques were used to systematically analyze the physicochemical properties of the Fe(NiFe)O4–SiO2 nanocatalyst. Vibrating sample magnetometer analysis reveals low coercivity of Fe(NiFe)O4–SiO2 (6.991 G) compared with that of Fe3O4–SiO2 (27.323 G), which is attributed to highly dispersed Ni species in the Fe(NiFe)O4–SiO2 catalyst. HRTEM images indicated the nanosized nature of the Fe(NiFe)O4–SiO2 catalyst with an average diameter of ∼14.32 nm. The Fe(NiFe)O4–SiO2 catalyst showed a superior BET surface area (259 m2/g), which is due to the formation of nanosized particles. The magnetic Fe(NiFe)O4–SiO2 nanocatalyst shows a remarkable performance with 94.3 and 93.5% conversions of furfural and ∼100% selectivity of furfuryl alcohol at 9...

Synthesis of Furan-Oxazole Conjugated Fluorescent Materials from Biomass-Derived Furfural through Cross-Coupling Reactions

Synthesis of Furan-Oxazole Conjugated Fluorescent Materials from Biomass-Derived Furfural through Cross-Coupling Reactions

Preparation of Fluorescent Materials from Biomass-Derived Furfural and Natural Amino Acid Cysteine through Cross-Coupling Reactions for Extended π-Conjugation

Preparation of 2-furylthiazole-4-carboxylic acid methyl ester is achieved in four steps from biomass-derived heteroaromatic compound furfural and a natural amino acid <sc>l</sc>-cysteine. One-pot bromination and following palladium-catalyzed arylation with arylboronates of the thus obtained furylthiazole at the furan ring gives arylated furylthiazole in excellent yields. Further arylation at the C–H bond of the thiazole ring (5-position) in the presence of AgF as an additive leads to di­arylated furylthiazoles, which show strong photoluminescence. Homocoupling at the C–H bond of thiazole is also carried out with AgF to afford the corresponding further conjugated product composed of eight (hetero)aromatic rings.

Facile Green Synthesis of Palladium Nanoparticles for Efficient Liquid-Phase Hydrogenation of Biomass-Derived Furfural

Facile Green Synthesis of Palladium Nanoparticles for Efficient Liquid-Phase Hydrogenation of Biomass-Derived Furfural

Facile synthesis of Pd nanoparticles on SiO2 for hydrogenation of biomass-derived furfural

This report shows that furfuryl alcohol can be selectively produced from the hydrogenation of furfural using supported Pd nanoparticles. Furfuryl alcohol is widely used as solvent and chemical intermediate for the synthesis of fine chemicals. Here, various Pd nanoparticles supported on mesoporous SiO2 (Pd/SiO2) were simply fabricated by a wet impregnation using palladium nitrate. Physical properties of Pd/SiO2 nanoparticles were studied by X-ray diffraction, energy-dispersive, X-ray analysis, N2 adsorption and desorption isotherms and transmission electron microscopy. Results show a high dispersion of Pd nanoparticles with small size. Pd nanoparticles catalyzed very efficiently the hydrogenation of furfural to furfuryl alcohol with 76 % selectivity under mild conditions. Overall, the catalyst developed could find applications for the production of chemicals from biomass.