1917-65-3Relevant academic research and scientific papers
Synthesis of 5-ethoxymethylfurfural from fructose and inulin catalyzed by a magnetically recoverable acid catalyst
Zhang, Zehui,Wang, Yimei,Fang, Zhongfeng,Liu, Bing
, p. 233 - 240 (2014)
A magnetically recoverable catalyst was conveniently synthesized by the immobilization of sulfonic acid on the surface of silica-encapsulated Fe 3O4 nanoparticles, and it was used to catalyze the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural (EMF). A high EMF yield of 89.3 % was obtained from the etherification of 5-hydroxymethylfurfural at 100 °C for 10 h. The one-pot conversion of fructose could produce EMF with a yield of 72.5 %. More importantly, EMF was also obtained in a satisfactory yield of 63.3 % when the polysaccharide inulin was used as the starting material. The excellent EMF yield showed that the catalyst had strong and sufficient acidic sites, which were responsible for the good catalytic performance. After the reaction, the catalyst could be readily removed from the reaction mixture by means of an external magnetic field, and the catalyst could be reused several times without significant loss in its catalytic activity. Incidentally, the product EMF was easily obtained through the evaporation of the solvent, ethanol, under reduced pressure at low temperature (ca. 40 °C), and the ethanol could also be reused. The integrated utilization of a biorenewable feedstock, magnetically recoverable catalyst, and bio-based green solvent is a typical example of an ideal green chemical process to produce potential liquid fuels. Copyright
Selective etherification of hydroxymethylfurfural to biofuel additives over Cs containing silicotungstic acid catalysts
Raveendra,Rajasekhar,Srinivas,Sai Prasad,Lingaiah
, p. 105 - 113 (2016)
A series of Cs exchanged silicotungstic acid (STA) catalysts were prepared and their physico-chemical properties were derived from FT-Infrared, X-ray diffraction, Laser Raman, temperature programmed desorption of ammonia and BET surface area. The characterization results revealed that the Keggin structure of STA remained intact even after Cs ions replaced its protons. The catalysts activity was evaluated for the selective etherification of 5-hydroxymethylfurfural (HMF) with ethanol for the synthesis of 5-ethoxymethylfurfural (EMF). The partial exchange of Cs ions with protons of STA resulted an increase in acidity and the catalysts with two Cs ions in STA showed highest acidity. The activity was explained based on the acidity, surface and structural properties of the catalysts. A detailed study was made on the effect of various reaction parameters such as influence of reaction temperature, reaction time, Cs content on STA to unveil the optimize reaction conditions. The catalyst was recovered easily from the reaction mixture and reused at least four times with constant activity.
Efficient production of 5-ethoxymethylfurfural from fructose by sulfonic mesostructured silica using DMSO as co-solvent
Morales,Paniagua,Melero,Iglesias
, p. 305 - 316 (2017)
The use of sulfonic acid-functionalized heterogeneous catalysts in conjunction with the use of dimethyl sulfoxide (DMSO) as co-solvent in the catalytic transformation of fructose in ethanol to produce 5-ethoxymethyl furfural (EMF) is shown as an interesting alternative route for the production of this advanced biofuel. Arenesulfonic acid-modified SBA-15 mesostructured silica (Ar-SO3H-SBA-15) has been the most active catalyst, ascribing its higher catalytic performance to the combination of excellent textural properties, acid sites surface concentration and acid strength. Noticeably, DMSO promotes the formation of EMF and HMF, reducing the extent of side reactions. Reaction conditions (temperature, catalyst loading and DMSO concentration) where optimized for Ar-SO3H-SBA-15 via response surface methodology leading to a maximum EMF yield of 63.4% at 116 °C, 13.5 mol% catalyst loading based on starting fructose and 8.3 vol.% of DMSO in ethanol after 4 h of reaction. Catalyst was reused up to 4 consecutive times, without regeneration treatment, showing a slight gradual decay in activity attributed to the formation of organic deposits on the catalyst's surface.
Sulfonated graphene oxide as effective catalyst for conversion of 5-(hydroxymethyl)-2-furfural into biofuels
Antunes, Margarida M.,Russo, Patrícia A.,Wiper, Paul V.,Veiga, Jacinto M.,Pillinger, Martyn,Mafra, Luís,Evtuguin, Dmitry V.,Pinna, Nicola,Valente, Anabela A.
, p. 804 - 812 (2014)
The acid-catalyzed reaction of 5-(hydroxymethyl)-2-furfural with ethanol is a promising route to produce biofuels or fuel additives within the carbohydrate platform; specifically, this reaction may give 5-ethoxymethylfurfural, 5-(ethoxymethyl)furfural diethylacetal, and/or ethyl levulinate (bioEs). It is shown that sulfonated, partially reduced graphene oxide (S-RGO) exhibits a more superior catalytic performance for the production of bioEs than several other acid catalysts, which include sulfonated carbons and the commercial acid resin Amberlyst-15, which has a much higher sulfonic acid content and stronger acidity. This was attributed to the cooperative effects of the sulfonic acid groups and other types of acid sites (e.g., carboxylic acids), and to the enhanced accessibility to the active sites as a result of the 2D structure. Moreover, the acidic functionalities bonded to the S-RGO surface were more stable under the catalytic reaction conditions than those of the other solids tested, which allowed its efficient reuse. Graphene on the scene: Sulfonated, partially reduced graphene oxide (S-RGO) exhibits a superior catalytic performance than other carbocatalysts and Amberlyst-15 in the acid-catalyzed conversion of 5-(hydroxymethyl)-2-furfural to products for biofuels. The beneficial effects are associated with the 2D structure of S-RGO and its acidic surface enriched with sulfur and oxygen functionalities.
One-pot conversions of lignocellulosic and algal biomass into liquid fuels
De, Sudipta,Dutta, Saikat,Saha, Basudeb
, p. 1826 - 1833,8 (2012)
The one-pot conversion of lignocellulosic and algal biomass into a liquid fuel, 2,5-dimethylfuran (DMF), has been achieved by using a multicomponent catalytic system comprising [DMA]+[CH3SO3] - (DMA=N,N-dimethylacetamide), Ru/C, and formic acid. The synthesis of DMF from all substrates was carried out under mild reaction conditions. The reaction progressed via 5-hydroxyemthylfurfural (HMF) in the first step followed by hydrogenation and hydrogenolysis of HMF with the Ru/C catalyst and formic acid as a hydrogen source. This report discloses the effectiveness of the Ru/C catalyst for the first time for DMF synthesis from inexpensive and readily abundant biomass sources, which gives a maximum yield of 32 % DMF in 1 h. A reaction route involving 5-(formyloxymethyl)furfural (FMF) as an intermediate has been elucidated based on the 1H and 13C NMR spectroscopic data. Another promising biofuel, 5-ethoxymethylfurfural (EMF), was also synthesized with high selectivity from polymeric carbohydrate-rich biomass substrates by using a Bronsted acidic ionic liquid catalyst, that is [DMA]+[CH3SO3]-, by etherification of HMF in ethanol. Copyright
Lewis acidity induced heteropoly tungustate catalysts for the synthesis of 5-ethoxymethyl furfural from fructose and 5-hydroxymethylfurfural
Kumari, P. Krishna,Rao, B. Srinivasa,Padmakar,Pasha, Nayeem,Lingaiah
, p. 108 - 115 (2018)
Heteropoly tungstate with tantalum ions in its secondary structure were prepared and subsequently dispersed on tin oxide. The prepared materials physical and chemical properties were estimated by different spectroscopic methods Characterization results indicate that the stable Keggin ion of tantalum heteropoly tungstate was well preserved on support. New Lewis acidic sites were generated with the presence of Ta ions in heteropoly tungstate. These samples were tested for their catalytic performance towards conversion of fructose to 5-ethoxy methyl furfural (EMF) and selective etherification of 5-hydroxymethylfurfural (HMF) with ethanol. The catalyst with 30 wt% of active component on SnO2 exhibited highest HMF etherification activity with 90% of 5-ethoxymethylfurfural yield with in 45 min. The catalysts also able to converted fructose into EMF in one-pot with a yield of 68%. The etherification activity over these catalysts was studied under the influence of different reaction parameters such as reaction temperature, reaction time, catalyst weight and reactants mole ratio.
Silica coated magnetic Fe3O4 nanoparticles supported phosphotungstic acid: A novel environmentally friendly catalyst for the synthesis of 5-ethoxymethylfurfural from 5-hydroxymethylfurfural and fructose
Wang, Shuguo,Zhang, Zehui,Liu, Bing,Li, Jinlin
, p. 2104 - 2112 (2013)
In this study, a magnetically-recoverable catalyst (Fe3O 4@SiO2-HPW) was prepared by the application of phosphotungstic acid (HPW) supported on silica-coated Fe3O 4 nanoparticles. The prepared samples were characterized by XRD, TEM, FT-IR, and N2-adsorption-desorption isotherms. The content of W in Fe3O4@SiO2-HPW was measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and its surface acidity was determined by a potentiometric titration with n-butylamine. Fe 3O4@SiO2-HPW showed an excellent catalytic activity for the synthesis of EMF from HMF and fructose. Under optimal reaction conditions, EMF was obtained in a high yield of 83.6% by the etherification of 5-hydroxymethylfurfural. EMF could also be synthesized directly from fructose in a yield of 54.8% via a one-pot reaction strategy. After reaction, the catalyst Fe3O4@SiO2-HPW could be easily separated from the reaction mixture with an external magnetic field, and it could be reused at least five times without any loss of its catalytic activity.
Production of biomass-derived furanic ethers and levulinate esters using heterogeneous acid catalysts
Neves, Patricia,Antunes, Margarida M.,Russo, Patricia A.,Abrantes, Joana P.,Lima, Sergio,Fernandes, Auguste,Pillinger, Martyn,Rocha, Silvia M.,Ribeiro, Maria F.,Valente, Anabela A.
, p. 3367 - 3376 (2013)
Mesoporous aluminosilicates of the type Al-TUD-1, prepared via "green", low-cost, non-surfactant templating routes, are effective and versatile heterogeneous acid catalysts for the production of useful bio-based furanic ethers and levulinate esters, via the reactions of the biorenewable substrates 5-hydroxymethyl-2-furfural (Hmf) or furfuryl alcohol (FA) with aliphatic alcohols. The identification of reaction intermediates and products by comprehensive two-dimensional gas chromatography combined with time-of-flight mass spectrometry was carried out, giving mechanistic insights. Ethyl levulinate (EL) was formed from FA or Hmf as substrates, with higher EL yields being reached in the former case. Different types of alkyl levulinates may be synthesized from FA using Al-TUD-1 catalysts. On the other hand, 5-(ethoxymethyl)furan-2-carbaldehyde may be formed as the main product from Hmf. Modifications of the properties of Al-TUD-1 involved varying the Si/Al ratio and applying a post-synthesis acid treatment. The influence of these factors and of the reaction conditions on the catalytic reactions was investigated. The efficient regeneration and recyclability of Al-TUD-1 was assessed.
Facile single-step conversion of macroalgal polymeric carbohydrates into biofuels
Kim, Bora,Jeong, Jaewon,Shin, Seunghan,Lee, Dohoon,Kim, Sangyong,Yoon, Hyo-Jin,Cho, Jin Ku
, p. 1273 - 1275 (2010)
Red macroalgae-derived agar is a renewable and sustainable resource. For the synthesis of HMF under solid Br?nsted acid conditions, agar shows a unique reaction pattern and affords higher yields than land plant-based polymeric carbohydrates. Agar can be directly converted into next-generation biofuels by one-pot reactions and readily isolated by using a general workup procedure, which is crucial for a large-scale process.
Graphene oxide as a facile acid catalyst for the one-pot conversion of carbohydrates into 5-ethoxymethylfurfural
Wang, Hongliang,Deng, Tiansheng,Wang, Yingxiong,Cui, Xiaojing,Qi, Yongqin,Mu, Xindong,Hou, Xianglin,Zhu, Yulei
, p. 2379 - 2383 (2013)
Graphene oxide obtained by the Hummers method was discovered to be an efficient and recyclable acid catalyst for the conversion of fructose-based biopolymers into 5-ethoxymethylfurfural (EMF). EMF yields of 92%, 71%, 34% and 66% were achieved when 5-hydroxymethylfurfural (HMF), fructose, sucrose and inulin were used as starting materials, respectively.
