1917-65-3Relevant articles and documents
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
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.
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
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.
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.
One-step fabrication of carbonaceous solid acid derived from lignosulfonate for the synthesis of biobased furan derivatives
Yu, Xin,Peng, Lincai,Gao, Xueying,He, Liang,Chen, Keli
, p. 15762 - 15772 (2018)
An eco-friendly and low-cost lignosulfonate-based acidic carbonaceous catalyst (LS-SO3H) was effectively fabricated using the sulfite pulping by-product of sodium lignosulfonate as a precursor by facile one-step simultaneous carbonization and s
Direct transformation of carbohydrates to the biofuel 5-ethoxymethylfurfural by solid acid catalysts
Li, Hu,Saravanamurugan, Shunmugavel,Yang, Song,Riisager, Anders
, p. 726 - 734 (2016)
The direct conversion of glucose to 5-ethoxymethylfurfural (EMF) is a promising biomass transformation due to the potential application of the product as a biofuel. Here, the conversion of glucose to EMF was examined over several solid acid catalysts in ethanol between 96 and 125°C. Among the catalysts employed, dealuminated beta zeolites [DeAl-H-beta-12.5 (700)] gave a moderate yield of EMF (37%) in a single step catalytic process. A combined catalytic system consisting of H-form zeolite and Amberlyst-15 was found to be more efficient for the transformation of glucose to EMF (46%) via a one-pot, two-step reaction protocol. Alternative biomass-based mono-, di- and polysaccharides also gave moderate to good yields of EMF with the catalytic systems, including fructose which yielded 67% of EMF and 4% of ethyl levulinate (ELevu) along with 10% 5-hydroxymethyl furfural (HMF) in the combined reaction protocol. A significant amount of ELevu (1-16%), a rehydrated product of EMF and a promising fuel additive, was observed in this study. Recyclability studies suggested that it was possible to reuse the DeAl-H-beta-12.5 (700) catalyst in consecutive reactions without significant changes in product yields due to its easy recovery and thermal stability during regeneration.
Synthesis of phenols from hydroxymethylfurfural (HMF)
T?upova, Svetlana,Rominger, Frank,Rudolph, Matthias,Hashmi, A. Stephen K.
, p. 5800 - 5805 (2016)
This study describes the use of hydroxymethylfurfural (HMF) as a precursor to phenols that are accessible within a few simple catalytic steps. A key step is an efficient transformation of HMF into its propargyl ether derivative under flow conditions. The latter was subsequently functionalised and used for gold-catalysed conversion into aromatic phenol derivatives. Special attention was paid on performing all of the chemical transformations under mild and environmentally benign conditions.
Tungstophosphoric acid supported on mesoporouus niobiumoxophosphate: an efficient solid acid catalyst for etherification of 5-hydroxymethylfurfural to 5-ethoxymethylfurfural
Kumari, P. Krishna,Rao, B. Srinivasa,Dhana Lakshmi,Sai Paramesh, N. Ruthwik,Sumana,Lingaiah
, p. 53 - 60 (2019)
Tungstophosphoric (TPA) supported on mesoporouus niobiumoxophosphate (NbP) catalysts were prepared with different loadings. The synthesized materials employed as heterogeneous solid acid catalysts for selective etherification of 5-hydroxymethylfurfural to 5-ethoxymethylfurfural. Physico-chemical properties of the catalysts were obtained by different spectroscopic techniques and their results exposed that TPA was a highly dispersed state on NbP and acidity of the catalyst enhanced due to its dispersion. The higher catalytic performance can be allied to the total acidity of the catalysts with appropriate number of Br?nsted-Lewis acid sites which were directed by the contact and dispersion of TPA on support. Different reaction parameters were premeditated and 25 wt% TPA/NbP catalyst exhibited highest catalytic activity with 95% of HMF conversion and 89% of EMF yield. The catalyst is reusable without noticeable turn down in catalytic performance up to five cycles. A kinetic model for etherification of HMF was also derived.
HMF etherification using NH4-exchanged zeolites
Barbera, Katia,Lanzafame, Paola,Perathoner, Siglinda,Centi, Gabriele,Migliori, Massimo,Aloise, Alfredo,Giordano, Girolamo
, p. 4300 - 4306 (2016)
The properties of BEA, MFI and Silicalite-1 zeolites in the ammonium and protonic forms are studied in the etherification of HMF (5-hydroxymethylfurfural) in anhydrous ethanol and compared with FTIR data on ammonium ion siting and displacement by competitive adsorption, as well as data on ammonium ion dissolution in aqueous solution. For the first time it is demonstrated that ammonium-exchanged zeolites are active and show better performances (particularly for the BEA structure) in the acid-catalyzed etherification reaction. This behavior is associated to a reversible dissociation of NH4+ ions, which is favored by the BEA zeolite structure. A critical condition for enhanced catalytic performances is that dissociated ammonia remains in the zeolite cages, and may be reversibly re-adsorbed. It is thus likely that the dissociated ammonia participates in the reaction or induces a confinement effect.
Direct versus acetalization routes in the reaction network of catalytic HMF etherification
Lanzafame,Papanikolaou,Perathoner,Centi,Migliori,Catizzone,Aloise,Giordano
, p. 1304 - 1313 (2018)
The etherification of HMF (5-hydroxymethylfurfural) to EMF (5-(ethoxymethyl)furan-2-carbaldehyde) is studied over a series of MFI-type zeolite catalysts containing different heteroatoms (B, Fe, Al), aiming to understand the effect of different isomorph substitutions in the MFI framework on the reaction pathways of HMF conversion. The rate constants in the reaction network are determined for these different catalysts and analyzed with respect to the amount of Br?nsted and Lewis acid sites determined by FT-IR pyridine adsorption. Two different pathways of EMF formation, i.e. direct etherification and via acetalization, were evidenced. The Lewis acid sites generated from the presence of aluminum are primarily active in catalyzing direct HMF etherification to EMF, which has a rate constant about one order of magnitude lower than the etherification of the corresponding acetals. This behaviour is due to the competitive chemisorption between hydroxyl and aldehyde groups (both present in HMF) on the Lewis acid sites catalyzing the etherification. A cooperation phenomenon between Br?nsted and Lewis acid sites is observed for the HMF acetal etherification to EMF acetal. In the reactions of direct HMF acetalization and deacetalization of the EMF acetal, the turnover frequencies for Silicalite-1 and B-MFI samples are about twice those for Fe-MFI and Al-MFI samples. This is attributed to the different reactivity of strong silanol groups associated with surface defects on the external surface in Silicalite-1 and B-MFI. These sites are also responsible for the EMF-to-EOP (ethyl 4-oxopentanoate) reaction step. In the deacetalization reaction of the EMF acetal, the behavior is determined from the presence of water (product of reaction) favouring the back reaction (aldehyde formation).
Selective conversion of fructose into 5-ethoxymethylfurfural over green catalyst
Maneechakr, Panya,Karnjanakom, Surachai
, p. 743 - 756 (2019)
Abstract: In this study, selective formation of 5-ethoxymethylfurfural (EMF) from one-pot conversion of fructose in a co-solvent of ethanol with tetrahydrofuran over green SO3H-CD carbon was investigated for the first time using an ultrasonic system. The maximum EMF yield of 74% with 100% fructose conversion was achieved in mild conditions. Moreover, the better selectivity and the longer recyclability (eight cycles) for EMF production via particular reactions such as fructose dehydration and etherification were obviously found while the formation of 5-hydroxymethylfurfual, ethyl levulinate or humins was inhibited using SO3H-CD carbon, comparing to commercial catalysts such as Amberlyst-35, SiO2-Tosic acid and Al2O3. Graphical abstract: [Figure not available: see fulltext.].
Ethanolysis of selected catalysis by functionalized acidic ionic liquids: An unexpected effect of ILs structural functionalization on selectivity phenomena
Nowakowska-Bogdan, Ewa,Nowicki, Janusz
, p. 1857 - 1866 (2022/02/05)
A series of functionalized hydrogen sulfate imidazolium ILs were synthesized and applied as catalysts in the reaction of glucose, xylose and fructose with ethanol. In this research, an unexpected selectivity phenomenon was observed. It showed that in this reaction functionalized ILs should be considered as a special type of catalyst. Functionalization of alkyl imidazolium ILs, especially the addition of electronegative OH groups, causes a clear and unexpected effect manifested via visible changes in the selectivity of the reaction studied. In the case of fructose, an increase in the number of OH groups affects an increase in the selectivity towards ethyl levulinate from 14.2% for [bmim]HSO4 to 20.1% for [glymim]HSO4 with an additional increase in selectivity to 5-hydroxymethyfurfural. In turn, for xylose, the introduction of OH groups to the alkyl chain was manifested by a decrease in selectivity to furfural as its ethyl acetal and an increase in selectivity to ethylxylosides. This journal is
Method for preparing 5-ethoxyl methylfurfural
-
Paragraph 0024-0059, (2021/06/06)
The invention relates to a method for preparing 5-ethyoxyl methylfurfural, which comprises the following step: carrying out etherification reaction by taking 5-hydroxymethylfurfural as a reaction substrate and a sulfonic acid type high-molecular nitrogen-containing polymer as a catalyst to obtain the 5-ethyoxyl methylfurfural. The method has the advantages of mild reaction conditions, short reaction time, simple process, high catalytic etherification efficiency, few byproducts, high product selectivity and low production cost; the sulfonic acid type high-molecular nitrogen-containing polymer catalyst used in the invention has high activity; according to a preferable scheme, the catalyst is simple in preparation process and low in preparation cost.
Direct Conversion of 5-Hydroxymethylfurfural to Furanic Diether by Copper-Loaded Hierarchically Structured ZSM-5 Catalyst in a Fixed-Bed Reactor
Hu, Hualei,Xue, Tingting,Zhang, Zhenxin,Gan, Jiang,Chen, Liangqi,Zhang, Jian,Qu, Fengzuo,Cai, Weijie,Wang, Lei
, p. 3461 - 3469 (2021/06/01)
The highly-efficient conversion of 5-hydroxymethylfurfural (HMF) to 2,5-bis(ethoxymethyl)furan (BEMF) was achieved over the copper-loaded hierarchically structured ZSM-5 (Cu/HSZ) catalysts in the continuous fixed-bed reactor. The main reaction path for BEMF synthesis on the Cu/HSZ catalysts was confirmed as following: HMF was firstly hydrogenated to BHMF intermediates over metal sites and then the formed BHMF was etherified by acid sites. Benefiting from the ammonia evaporation (AE) method promoted the dispersion of copper and reduced the acidity, the Cu/HSZ-AE catalyst exhibited more excellent BEMF yield and stability than the catalyst prepared by conventional incipient-wetness impregnation (Cu/HSZ-IW). Indeed, the inactivation of Cu/HSZ-IW catalyst was mainly attributed to the deactivation of copper by carbon species deposition.
