- Synthesis of 5-ethoxymethylfurfural from fructose and inulin catalyzed by a magnetically recoverable acid catalyst
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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
- Zhang, Zehui,Wang, Yimei,Fang, Zhongfeng,Liu, Bing
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- Selective etherification of hydroxymethylfurfural to biofuel additives over Cs containing silicotungstic acid catalysts
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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.
- Raveendra,Rajasekhar,Srinivas,Sai Prasad,Lingaiah
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- Efficient production of 5-ethoxymethylfurfural from fructose by sulfonic mesostructured silica using DMSO as co-solvent
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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.
- Morales,Paniagua,Melero,Iglesias
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- Sulfonated graphene oxide as effective catalyst for conversion of 5-(hydroxymethyl)-2-furfural into biofuels
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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.
- Antunes, Margarida M.,Russo, Patrícia A.,Wiper, Paul V.,Veiga, Jacinto M.,Pillinger, Martyn,Mafra, Luís,Evtuguin, Dmitry V.,Pinna, Nicola,Valente, Anabela A.
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- One-pot conversions of lignocellulosic and algal biomass into liquid fuels
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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
- De, Sudipta,Dutta, Saikat,Saha, Basudeb
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- Lewis acidity induced heteropoly tungustate catalysts for the synthesis of 5-ethoxymethyl furfural from fructose and 5-hydroxymethylfurfural
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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.
- Kumari, P. Krishna,Rao, B. Srinivasa,Padmakar,Pasha, Nayeem,Lingaiah
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- Silica coated magnetic Fe3O4 nanoparticles supported phosphotungstic acid: A novel environmentally friendly catalyst for the synthesis of 5-ethoxymethylfurfural from 5-hydroxymethylfurfural and fructose
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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.
- Wang, Shuguo,Zhang, Zehui,Liu, Bing,Li, Jinlin
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- Production of biomass-derived furanic ethers and levulinate esters using heterogeneous acid catalysts
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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.
- 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.
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- Facile single-step conversion of macroalgal polymeric carbohydrates into biofuels
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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.
- Kim, Bora,Jeong, Jaewon,Shin, Seunghan,Lee, Dohoon,Kim, Sangyong,Yoon, Hyo-Jin,Cho, Jin Ku
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- Graphene oxide as a facile acid catalyst for the one-pot conversion of carbohydrates into 5-ethoxymethylfurfural
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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.
- Wang, Hongliang,Deng, Tiansheng,Wang, Yingxiong,Cui, Xiaojing,Qi, Yongqin,Mu, Xindong,Hou, Xianglin,Zhu, Yulei
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- One-step fabrication of carbonaceous solid acid derived from lignosulfonate for the synthesis of biobased furan derivatives
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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
- Yu, Xin,Peng, Lincai,Gao, Xueying,He, Liang,Chen, Keli
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- Catalytic etherification of 5-hydroxymethylfurfural into 5-ethoxymethyfurfural over sulfated bimetallic SO42?/Al-Zr/KIT-6, a Lewis/Br?nsted acid hybrid catalyst
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A series of mesoporous composites of SO42?/Al-Zr/KIT-6, with varied ratios of ZrO2 to Al2O3 and degrees of sulfation have been synthesized as an efficient, clean, facile and environmental-friendly nano-catalyst for the selective etherification of biomass-derived 5 hydroxymethylfurfural (HMF) to produce 5-ethoxymethylfurfural (EMF) as a biofuel candidate in a one pot process. Structure/property relationships of the catalyst have been determined and optimized in terms of EMF yield and HMF conversion. The resulting catalyst has been further tuned through tailored reaction conditions to produce an EMF yield of 89.8 % and HMF conversion of 99 %.
- Collins, Maurice N.,Hafizi, Hamid,Iqbal, Javed,Leahy, J. J.,Walker, Gavin
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- Direct transformation of carbohydrates to the biofuel 5-ethoxymethylfurfural by solid acid catalysts
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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.
- Li, Hu,Saravanamurugan, Shunmugavel,Yang, Song,Riisager, Anders
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- Mesoporous carbon-silica solid acid catalysts for producing useful bio-products within the sugar-platform of biorefineries
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Useful bio-products are obtainable via the catalytic conversion of biomass or derived intermediates as renewable carbon sources. In particular, furanic ethers and levulinate esters (denoted bioEs) have wide application profiles and can be synthesised via acid-catalysed reactions of intermediates such as fructose, 5-hydroxymethyl-2-furaldehyde (HMF) and furfuryl alcohol (FA) with ethanol. Solid acid catalysts are preferred for producing the bioEs with environmental benefits. Furthermore, the versatility of the catalyst in obtaining the bioEs from different intermediates is attractive for process economics, and in the case of porous catalysts, large pore sizes can be beneficial for operating in the kinetic regime. Carbon-based materials are attractive acid catalysts due to their modifiable surface, e.g. with relatively strong sulfonic acid groups (SO3H). Considering these aspects, here, we report the preparation of mesoporous (SO3H)-functionalised-carbon/ silica (C/S) composites with large pores and high amounts of acid sites (up to 2.3 mmol g-1), and their application as versatile solid acid catalysts for producing bioEs from fructose, HMF and FA. The mesoporous composites were prepared by activation of an organic compound deposited on the ordered mesoporous silicas MCF (mesostructured cellular foam) and SBA-15, where the organic compound (p-toluenesulfonic acid) acted simultaneously as the carbon and SO3H source. The atomic-level characterisation of the acid nature and strengths was performed by 31P solid-state NMR studies of an adsorbed base probe, in combination with FT-IR and XPS. Comparative catalytic studies showed that the C/S composites are interesting catalysts for obtaining bioEs in high yields, in comparison with classical solid acid catalysts such as sulfonic acid resin Amberlyst-15 and nanocrystalline (large pore) zeolite H-beta. the Partner Organisations 2014.
- Russo, Patricia A.,Antunes, Margarida M.,Neves, Patricia,Wiper, Paul V.,Fazio, Enza,Neri, Fortunato,Barreca, Francesco,Mafra, Luis,Pillinger, Martyn,Pinna, Nicola,Valente, Anabela A.
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- Synthesis of phenols from hydroxymethylfurfural (HMF)
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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.
- T?upova, Svetlana,Rominger, Frank,Rudolph, Matthias,Hashmi, A. Stephen K.
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- Three-step cascade over a single catalyst: Synthesis of 5-(ethoxymethyl)furfural from glucose over a hierarchical lamellar multi-functional zeolite catalyst
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The synthesis of hierarchical lamellar zeolites with a controlled meso-/microporous morphology and acidity is an expanding area of research interest for a wide range of applications. Here, we report a one-step synthesis of a hierarchical meso-/microporous
- Bai, Yuanyuan,Wei, Lu,Yang, Mengfei,Chen, Huiyong,Holdren, Scott,Zhu, Guanghui,Tran, Dat T.,Yao, Chunli,Sun, Runcang,Pan, Yanbo,Liu, Dongxia
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- Tungstophosphoric acid supported on mesoporouus niobiumoxophosphate: an efficient solid acid catalyst for etherification of 5-hydroxymethylfurfural to 5-ethoxymethylfurfural
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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.
- Kumari, P. Krishna,Rao, B. Srinivasa,Dhana Lakshmi,Sai Paramesh, N. Ruthwik,Sumana,Lingaiah
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- Efficient production of 5-hydroxymethylfurfural and alkyl levulinate from biomass carbohydrate using ionic liquid-based polyoxometalate salts
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Direct conversion of fructose into 5-hydroxymethylfurfural (HMF) and alkyl levulinate is achieved by making use of ionic liquid-based polyoxometalate salts (IL-POMs) as solid acid catalysts. Among these solid acids, phosphotungstic acid-derived IL-POM shows the highest catalytic performance in both the HMF and ethyl levulinate (EL) formation. A study for optimizing the reaction conditions such as the reaction time and the temperature has been performed. High HMF and EL yields of up to 99% and 82%, respectively, are obtained from fructose under the investigated conditions. Moreover, the generality of the catalyst is further demonstrated by processing representative di- and polysaccharides such as sucrose and inulin with good yields to HMF (76% from inulin and 48% from sucrose) and EL (67% from inulin and 45% from sucrose), again under mild conditions, thereby eliminating the separate hydrolysis step before the dehydration reaction. The catalyst recycling experiment indicates that the adsorption and accumulation of oligomeric products on the catalyst surface results in a partial deactivation of catalyst. The mechanism research reveals that a major pathway for EL formation involves a fructose-to-HMF transformation followed by HMF etherification and rehydration of HMF-ether to give EL. The research highlights an efficient, environment-friendly and recyclable solid acid for biomass valorization.
- Chen, Jinzhu,Zhao, Guoying,Chen, Limin
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- HMF etherification using NH4-exchanged zeolites
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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.
- Barbera, Katia,Lanzafame, Paola,Perathoner, Siglinda,Centi, Gabriele,Migliori, Massimo,Aloise, Alfredo,Giordano, Girolamo
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- Dual acidic titania carbocatalyst for cascade reaction of sugar to etherified fuel additives
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An inexpensive carbocatalyst containing Br?nsted acidic sulfonic acid group and Lewis acidic Ti4+ is found to be effective for cascade conversion of C6 sugar to 5-ethoxymethylfurfural (EMF) via sequential dehydration, and etherification reactions. HMF and fructose conversions at mild conditions achieved 91% and 64% EMF yields, respectively. The results indicate that the two acid sites interplay synergistically for high EMF yield and minimal ring-opened product ethyl levulinate (EL), another promising biofuel additive. Etherification of 2,5-bis(hydroxymethyl)furan (BHMF) with alcohols of varying carbon lengths formed alkoxymethylfurans (AMF) with high yields. The catalyst retained good activity upon recycling. The nature and strength of the acid sites are elucidated.
- Gupta, Dinesh,Saha, Basudeb
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- Direct versus acetalization routes in the reaction network of catalytic HMF etherification
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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).
- Lanzafame,Papanikolaou,Perathoner,Centi,Migliori,Catizzone,Aloise,Giordano
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- Dehydration of glucose to 5-hydroxymethylfurfural and 5-ethoxymethylfurfural by combining Lewis and Br?nsted acid
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In this work, glucose was transformed into 5-hydroxymethylfurfural (HMF) and 5-ethoxymethylfurfural (EMF) in the presence of AlCl3·6H2O and a Br?nsted solid acid catalyst (PTSA-POM). GVL (γ-valerolactone)-water and ethanol-water solvent systems were evaluated in the dehydration reaction of glucose into HMF and EMF, respectively. Water content and dosage of AlCl3·6H2O were examined in the conversion of glucose into HMF, and some valuable chlorides (FeCl3·6H2O, NiCl2·6H2O, CrCl3·6H2O etc.) were also used in contrast with AlCl3·6H2O. Some different organic solvents were added to the ethanol-water system to explore whether it would be beneficial to the generation of EMF. A high yield of HMF (60.7%) was obtained at 140 °C within 60 min in GVL-water (10:1) solvent system, and total yield 42.1% of EMF and HMF (30.6% EMF, 11.5% HMF) was achieved at 150 °C after 30 min in an ethanol-water (9:1) solvent system.
- Xin, Haosheng,Zhang, Tingwei,Li, Wenzhi,Su, Mingxue,Li, Song,Shao, Qun,Ma, Longlong
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- Selective conversion of fructose into 5-ethoxymethylfurfural over green catalyst
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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.].
- Maneechakr, Panya,Karnjanakom, Surachai
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- Scalable Synthesis of Acidic Mesostructured Silica–Carbon Nanocomposite Catalysts by Rotary Evaporation
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A practical and scalable synthesis for the mass production of well-ordered mesoporous silica–carbon composites by using a fast rotary-evaporation-induced self-assembly method in the absence of any additional support is presented.
- Zhong, Ruyi,Peng, Li,Iacobescu, Remus Ion,Pontikes, Yiannis,Shu, Riyang,Ma, Longlong,Sels, Bert F.
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- Ethanolysis of selected catalysis by functionalized acidic ionic liquids: An unexpected effect of ILs structural functionalization on selectivity phenomena
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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
- Nowakowska-Bogdan, Ewa,Nowicki, Janusz
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p. 1857 - 1866
(2022/02/05)
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- Direct Conversion of 5-Hydroxymethylfurfural to Furanic Diether by Copper-Loaded Hierarchically Structured ZSM-5 Catalyst in a Fixed-Bed Reactor
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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.
- Hu, Hualei,Xue, Tingting,Zhang, Zhenxin,Gan, Jiang,Chen, Liangqi,Zhang, Jian,Qu, Fengzuo,Cai, Weijie,Wang, Lei
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p. 3461 - 3469
(2021/06/01)
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- Efficient synthesis of 5-ethoxymethylfurfural from biomass-derived 5-hydroxymethylfurfural over sulfonated organic polymer catalyst
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Herein, we investigated catalytic potential of a functionalized porous organic polymer bearing sulfonic acid groups (PDVTA-SO3H) to the etherification of 5-hydroxymethylfurfural (HMF) to 5-ethoxymethylfurfural (EMF) under solvent-free conditions. The PDVTA-SO3H material was synthesized via post-synthetic sulfonation of the porous co-polymer poly-divinylbenzene-co-triallylamine by chlorosulfonic acid. The physicochemical properties of the PDVTA-SO3H were characterized by FT-IR, SEM, TG-DTG, and N2 adsorption isotherm techniques. PDVTA-SO3H had high specific surface area (591 m2 g-1) and high density of -SO3H group (2.1 mmol g-1). The reaction conditions were optimized via Box-Behnken response surface methodology. Under the optimized conditions, the PDVTA-SO3H catalyst exhibited efficient catalytic activity with 99.8% HMF conversion and 87.5% EMF yield within 30 min at 110 °C. The used PDVTA-SO3H catalyst was readily recovered by filtration and remained active in recycle runs.
- Xiang, Yanping,Wen, Sha,Tian, Yi,Zhao, Kangyu,Guo, Dongwen,Cheng, Feng,Xu, Qiong,Liu, Xianxiang,Yin, Dulin
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p. 3585 - 3595
(2021/02/03)
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- Sulfonic acid-functionalized PCP(Cr) catalysts with Cr3+and -SO3H sites for 5-ethoxymethylfurfural production from glucose
-
5-Ethoxymethylfurfural (EMF) has been identified as a potential biofuel and fuel additive, for which the production from glucose (the most abundant and inexpensive monosaccharide) in a one-step process would be highly desirable. Here, the synthesis of sulfonic acid-functionalized porous coordination polymers (PCPs) and their application as catalysts for EMF synthesis are reported. PCP(Cr)-BA (PCP material with Cr3+ ions and H2BDC-SO3H linkers) and PCP(Cr)-NA (PCP material with Cr3+ ions and H2NDC(SO3H)2 linkers) materials containing both Cr3+ sites and Br?nsted-acidic -SO3H sites were prepared. The morphology, pore structure, acidity, chemical composition, and thermal stability of the two functionalized PCP(Cr) catalysts were analyzed by systematic characterization. The catalysts featured a porous morphology and dual Cr3+ and -SO3H sites, which enabled the cascade conversion of glucose to EMF. PCP(Cr)-BA exhibited higher performance than PCP(Cr)-NA with an EMF yield of 23.1% in the conversion of glucose at 140 °C after 22 h in an ethanol/water system. In addition, the as-prepared catalyst exhibited a high stability in the current catalytic system for EMF production from glucose with a constant catalytic activity in a four-run recycling test without an intermediate regeneration step. This journal is
- Liu, Yuting,Sun, Ruijun,Yi, Simin,Zhang, Luxin
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p. 33969 - 33979
(2021/12/08)
-
- Method for preparing 5-ethoxyl methylfurfural
-
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.
- -
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Paragraph 0024-0059
(2021/06/06)
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- Etherification of biomass-derived furanyl alcohols with aliphatic alcohols over silica-supported nickel phosphide catalysts: Effect of surplus P species on the acidity
-
The acidity of nickel phosphide (Ni2P) catalysts plays a crucial role in producing a desired hydrodeoxygenation molecule from biomass-derived substrates; yet, it has never been explored in acid-catalyzed reactions. Herein, we demonstrated the activity of silica-supported Ni2P catalyst prepared with the nominal P/Ni ratio of 2 (Ni2P/SiO2-2P) in the etherification of furanyl alcohols (particularly, 5-(hydroxymethyl)furfural) with aliphatic alcohols including ethanol. By comparing the characteristics of Ni/SiO2, PxOy/SiO2, and Ni2P/SiO2-xP (x = 0.5 and 1), Ni2P/SiO2-2P was revealed to contain the Br?nsted and Lewis acid sites of which both contributed to the etherification reaction. Notably, the Br?nsted acidity was associated with the surplus P species added to produce the Ni2P phase. Consequently, supported Ni2P catalysts can work in acid-catalyzed reactions if an adequate ratio of Br?nsted to Lewis acid sites is provided by the amount of the surplus P species determined by adjusting the P/Ni ratio.
- Kim, Jinsung,Shin, Mi,Suh, Young-Woong
-
-
- A PROCESS FOR THE PREPARATION OF PLATFORM CHEMICALS FROM SUGAR USING ACID CATALYST
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The present invention relates to a process for the preparation of value added chemicals such as ethyl levulinate from a glucose or other sugars catalyzed by a mixture of a Lewis and a Bronsted acid catalyst.
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Page/Page column 8
(2020/07/31)
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- Importance of the synergistic effects between cobalt sulfate and tetrahydrofuran for selective production of 5-hydroxymethylfurfural from carbohydrates
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In this study, an effective catalytic system (CoSO4·7H2O/THF) for selective conversion of fructose to 5-hydroxymethylfurfural (HMF; yield: 88%) was developed. The synergistic effects among Co2+, SO42-, crystal water and tetrahydrofuran (THF) were crucial for achieving selective dehydration of fructose to HMF. Co2+ worked as a Lewis acid for catalyzing mainly dehydration of fructose to HMF but not the further decomposition of HMF to levulinic acid. THF could help to retain HMF while CoSO4 could coordinate with HMF, enhancing the thermal stability of HMF in THF. The crystal water in cobalt sulfate could help to coordinate with fructose, which facilitated the conversion of fructose via dehydration reactions. The CoSO4·7H2O/THF catalytic system could also catalyze the conversion of inulin and cellulose into HMF. The main advantages of the CoSO4·7H2O/THF catalytic system are the low cost, the easy recycling of the CoSO4·7H2O catalyst and the easy separation of HMF from volatile THF.
- Dong, Dehua,Hu, Xun,Li, Qingyin,Li, Xueli,Shao, Yuewen,Sun, Kai,Wang, Yi,Ye, Zhengmao,Zhang, Lijun,Zhang, Shu
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p. 2293 - 2302
(2020/04/20)
-
- Etherification of 5-hydroxymethylfurfural using a heteropolyacid supported on a silica matrix
-
In this work, Preyssler-type heteropolyacids and their silica-included counterparts were employed in the etherification reaction of HMF and n-BuOH. Materials were synthesized with a Preyssler acid load of 12.5percent w/w using the sol-gel technique, which improved surface areas and modulated their acid strength. Prepared materials were used as heterogeneous solid acid catalysts in the selective etherification of 5-hydroxymethylfurfural (HMF) to 5-butoxymethylfurfural (5BMF). The high catalytic performance of the bulk Preyssler acids is related to their high acid strength, while selectivity related to the decrease in acidity by the inclusion effects. Different reaction parameters were optimized, with PWMo(12.5percent)&at;SiO2 exhibited the highest catalytic activity with 89percent of HMF conversion and 73percent of 5BMF selectivity. The catalyst is reusable up to five cycles without noticeable decrease in selectivity.
- Casella, Mónica,Lick, Daniela I.,Luque, Rafael,Martínez, José J.,Portilla-Zu?iga, Omar M.,Romanelli, Gustavo P.,Sathicq, ángel G.
-
-
- FeVO4 decorated –SO3H functionalized polyaniline for direct conversion of sucrose to 2,5-diformylfuran & 5-ethoxymethylfurfural and selective oxidation reaction
-
In this study, a multi-functional catalyst, FeVO4 supported –SO3H functionalized polyaniline is prepared. First FeVO4 supported polyaniline is prepared. Then the resultant material is sulfonated using chlorosulphonic acid to obtain FeVO4 supported –SO3H functionalized polyaniline. This multi-functional catalyst exhibits excellent activity in the synthesis of 5-hydroxymethylfurfural from sucrose and oxidation of a wide range of aromatic and aliphatic alcohols. Further, the catalyst exhibits very good activity in the one-pot direct conversion of sucrose/fructose to 2,5-diformylfuran (DFF) and 5-ethoxymethylfurfural (EMF). This catalytic process involves the economical sucrose as a reactant and economical multi-functional catalyst based on polyaniline. In this one-pot, two-step process, -SO3H functionalized polyaniline is used in the first step for the conversion of sucrose to 5-hydroxymethylfurfural (HMF) followed by selective oxidation of HMF to DFF using FeVO4 sites present in the multi-functional catalyst. Moreover, acidic sites present in the multi-functional catalyst are suitable for the conversion of sucrose/fructose/HMF to EMF. Furthermore, molecular oxygen (1 atmosphere, 10 ml/min) is used as an eco-friendly and economical oxidant for the selective oxidation of a wide range of aromatic and aliphatic alcohols to aldehydes. The multi-functional catalyst presented here has been easily separated and recycled that make the process sustainable and economical for commercial perspectives.
- Kumar, Abhinav,Srivastava, Rajendra
-
-
- Topotactic transformation of homogeneous phosphotungastomolybdic acid materials to heterogeneous solid acid catalyst for carbohydrate conversion to alkyl methylfurfural and alkyl levulinate
-
The strong interaction of higher transition metal oxides with inorganic non-metals can be promising for generating highly acidic three-dimensional materials by design. A comprehensive controlled acidity of heteropolyacid-like catalyst and interpretation of the microstructure and mechanism of the formation of a versatile heterogeneous solid acid catalyst, HPW4Mo10Ox has been heterogenized by biomass-derived cystine as organic linkers to control the acidity of as-synthesized materials, which have greater acidity and complexity in separation from the reaction mixture. The new and unique results obtained in catalysis done in biphasic reaction. Cystine binds to the surface of HPW4Mo10Ox, and the topotactic transition occurred, change the morphology and lattice parameter. We described here a sustainable transformation of highly acidic (0.84 mmol g-1) heteropoly acid (HPW4Mo10Ox) to cystine anchored on the active surface of the heteropoly acid and controlled the acidity (0.63 mmol g-1) and heterogenized the materials. As synthesized materials have been showing that for the direct formation of alkyl levulinate and furanics intermediate from carbohydrates. HPW4Mo10Ox and HPW4Mo10Ox-Cys, act as acidic catalyst, and catalyse the mono- and disaccharides that are dissolved in primary and secondary alcohols to alkyl levulinate (AL) and alkyl methylfurfural at 170 °C under microwave irradiation with glucose as the substrate, AL yield reaches 62% with 84.95% selectivity. The catalyst can be easily recovered by filtration and minimum five times reused after calcination without any substantial change in the product selectivity. The analytical analysis of as-synthesis materials done by NH3-TPD, BET, XRD, FESEM, TEM, HRTEM, FTIR, ATR, TGA, DTA to stabilized the morphology and acidity controlled mechanism.
- Gupta, Dinesh,Mukesh, Chandrakant,Pant, Kamal K.
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p. 705 - 718
(2020/01/23)
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- HReO4 as highly efficient and selective catalyst for the conversion of carbohydrates into value added chemicals
-
This work describes the first catalyst (HReO4) that promotes the efficient and selective conversion of several carbohydrates into four compounds, ethyl levulinate (EL), 5-ethoxymethylfurfural (EMF), 5-hydroxymethylfurfural (HMF) and levulinic acid (LA), through a one-pot reaction strategy adjusting the reaction conditions. The reaction of fructose in ethanol at 160 °C gave EL in 80% yield after 16 h and in a mixture of ethanol/THF at 140 °C produced EMF in 73% yield after 1 h. HMF and LA can also be obtained selectively with 100% yield from fructose at 140 °C after 1 h, in DMSO or 1,4-dioxane, respectively. EL, HMF, LA and EMF were also produced in moderate to good yields from other carbohydrates such as inulin and sucrose. The catalyst HReO4 can be used in gram scale for the production of EL, EMF, HMF and LA with good yields and in at least 8 catalytic cycles on the conversion of fructose into EL with no significant reduction in its activity.
- Bernardo, Joana R.,Oliveira, M. Concei??o,Fernandes, Ana C.
-
-
- Highly selective synthesis under benign reaction conditions of furfural dialkyl acetal using SnCl2 as a recyclable catalyst
-
A new and mild route of furfural acetalization with various alkyl alcohols catalyzed by cheap and simple SnCl2 has been developed. This process consists of the conversion of furfural to alkyl acetals under benign and mild reaction conditions (i.e., room temperature, without solvent, recyclable catalyst), achieving a very good selectivity (97-100%) and almost complete conversion of furfural. Various tin(ii) salts were used as catalysts for the upgrading of furfural to alkyl acetal in an alcoholic solution at room temperature. SnCl2 was the most active and selective catalyst toward furfural diethyl acetal. Tin(ii) chloride is a commercially available and water tolerant Lewis acid and was demonstrated to be an efficient and recyclable catalyst for the synthesis of furfural alkyl acetal. The effects of the main variables of the reaction such as the catalyst load, temperature, reaction time and alcohol nature were assessed. SnCl2 was easily recovered and reused without loss of activity and selectivity.
- Da Silva, Márcio José,Teixeira, Milena Galdino,Natalino, Ricardo
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p. 8606 - 8612
(2019/06/14)
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- Fructose Transformations in Ethanol using Carbon Supported Polyoxometalate Acidic Solids for 5-Ethoxymethylfurfural Production
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A series of carbon supported polyoxometalates have been prepared and studied as acid catalysts for the fructose dehydration. The catalytic supports, microporous activated carbon (AC, SBET=1190 m2/g) and high surface area graphite (HSAG, SBET=400 m2/g), were loaded with 15 wt% of polyoxometalates: phosphotungstic acid (TPA) or tungstosilicic acid (STA). The four resulting catalysts were tested in the fructose reaction at moderate temperature 140 °C, using water and ethanol solvents. Catalytic properties have been compared with those of an acidic resin, Amberlyst 15. As relevant findings the specific interactions of carbon supports and polyoxometalates let the inhibition of active phase lixiviation. An improved catalyst (STA-HSAG) in terms of selectivity to valuable products (ethoxymethylfurfural and ethyl levulinate) and high specific catalytic activity using ethanol as solvent has been developed. This catalyst can be reused after regeneration by washing with organic solvents.
- García-Bosch, Nadia,Bachiller-Baeza, Belén,Rodríguez-Ramos, Inmaculada,Guerrero-Ruiz, Antonio
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p. 3746 - 3753
(2018/08/07)
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- Design of Ordered Mesoporous Sulfonic Acid Functionalized ZrO2/organosilica Bifunctional Catalysts for Direct Catalytic Conversion of Glucose to Ethyl Levulinate
-
Ordered mesoporous sulfonic acid functionalized ZrO2/organosilica catalysts (SO42?/ZrO2-PMO-SO3H) bearing tunable Br?nsted, and Lewis acid site distributions were prepared by a P123-directed sol-gel co-condensation route followed by ClSO3H functionalization. As-prepared catalysts were applied in the conversion of glucose to ethyl levulinate in ethanol medium. The SO42?/ZrO2-PMO-SO3H-catalyzed target reaction followed a glucose-ethyl glucoside-ethyl fructoside-5-ethoxymethylfurfural-ethyl levulinate pathway dominated by the synergistic effect of the super strong Br?nsted acidity, and moderate Lewis acidity of the catalysts. Additionally, by combining the advantages of the considerably high Br?nsted (696 μeq g?1), Lewis acid site density (703 μeq g?1), optimal Br?nsted/Lewis molar ratio (0.99), and excellent porosity properties, the SO42?/ZrO2-PMO-SO3H1.0 obtained at an initial Si/Zr molar ratio of 1.0 exhibited the highest ethyl levulinate yield (42.3 %) among the various tested catalysts. Moreover, the SO42?/ZrO2-PMO-SO3H can be reused three times without obvious changes in activity, morphology, and chemical structure.
- Song, Daiyu,Zhang, Qingqing,Sun, Yingnan,Zhang, Panpan,Guo, Yi-Hang,Hu, Jiang-Lei
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p. 4967 - 4979
(2018/10/02)
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- SWEET TASTE MODULATORS
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Sweet taste modulators for enhancing sweetness of an oral consumer product having a sweetener are described. The sweet taste modulators include 5-ethoxymethyl-2-furaldehyde, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid and 3,4,5-trihydroxybenzoic acid, syringic aldehyde, sinapic aldehyde, ester of 5-hydroxymethylfurfural and vanillic acid, 4-hydrozybenzaldehyde, and 5-methoxymethylfurfural. A method of making 5-ethoxymethyl-2-furaldehyde and a method of making an oral consumer product are also described.
- -
-
Paragraph 0071-0075
(2018/11/02)
-
- PRODRUG AND PROTECTED FORMS OF 5-HYDROXYMETHYLFURFURANAL (5-HMF) AND ITS DERIVATIVES
-
Prodrugs and derivatives of 5-hydoxymethyl-2-furfural (5-HMF) with protected or modified aldehyde and/or alcohol moieties are provided. The prodrugs or derivatives exhibit increased bioavailability, e.g. due to having extended half-lives in circulation. The drugs are therefore administered i) at lower doses and/or ii) less frequently than 5-HMF, while still maintaining the beneficial therapeutic effects of 5-HMF.
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Page/Page column 35
(2018/02/27)
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- Facile isomerization of glucose into fructose using anion-exchange resins in organic solvents and application to direct conversion of glucose into furan compounds
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The facile isomerization of glucose into fructose has been developed using commercially available anion-exchange resins (AERs) in organic solvents. Following extensive screening for the amount and type of AERs, solvents and reaction time, glucose was transformed into fructose in yields of up to 50% using Amberlite A-26 with macroreticular morphology and tertiary amine functionality in a protic solvent (ethanol). AERs could be used five times without a significant loss of activity. This isomerization method could be applied to the direct conversion of glucose into furan compounds by integrating the dehydration of fructose with cation-exchange resins.
- Mun, Dasom,Huynh, Nhan Thanh Thien,Shin, Seunghan,Kim, Yong Jin,Kim, Sangyong,Shul, Yong-Gun,Cho, Jin Ku
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p. 5495 - 5506
(2017/09/23)
-
- Design, Synthesis, and Biological Evaluation of Ester and Ether Derivatives of Antisickling Agent 5-HMF for the Treatment of Sickle Cell Disease
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Candidate drugs to counter intracellular polymerization of deoxygenated sickle hemoglobin (Hb S) continue to represent a promising approach to mitigating the primary cause of the pathophysiology associated with sickle cell disease (SCD). One such compound is the naturally occurring antisickling agent, 5-hydroxymethyl-2-furfural (5-HMF), which has been studied in the clinic for the treatment of SCD. As part of our efforts to develop novel efficacious drugs with improved pharmacologic properties, we structurally modified 5-HMF into 12 ether and ester derivatives. The choice of 5-HMF as a pharmacophore was influenced by a combination of its demonstrated attractive hemoglobin modifying and antisickling properties, well-known safety profiles, and its reported nontoxic major metabolites. The derivatives were investigated for their time- and/or dose-dependent effects on important antisickling parameters, such as modification of hemoglobin, corresponding changes in oxygen affinity, and inhibition of red blood cell sickling. The novel test compounds bound and modified Hb and concomitantly increased the protein affinity for oxygen. Five of the derivatives exhibited 1.5- to 4.0-fold higher antisickling effects than 5-HMF. The binding mode of the compounds with Hb was confirmed by X-ray crystallography and, in part, helps explain their observed biochemical properties. Our findings, in addition to the potential therapeutic application, provide valuable insights and potential guidance for further modifications of these (and similar) compounds to enhance their pharmacologic properties.
- Xu, Guoyan G.,Pagare, Piyusha P.,Ghatge, Mohini S.,Safo, Ronni P.,Gazi, Aheema,Chen, Qiukan,David, Tanya,Alabbas, Alhumaidi B.,Musayev, Faik N.,Venitz, Jürgen,Zhang, Yan,Safo, Martin K.,Abdulmalik, Osheiza
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p. 3499 - 3511
(2017/10/11)
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- Cascade Reductive Etherification of Bioderived Aldehydes over Zr-Based Catalysts
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An efficient one-pot catalytic cascade sequence has been developed for the production of value-added ethers from bioderived aldehydes. Etherification of 5-(hydroxymethyl)furfural with different aliphatic alcohols over acidic Zr–montmorillonite (Zr-Mont) catalyst produced a mixture of 5-(alkoxymethyl)furfural and 2-(dialkoxymethyl)-5-(alkoxymethyl)furan. The latter was selectively converted back into 5-(alkoxymethyl)furfural by treating it with water over the same catalyst. The synthesis of 2,5-bis(alkoxymethyl)furan was achieved through a cascade sequence involving etherification, transfer hydrogenation, and re-etherification over a combination of acidic Zr-Mont and the charge-transfer hydrogenation catalyst [ZrO(OH)2]. This catalyst combination was further explored for the cascade conversion of 2-furfuraldehyde into 2-(alkoxymethyl)furan. The scope of this strategy was then extended for the reductive etherification of lignin-derived arylaldehydes to obtain the respective benzyl ethers in >80 % yield. Additionally, the mixture of Zr-Mont and ZrO(OH)2 does not undergo mutual destruction, which was proved by recycling experiments and XRD analysis. Both the catalysts were thoroughly characterized using BET, temperature-programmed desorption of NH3 and CO2, pyridine-FTIR, XRD, inductively coupled plasma optical emission spectroscopy, and X-ray photoelectron spectroscopy techniques.
- Shinde, Suhas,Rode, Chandrashekhar
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p. 4090 - 4101
(2017/10/18)
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- A continuous flow process for the production of 2,5-dimethylfuran from fructose using (non-noble metal based) heterogeneous catalysis
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The abundant carbohydrate fructose is converted into two biofuel molecules, namely 2,5-dimethylfuran (DMF) and ethyl levulinate (EL) in a simple cascade flow reactor. With an overall yield of 85% (38.5% of 2,5-dimethylfuran and 47% of ethyl levulinate), the main remainder is unconverted fructose. The two column flow reactor set-up enables the adjustment of temperatures and reaction times in such a way that the reactive intermediate hydroxymethylfurfural (5-HMF) is generated in optimal yields and converted into the stable DMF immediately. The process is so simple and fast (20 min) that economic and sustainable production of these fuels and platform chemicals can be envisioned. A remaining minor char formation is regarded to be the major problem which has to be addressed by catalyst development.
- Braun, Max,Antonietti, Markus
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p. 3813 - 3819
(2017/08/26)
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- Selective glucose conversion to 5-hydroxymethylfurfural (5-HMF) instead of levulinic acid with MIL-101Cr MOF-derivatives
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The catalytic conversion of glucose to 5-hydroxymethylfurfural (5-HMF) is highly desirable, but the 5-HMF yield obtained using heterogeneous catalysts is still low compared to homogeneous catalysts, and the mechanism is not elucidated completely. In addition, the isolation and purification of 5-HMF still present a challenge as degradation reactions take place and side products form. The formation of 5-HMF from glucose has been reported using several solid acid catalysts; still metal-organic framework (MOF) catalysts could, so far, catalyze the cascade reaction of glucose to 5-HMF only in low yields of less than 16%. Glucose conversion using MOFs is little investigated and here sulfonated MIL-101Cr (MIL-SO3H) was found to achieve 29% conversion of glucose to 5-HMF after 24 h in a THF:H2O (v:v 39:1) mixture. The conversion of maltose resulted in 50% 5-HMF yield (saccharide solutions were 5 wt%). When the reaction was carried out in pure THF using MIL catalysts no product was formed, revealing the indispensability of water for the glucose-to-5-HMF conversion. Importantly, MIL-SO3H preferentially leads to 5-HMF over levulinic acid (molar ratio 1:0.3), while the catalysts Amberlyst-15 and sulfuric acid form mostly levulinic acid in 5-HMF to levulinic acids ratios of 1:3 and 1:10, respectively. At the same time, MIL-NO2 is the most selective, yielding only 5-HMF and showing no formation of levulinic acid. Using 5-HMF as a substrate did not result in any conversion to levulinic acid in the presence of MIL-SO3H, thereby ruling out the catalytic formation of levulinic acid from 5-HMF. Catalyst recycle experiments showed that MIL-SO3H stays porous and crystalline, but becomes deactivated through fouling by humin formation. With the use of ethanol as an alternative reaction medium, the formation of insoluble humins could be prevented, but the yield of 5-HMF and 5-ethyl-HMF decreased.
- Herbst, Annika,Janiak, Christoph
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p. 7958 - 7967
(2016/09/09)
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- Application of glucose derived magnetic solid acid for etherification of 5-HMF to 5-EMF, dehydration of sorbitol to isosorbide, and esterification of fatty acids
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In this study, the catalytic activity of Glu-Fe3O4-SO3H was evaluated for three acid catalyzed reactions: etherification of 5-hydroxymethylfurfural (5-HMF) to 5-ethoxymethylfurfural (5-EMF) in ethanol, dehydration of sorbitol to isosorbide, and esterification of fatty acids with good yields and selectivity. Moreover, the catalyst can be easily separated from the reaction with an external magnetic force and reused at least five times without a significant decrease in catalytic activity.
- Thombal, Raju S.,Jadhav, Vrushali H.
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supporting information
p. 4398 - 4400
(2016/09/13)
-
- A fructose-based biomass catalytic conversion systems furan derivatives
-
A method for preparing furan derivatives by catalytic conversion of fructose-based biomass is characterized by: taking biomass such as fructose, cane sugar, inulin and the like as raw materials, taking low-boiling-point alcohols comprising aliphatic alcohols or alicyclic alcohols all with six or less than six carbon atoms as a solvent, and under the effect of a catalyst, performing reactions comprising hydrolysis, dehydration, etherfication and the like for coupling so as to obtain furan derivatives such as 5-alkoxymethyl furfural, levulinate esters, 5-hydroxymethylfurfural and the like. The method has the advantages of high raw material utilization rate, high in-situ coupling efficiency in the dehydration and etherfication reactions, and easily separated and purified system.
- -
-
Paragraph 0016
(2017/02/09)
-
- The role of oxide location in HMF etherification with ethanol over sulfated ZrO2 supported on SBA-15
-
The etherification of 5-hydroxymethyl-2-furfural (HMF) over ZrO2 and sulfated ZrO2-SBA-15 was chosen as a case study to analyze (i) the quantitative relationship between the concentration of Lewis and Bronsted acid sites and the catalytic behavior in the above reaction, which is also of industrial relevance for the production of biodiesel additives, and (ii) how the location of zirconia nanoparticles inside or outside the mesoporous channels of SBA-15 could significantly influence the specific reactivity in this reaction, both before and after sulfation. Depending on the loading of zirconia (about 10 or 35 wt%), the characterization data by different techniques (TEM, XRD, BET, Dr-UV-vis, and XPS) agree in indicating that zirconia is located predominantly outside the mesoporous channels as small zirconia nanoparticles for the lower loading, and predominantly inside the mesoporous channels for the higher loading. The concentration of medium-strong Lewis and Bronsted acid sites were determined by pyridine chemisorption monitored by IR spectroscopy. While the concentration of Bronsted acid sites (formed after sulfation) is linearly dependent on the amount of zirconia in SBA-15, a marked deviation is observed for Lewis acid sites. The same conclusion was derived from analysis of the dependence of the catalytic activity in Lewis- or Bronsted-acid-site-promoted reactions. The analysis of these results indicated that the characteristics of the zirconia nanoparticles deposited outside or inside the mesoporous silica channels differ in terms of acid features and in turn of catalytic reactivity.
- Barbera,Lanzafame,Pistone,Millesi,Malandrino,Gulino,Perathoner,Centi
-
-
- A continuous flow strategy for the coupled transfer hydrogenation and etherification of 5-(hydroxymethyl)furfural using lewis acid zeolites
-
Hf-, Zr- and Sn-Beta zeolites effectively catalyze the coupled transfer hydrogenation and etherification of 5-(hydroxymethyl)furfural with primary and secondary alcohols into 2,5-bis(alkoxymethyl)furans, thus making it possible to generate renewable fuel
- Lewis, Jennifer D.,Van De Vyver, Stijn,Crisci, Anthony J.,Gunther, William R.,Michaelis, Vladimir K.,Griffin, Robert G.,Roman-Leshkov, Yuriy
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p. 2255 - 2265
(2014/11/08)
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- Cascade of liquid-phase catalytic transfer hydrogenation and etherification of 5-hydroxymethylfurfural to potential biodiesel components over Lewis acid zeolites
-
We report a one-step process for the production of diesel fuel from biomass-derived 5-hydroxymethylfurfural (HMF). The reaction proceeds through the sequential transfer hydrogenation and etherification of HMF to 2,5-bis(alkoxymethyl)furan, a potential biodiesel additive, catalyzed by a Lewis acid zeolite, such as Sn-Beta or Zr-Beta. An alcohol is used as a hydrogen donor and as a reactant in etherification. This cascade reaction can selectively produce high yields of the biodiesel additive (>80 % yield) from HMF with the Sn-Beta catalyst and secondary alcohols, such as 2-propanol and 2-butanol. Diesel addiction: Biomass-derived 5-hydroxymethylfurfural (HMF) is converted to 2,5-bis(alkoxymethyl)furan, a potential biodiesel additive, through sequential transfer hydrogenation and etherification reactions catalyzed by a Lewis acid zeolite, such as Sn-Beta or Zr-Beta. Sn-Beta selectively produces high yields of the biodiesel additive (>80 % yield) with secondary alcohols, such as 2-propanol and 2-butanol, as hydrogen donors and as etherification agents. Copyright
- Jae, Jungho,Mahmoud, Eyas,Lobo, Raul F.,Vlachos, Dionisios G.
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p. 508 - 513
(2014/03/21)
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- Heterogeneous acidic TiO2 nanoparticles for efficient conversion of biomass derived carbohydrates
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Selective conversion of biomass derived carbohydrates into fine chemicals is of great significance for the replacement of petroleum feedstocks and the reduction of environmental impacts. Levulinic acid, 5-hydroxymethyl furfural (HMF) and their derivatives are recognized as important precursor candidates in a variety of different areas. In this study, the synthesis, characterization, and catalytic activity of acidic TiO2 nanoparticles in the conversion of biomass derived carbohydrates were explored. This catalyst was found to be highly effective for selective conversion to value-added products. The nanoparticles exhibited superior activity and selectivity towards methyl levulinate from fructose in comparison to current commercial catalysts. The conversion of fructose to methyl levulinate was achieved with 80% yield and high selectivity (up to 80%). Additionally, conversions of disaccharides and polysaccharides were studied. Further, the production of versatile valuable products such as levulinic esters, HMF, and HMF-derived ethers was demonstrated using the TiO2 nano-sized catalysts in different solvent systems.
- Kuo, Chung-Hao,Poyraz, Altug S.,Jin, Lei,Meng, Yongtao,Pahalagedara, Lakshitha,Chen, Sheng-Yu,Kriz, David A.,Guild, Curtis,Gudz, Anton,Suib, Steven L.
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p. 785 - 791
(2014/02/14)
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- Preparation of potential biofuel 5-ethoxymethylfurfural and other 5-alkoxymethylfurfurals in the presence of oil shale ash
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5-Ethoxymethylfurfural (EMF) can be prepared from the corresponding halomethylfurfural and absolute ethanol in good yield. The use of significantly more affordable 96% ethanol results in formation of levulinic acid or its ester in considerable amount (up to 16%), which is difficult to separate from the desired EMF. In the present study we report that the addition of oil shale ash prevents the hydrolysis of the furan ring and enables the use of 96% ethanol with great success. The developed procedure is applicable to a wide range of aqueous alcohols, is operationally simple and utilizes an inexpensive basic ash, which is deposited in millions of tons per year. Notably, the basicity of the ash is decreased during the process, making its deposits less hazardous to the environment.
- Viil, Indrek,Bredihhin, Aleksei,Maeeorg, Uno,Vares, Lauri
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p. 5689 - 5693
(2014/01/23)
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- METHOD OF PREPARING FURFURAL COMPOUNDS
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Provided is a two-step method of producing a compound of chemical formula 1 in the presence of an alcohol solvent and a Group 3B metal catalyst or a salt thereof, comprising a first step comprising alkylation or isomerization of an aldohexose-containing substrate to obtain an intermediate, and a second step comprising dehydration of the intermediate to produce a compound of chemical formula 1. Preferably, additional solvent and/or catalyst are not added in the second step.
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Paragraph 0064; 0065; 0070
(2014/05/20)
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- METHOD FOR PRODUCING 5-HYDROXYMETHYL-2-FURFURAL OR ALKYL ETHER DERIVATIVES THEREOF USING AN ION EXCHANGE RESIN IN THE PRESENCE OF AN ORGANIC SOLVENT
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The present invention relates to a method for producing a furan-based compound using an ion exchange resin in the presence of an organic solvent. In the method for producing a furan-based compound according to the present invention, a furan-based compound is made from an aldose-type hexose compound in the presence of an organic solvent by using an anion exchange resin and a cation exchange resin. Thus, the aldose-type hexose compound obtained from biomass by simultaneously or consecutively using the anion/cation exchange resins as catalysts can be made into 5-hydroxymethyl-2-furfural (HMF) or alkyl ether derivatives thereof such as 5-alkoxymethyl-2-furfural (AMF) without using an expensive reagent. Also, since the selection of an organic solvent is not limitative and a heterogeneous catalyst can be used, separation and purification is easy and chemically stable AMF can be directly obtained. Further, the conversion efficiency of the aldose-type hexose compound is excellent, and the hexose compound can be used at a high concentration.
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Paragraph 0095-0096
(2014/09/03)
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