- Catalytic Conversions in Water: a Novel Carbonylation Reaction Catalysed by Palladium Trisulfonated Triphenylphosphine Complexes
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The renewable basic chemical 5-hydroxymethylfurfural (HMF) is selectively carbonylated to the new compound 5-formylfuran-2-acetic acid using a water-soluble palladium complex of trisulfonated triphenylphosphine as the catalyst in an acidic aqueous medium at 70 deg C and 5 bar CO pressure; when hydrogen iodide is the acid component, the reaction follows a different course and HMF is selectively reduced to 5-methylfurfural.
- Papadogianakis, Georgios,Maat, Leendert,Sheldon, Roger A.
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- One-pot synthesis of furans from various saccharides using a combination of solid acid and base catalysts
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One-pot synthesis of furans from various saccharides such as arabinose, rhamnose, and lactose were performed over solid acid and base catalysts. The combination of Amberlyst-15 and hydrotalcite catalysts showed successful activity for corresponding furans formation such as 2-furaldehyde (furfural), 5-hydroxymethyl-2-furaldehyde (HMF), and 5-methyl- 2-furaldehyde (MF) via one-pot synthesis including isomerization and dehydration reactions. Moreover, the acidbase pair catalysts were also found to display excellent activity for the transformation from mixed-sources of sugars to furans. It was indicated that the isomerization of saccharides and successive dehydration in the one-pot synthesis of furans will be a great approach in a biorefinery.
- Tuteja, Jaya,Nishimura, Shun,Ebitani, Kohki
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- Green catalytic synthesis of 5-methylfurfural by selective hydrogenolysis of 5-hydroxymethylfurfural over size-controlled Pd nanoparticle catalysts
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A green approach for the conversion of 5-(hydroxymethyl)furfural (HMF) to 5-methylfurfural (MF) by using size-controlled palladium catalysts has been developed. Palladium nanoparticles (Pd NPs) with various sizes supported on activated carbon were prepared with polyvinylpyrrolidone (PVP) as the capping agent. The reaction results showed that all the PVP-assisted Pd catalysts achieved high selectivity whilst the hydrogenation ability of Pd NPs could be rationally tuned by varying the mole ratio of Pd/PVP. 2.5% Pd-PVP/C (1:2) presented a satisfactory activity with 80% MF yield and 90% selectivity. The reaction kinetics study showed that the transformation of HMF into MF over bifunctional PVP-assisted Pd NPs underwent an acid-catalyzed esterification followed by a Pd-catalyzed hydrogenolysis procedure. The role of formic acid in the transformation is not only as a hydrogen-donating agent but also as a reactant to form the key intermediate. This work provides a novel and environmentally-friendly method for the selective hydrogenation of bio-based HMF to MF.
- Sun, Guohan,An, Jiahuan,Hu, Hong,Li, Changzhi,Zuo, Songlin,Xia, Haian
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- Novel pathways to 2,5-Dimethylfuran via biomass-derived 5-(chloromethyl)furfural
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2,5-Dimethylfuran (DMF) is one of the most actively pursued biomass-derived chemicals due to the fact that it can serve both as a biofuel and an intermediate for drop-in terephthalate polymers. DMF can be accessed via catalytic hydrogenation of 5-(hydroxymethyl)furfural (HMF), but the difficult accessibility of HMF from cellulosic biomass is a major impediment to the commercial development of such a process. Alternatively, 5-(chloromethyl)furfural (CMF) is freely accessible in high yield directly from raw biomass and is shown here to be efficiently reduced to DMF under mild conditions via simple derivatives (aldimine, acetal).
- Dutta, Saikat,Mascal, Mark
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- Dehydration of carbohydrates to 2-furaldehydes in ionic liquids by catalysis with ion exchange resins
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The dehydration of several sugars, including pentoses, hexoses, di, tri, and polysaccharides, in ionic liquids with acidic ion-exchange resins as heterogeneous catalysts was investigated. Good 2-furaldehydes recovery yields, reaching 92% in some cases, were achieved when Dowex 50W ion-exchange resins and 1-n-butyl-3-methylimidazolium chloride ([C4mim]Cl) were used. Our results show that this aproach could represent a promising route towards the cost-efficient production of 2-furaldehydes from carbohydrate-based feedstocks.
- Heguaburu, Viviana,Franco, Jaime,Reina, Luis,Tabarez, Carlos,Moyna, Guillermo,Moyna, Patrick
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- Characteristic flavor formation of thermally processed N-(1-deoxy-α-D-ribulos-1-yl)-glycine: Decisive role of additional amino acids and promotional effect of glyoxal
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The role of amino acids and α-dicarbonyls in the flavor formation of Amadori rearrangement product (ARP) during thermal processing was investigated. Comparisons of the volatile compounds and their concentrations when N-(1-deoxy-α-D-ribulos-1-yl)-glycine r
- Zhan, Huan,Cui, Heping,Yu, Junhe,Hayat, Khizar,Wu, Xian,Zhang, Xiaoming,Ho, Chi-Tang
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- Direct Synthesis of 5-Methylfurfural from d-Fructose by Iodide-Mediated Transfer Hydrogenation
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Herein, a robust catalytic system was developed for the green synthesis of 5-methylfurfural (5-MF) by iodide-mediated transfer hydrogenation. Around 50 % of 5-MF was yielded from d-fructose within 7.5 min using NaI as the catalyst and formic acid as both the hydrogen source and co-catalyst. The catalytic system was used for six consecutive cycles without any decrease in the yield. Various starch and raw biomass could be used as promising starting materials for 5-MF synthesis with moderate yields, and the productivity of 5-MF from corn starch reached 103 mmol gcat?1 h?1, which is comparable with the best result from l-rhamnose. Moreover, the co-production of 5-MF and furfural from raw biomass makes this methodology more competitive than other routes.
- Xu, Jianwang,Miao, Xinge,Liu, Lei,Wang, Yantao,Yang, Weiran
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p. 5311 - 5319
(2021/11/01)
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- Radical induced disproportionation of alcohols assisted by iodide under acidic conditions
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The disproportionation of alcohols without an additional reductant and oxidant to simultaneously form alkanes and aldehydes/ketones represents an atom-economical transformation. However, only limited methodologies have been reported, and they suffer from a narrow substrate scope or harsh reaction conditions. Herein, we report that alcohol disproportionation can proceed with high efficiency catalyzed by iodide under acidic conditions. This method exhibits high functional group tolerance including aryl alcohol derivatives with both electron-withdrawing and electron-donating groups, furan ring alcohol derivatives, allyl alcohol derivatives, and dihydric alcohols. Under the optimized reaction conditions, a 49% yield of 5-methyl furfural and a 49% yield of 2,5-diformylfuran were obtained simultaneously from 5-hydroxymethylfurfural. An initial mechanistic study suggested that the hydrogen transfer during this redox disproportionation occurred through the inter-transformation of HI and I2. Radical intermediates were involved during this reaction.
- Huang, Yang,Jiang, Haiwei,Li, Teng,Peng, Yang,Rong, Nianxin,Shi, Hexian,Yang, Weiran
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supporting information
p. 8108 - 8115
(2021/10/29)
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- Green synthesis of heterogeneous copper-alumina catalyst for selective hydrogenation of pure and biomass-derived 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan
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In this work novel copper-alumina catalysts were prepared through a solvent-free solid-state grinding method ― a low cost and green catalyst preparation method for selective hydrogenation of 5-hydroxymethylfurfural (5-HMF) into 2,5-bis(hydroxymethyl)furan (BHMF). Under the optimized reaction conditions (3 MPa H2, 130 °C, 1 h), >99 % 5-HMF conversion and 93 % BHMF yield were obtained by using a 20CA (20 mol%Cu-Al2O3) catalyst. The catalyst characterization results could reveal that the high catalytic activity and selectivity could be attributed to the presence of both metallic and electrophilic copper (Cu°/Cu2+) species and the uniformly distributed copper nanoparticles. Furthermore, an integrated catalytic process was demonstrated for the first time for direct conversion of mono, di, and polysaccharides into the corresponding BHMF, obtained overall BHMF yield in the range of 25 %–48 %.
- Hu, Yulin,Rao, Kasanneni Tirumala Venkateswara,Xu, Chunbao Charles,Yuan, Zhongsun,Zhang, Yongsheng
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- Iodine-catalyzed alcohol disproportionation method
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The invention relates to the technical field of catalysis, in particular to an iodine-catalyzed alcohol disproportionation method which comprises the following steps: sequentially adding alcohol, iodine and a solvent into a high-temperature and high-pressure reaction kettle, introducing a certain amount of nitrogen, conducting reacting for a certain time, collecting an organic phase after the reaction is ended, and conducting fractionating to obtain corresponding alkane and aldehyde/ketone. Alcohol disproportionation is efficient and atom-economical conversion without any additional oxidizing agent and reducing agent, and hydrocarbon and aldehyde/ketone molecules which are easy to separate can be formed at the same time. Meanwhile, the method has wide functional group tolerance, various substrate samples including aryl alcohol derivatives, heterocyclic alcohol derivatives, allyl alcohol derivatives and dihydric alcohol are tested, and the result shows that most of the substrate samples show good or extremely good yield.
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Paragraph 0026-0027
(2021/06/13)
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- Tandem catalyzing the hydrodeoxygenation of 5-hydroxymethylfurfural over a Ni3Fe intermetallic supported Pt single-atom site catalyst
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Single-atom site catalysts (SACs) have been used in multitudinous reactions delivering ultrahigh atom utilization and enhanced performance, but it is challenging for one single atom site to catalyze an intricate tandem reaction needing different reactive sites. Herein, we report a robust SAC with dual reactive sites of isolated Pt single atoms and the Ni3Fe intermetallic support (Pt1/Ni3Fe IMC) for tandem catalyzing the hydrodeoxygenation of 5-hydroxymethylfurfural (5-HMF). It delivers a high catalytic performance with 99.0% 5-HMF conversion in 30 min and a 2, 5-dimethylfuran (DMF) yield of 98.1% in 90 min at a low reaction temperature of 160 °C, as well as good recyclability. These results place Pt1/Ni3Fe IMC among the most active catalysts for the 5-HMF hydrodeoxygenation reaction reported to date. Rational control experiments and first-principles calculations confirm that Pt1/Ni3Fe IMC can readily facilitate the hydrodeoxygenation reaction by a tandem mechanism, where the single Pt site accounts for C-O group hydrogenation and the Ni3Fe interface promotes the C-OH bond cleavage. This interfacial tandem catalysis over the Pt single-atom site and Ni3Fe IMC support may develop new opportunities for the rational structural design of SACs applied in other heterogeneous tandem reactions.
- Meng, Ge,Ji, Kaiyue,Zhang, Wei,Kang, Yiran,Wang, Yu,Zhang, Ping,Wang, Yang-Gang,Li, Jun,Cui, Tingting,Sun, Xiaohui,Tan, Tianwei,Wang, Dingsheng,Li, Yadong
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p. 4139 - 4146
(2021/04/02)
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- Formic Acid-Assisted Selective Hydrogenolysis of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N-Doped Mesoporous Carbon
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Biomass-derived 5-hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5-dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N-containing and N-free mesoporous carbon materials were prepared, characterized, and applied in the hydrogenolysis of HMF to DMF under mild reaction conditions. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid (FA) and H2 over Pd/NMC within 2 h. The reaction mechanism, especially the multiple roles of FA, was explored through a detailed comparative study by varying hydrogen source, additive, and substrate as well as by applying in situ ATR-IR spectroscopy. The major role of FA is to shift the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via the protonation by FA at the C-OH group, lowering the activation barrier of the C?O bond cleavage and thus significantly enhancing the reaction rate. XPS results and DFT calculations revealed that Pd2+ species interacting with pyridine-like N atoms significantly enhance the selective hydrogenolysis of the C?OH bond in the presence of FA due to their high ability for the activation of FA and the stabilization of H?.
- Hu, Bin,Warczinski, Lisa,Li, Xiaoyu,Lu, Mohong,Bitzer, Johannes,Heidelmann, Markus,Eckhard, Till,Fu, Qi,Schulwitz, Jonas,Merko, Mariia,Li, Mingshi,Kleist, Wolfgang,H?ttig, Christof,Muhler, Martin,Peng, Baoxiang
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supporting information
p. 6807 - 6815
(2021/02/01)
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- Magnetic gold-cobalt composite catalyst as well as preparation method and application thereof
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The invention provides a magnetic gold-cobalt composite catalyst and a preparation method and application thereof, and belongs to the technical field of catalysts. The magnetic cobalt-cobalt composite catalyst comprises a magnetic cobalt oxide carrier and a gold-cobalt alloy loaded on the surface of the magnetic cobalt oxide carrier. The chemical composition of the magnetic cobalt oxide carrier is CoO. x , 1 _AOMARKENCODTX0AOA x _AOMARKENCODELTA AOA 1.5. In the catalyst provided by the invention, a metal synergistic effect is generated between gold and cobalt in the gold-cobalt alloy. CoOx A large number of surface defects are found in the invention, and a large number of reaction active sites are provided. The catalytic activity of the catalyst for 5 -hydroxymethylfurfural hydrogenation preparation 2, 5 -dimethylfuran is improved, the conversion rate 5 - hydroxymethylfurfural is high, 2,5 -dimethylfuran is high in yield and selectivity.
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Paragraph 0094-0098; 0101-0106
(2021/08/25)
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- Homogeneous CuCl2/TMEDA/TEMPO-Catalyzed chemoselective base- and halogen- free aerobic oxidation of primary alcohols in mild conditions
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This article describes the developing of a base- and halogen- free homogeneous system aiming to chemoselectively oxidize allyl, furyl, aryl and heteroaryl primary alcohols. The current easy-to-handle aerobic system uses few amounts of CuCl2/TMEDA/TEMPO system under mild reaction conditions to produce aldehydes in high yields. Moreover, the CuCl2/TMEDA cyclic voltammetry was measured for the first time, disclosing that TMEDA as ligand substantially affects the redox potential (E1/2) of the couple E1/2Cu2+/Cu+ to E1/2Cu2+/Cu+-TMEDA by 454 mV in the redox system.
- Alves, Otávio A. L.,Chagas, Rafael C. R.,Princival, Jefferson L.,Ribeiro, RogérioT.,Silva, Emmanuel D.,Villar, José A. F. P.
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- Ni-Al/CoOx-catalyzed hydrodeoxygenation of 5-hydroxymethylfurfural into 2,5-dimethylfuran at low temperatures without external hydrogen
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Catalytic hydrodeoxygenation of 5-hydroxymethylfurfural into 2,5-dimethylfuran has received great interest in recent years. In this work, a ternary Ni-Al/CoOx-1 catalyst was fabricated, which provided 96% yield of DMF from in situ hydrodeoxygenation of HMF under mild reaction conditions. XRD, TEM and TPR revealed that the addition of Al to the Ni-Co bimetallic system could make the structure more stable and improve the dispersion of Ni and Co species. XPS, CO-DRIFTS and EPR verified that an enhanced electron transfer from Co species to Ni occurred on Ni-Al/CoOx-1. Reaction mechanism studies unraveled that the Al addition results in promoting in situ H2 production from 2-propanol and accelerating the aldehyde group hydrogenation to a hydroxymethyl group and the subsequent hydrogenolysis into a methyl group, due to the formation of a charge separated metal-couple-site (Niδ-Coδ+) and stronger Lewis acid sites in Ni-Al/CoOx-1. In addition, this ternary Ni-Al/CoOx-1 catalyst exhibits superior recyclability without significant loss of activity for 7 cycles.
- An, Yadan,Bai, Guoyi,Bian, Gang,Li, Tianming,Niu, Libo,Xia, Zhanghui
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p. 7763 - 7772
(2021/10/12)
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- The thermal stability and safety of 2, 5-dimethylfuran (DMF) oxidation
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DMF is renewable energy obtained from glucose, its thermal stability and safety need to be investigated. Accelerated rate calorimeter (ARC) is widely used to evaluate the risk of hazardous materials. In this paper, the thermal stability and safety of DMF oxidation were investigated using an ARC. DMF does not react even when the temperature reaches 452 K under nitrogen atmosphere. In oxygen atmosphere, the onset temperature (T0) of DMF oxidation is 323.49 K, and the activation energy (Ea) is 172.35 kJ/mol. The peroxide concentration of oxidation process was determined by iodometry, and the oxidation products were analyzed by gas chromatography - mass spectrometry. The pressure and exothermic behavior of ARC are related to the reaction mechanism. A simple three steps mechanism of DMF oxidation was described: fist DME reacts with oxygen to form peroxide; second is the main oxidation stage, oxidation products are complex; the third step is thermal decomposition.
- Huang, Pinxian,Kubota, Shiro,Liu, Pin,Liu, Xiongmin,Saburi, Tei,Wada, Yuji
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- Photo-on-Demand Synthesis of Vilsmeier Reagents with Chloroform and Their Applications to One-Pot Organic Syntheses
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The Vilsmeier reagent (VR), first reported a century ago, is a versatile reagent in a variety of organic reactions. It is used extensively in formylation reactions. However, the synthesis of VR generally requires highly toxic and corrosive reagents such as POCl3, SOCl2, or COCl2. In this study, we found that VR is readily obtained from a CHCl3 solution containing N,N-dimethylformamide or N,N-dimethylacetamide upon photo-irradiation under O2 bubbling. The corresponding Vilsmeier reagents were obtained in high yields with the generation of gaseous HCl and CO2 as byproducts to allow their isolations as crystalline solid products amenable to analysis by X-ray crystallography. With the advantage of using CHCl3, which bifunctionally serves as a reactant and a solvent, this photo-on-demand VR synthesis is available for one-pot syntheses of aldehydes, acid chlorides, formates, ketones, esters, and amides.
- Liang, Fengying,Eda, Kazuo,Okazoe, Takashi,Wada, Akihiro,Mori, Nobuaki,Konishi, Katsuhiko,Tsuda, Akihiko
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p. 6504 - 6517
(2021/05/06)
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- Highly active bifunctional Pd-Co9S8/S-CNT catalysts for selective hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran
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A series of Pd-Co bimetallic catalysts were smoothly synthesized using sulfur-modified carbon nanotubes (S-CNT) as support by impregnation method. Those catalysts were characterized by XRD, XPS, TEM, SEM, H2-TPR, TGA, and nitrogen adsorption-de
- Liao, Weiping,Zhu, Zhiguo,Chen, Naimeng,Su, Ting,Deng, Changliang,Zhao, Yuchao,Ren, Wanzhong,Lü, Hongying
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- Self-tuned properties of CuZnO catalysts for hydroxymethylfurfural hydrodeoxygenation towards dimethylfuran production
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5-Hydroxymethylfurfural (HMF) is a very valuable platform molecule obtained from biomass. It can be catalytically transformed to many industrially relevant products of both oxidation and reduction reactions. In this work, we showed that robust CuZnO can be an efficient, self-tuned catalyst for 2,5-dimethylfuran (DMF) (biofuel additive) synthesis. We showed that CuZnO catalysts can be further activated in the reaction environment and this process depends strongly on the initial catalyst properties and therefore on the catalyst preparation method. Smaller copper particles are more active but more prone to carbon deposit formation. Based on activity tests and extensive characterization, we have concluded that both Cun+ and Cu0 sites are necessary for high HMF conversion. While these two sites favor high conversion and high 2,5-bishydroxymethylfuran (BHMF) yield, the in situ formation of Lewis acid sites is proposed to be necessary for achieving a high DMF yield.
- Brzezińska, Magdalena,Keller, Nicolas,Ruppert, Agnieszka M.
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p. 658 - 670
(2020/02/27)
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- Production of 5-(formyloxymethyl)furfural from biomass-derived sugars using mixed acid catalysts and upgrading into value-added chemicals
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In this work, 5-(formyloxymethyl)furfural (FMF) has been produced from biomass-derived hexose sugars within a biphasic reaction mixture consisting of aqueous formic acid (85%), a strong Br?nsted acid catalyst, and 1,2-dichloroethane as an organic extractant. Using a combination of aqueous hydrobromic acid and formic acid, under optimized condition (80 °C, 8 h, 10 wt% substrate loading), 68% isolated yield of FMF was obtained from fructose. FMF has been demonstrated as a renewable chemical building block for the synthesis of renewable chemicals of commercial significance such as 5-methylfurfural, 2,5-diformylfuran, and 2,5-furandicarboxylic acid in good to excellent isolated yields.
- Dutta, Saikat
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- Flow hydrogenation of 5-acetoxymethylfurfural over Cu-based catalysts
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5-Acetoxymethylfurfural (AMF) is a promising starting material for synthesis of the valuable furan derivatives. The catalytic properties of Cu-based catalysts obtained from layered double hydroxides were studied in flow hydrogenation of AMF to 5-(acetoxymethyl)-2-furanmethanol (AMFM) in the present work. The resulting product can be easily converted to 2,5-bis(hydroxymethyl)furan which has significant potential in the production of polymers and pharmaceuticals. It was found that hydrogenation of AMF gives AMFM with selectivity of 98 percent at the full conversion of the substrate under mild reaction conditions (90°C and 10 bar). The influence of the solvent nature, Cu/Al ratio and calcination temperature on the catalyst performance was investigated.
- Bukhtiyarova, Galina A.,Bukhtiyarova, Marina V.,Bulavchenko, Olga A.,Nuzhdin, Alexey L.
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- Synthesis of renewable C-C cyclic compounds and high-density biofuels using 5-hydromethylfurfural as a reactant
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The major challenge in the synthesis of high-density biofuels is to identify the bio-based source for C-C cyclic compounds and C-C coupling reactions with a suitable selectivity. Herein, we selectively synthesize 1,2,4-benzenetriol (BTO) with a yield of 51.4% from cellulose-derived 5-hydromethylfurfural via a ring-rearrangement reaction. The cellulose-derived route is a more meaningful route for the C-C cyclic compounds compared to the traditional hemicellulose- and lignin-derived routes. Furthermore, BTO is very easily dimerized via a C-C oxidative coupling reaction, showing a yield of 94.4% and selectivity of nearly 100% under environmentally friendly reaction conditions. After hydrodeoxygenation, bicyclohexane is obtained with a yield of 87.4%. This work not only provides a promising route to produce C-C cyclic fine compounds based on a cellulose-derived route, but also shows a highly efficient synthesis route for high-density biofuels via the C-C oxidative coupling reaction.
- Cai, Taimei,Deng, Qiang,Deng, Shuguang,Gao, Rui,Peng, Hailong,Wang, Jun,Zeng, Zheling,Zhong, Jin,Zou, Ji-Jun
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p. 2468 - 2473
(2020/05/14)
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- Multistep Engineering of Synergistic Catalysts in a Metal-Organic Framework for Tandem C-O Bond Cleavage
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Cleavage of strong C-O bonds without breaking C-C/C-H bonds is a key step for catalytic conversion of renewable biomass to hydrocarbon feedstocks. Herein we report multistep sequential engineering of orthogonal Lewis acid and palladium nanoparticle (NP) catalysts in a metal-organic framework (MOF) built from (Al-OH)n secondary building units and a mixture of 2,2′-bipyridine-5,5′-dicarboxylate (dcbpy) and 1,4-benzenediacrylate (pdac) ligands (1) for tandem C-O bond cleavage. Ozonolysis of 1 selectively removed pdac ligands to generate Al2(OH)(OH2) sites, which were subsequently triflated with trimethylsilyl triflate to afford strongly Lewis acidic sites for dehydroalkoxylation. Coordination of Pd(MeCN)2Cl2 to dcbpy ligands followed by in situ reduction produced orthogonal Pd NP sites in 1-OTf-PdNP as the hydrogenation catalyst. The selective and precise transformation of 1 into 1-OTf-PdNP was characterized step by step using powder X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, inductively coupled plasma mass spectrometry, infrared spectroscopy, and X-ray absorption spectroscopy. The hierarchical incorporation of orthogonal Lewis acid and Pd NP active sites endowed 1-OTf-PdNP with outstanding catalytic performance in apparent hydrogenolysis of etheric, alcoholic, and esteric C-O bonds to generate saturated alkanes via a tandem dehydroalkoxylation-hydrogenation process under relatively mild conditions. The reactivity of C-O bonds followed the trend of tertiary carbon > secondary carbon > primary carbon. Control experiments demonstrated the heterogeneous nature and recyclability of 1-OTf-PdNP and its superior catalytic activity over the homogeneous counterparts. Sequential engineering of multiple catalytic sites in MOFs thus presents a unique opportunity to address outstanding challenges in sustainable catalysis.
- Brzezinski, Carter,Chen, Justin S.,Feng, Xuanyu,Lin, Wenbin,Song, Yang,Xu, Ziwan
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supporting information
p. 4872 - 4882
(2020/04/01)
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- Hydroconversion of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran and 2,5-Dimethyltetrahydrofuran over Non-promoted Ni/SBA-15
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The selective hydroconversion of 5-hydroxymethylfurfural (HMF) to biofuels is currently highly sought-for. While the literature has demonstrated that this reaction is possible on promoted Ni catalysts, we show here that a monometallic, non-promoted Ni/SBA-15 catalyst, prepared by incipient wetness impregnation, can convert HMF to 2,5-dimethylfuran (DMF) and to 2,5-dimethyltetrahydrofuran (DMTHF) at 180 °C, in a consecutive way. Through a control over reaction time, high yields to DMF (71 %, at conversion of 93 %) or DMTHF (97 %, at conversion of 100 %) can be achieved. Kinetic modelling suggests a preferential route to DMF via 5-methylfurfural (MFFR) as intermediate, though the route via 2,5-bis(hydroxylmethyl)furan (BHMF) is also present. The favored route in the experimental conditions involves the hydrogenolysis of the hydroxyl group of HMF as first step, followed by the hydrogenation of the aldehyde function, to methylfurfuryl alcohol (MFOL). It is suggested a higher reaction rate of hydrogenation or hydrogenolysis of the side group is linked to the presence of a methyl group in the molecule. No hydrogenation of the furan ring is detected on the intermediates.
- Chen, Shuo,Ciotonea, Carmen,De Oliveira Vigier, Karine,Jér?me, Fran?ois,Wojcieszak, Robert,Dumeignil, Franck,Marceau, Eric,Royer, Sebastien
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p. 2050 - 2059
(2020/03/04)
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- Rediscovering aminal chemistry: Copper(ii) catalysed formation under mild conditions
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Aminals, the N,N analogues of acetals, have been thoroughly explored in organic chemistry, with a particular focus on heteroaromatic aldehyde lithiation. Nevertheless, the existing methodologies for their formation typically employ harsh conditions limiting their usefulness. In this work, we present an efficient and mild methodology for the preparation of aminals from aromatic aldehydes, including furanic platforms. These mild conditions allowed ease of access to a plethora of aminals and as such we set out to explore previously unaccessible potential applications. By studying the stability of various aminals, we were able to develop a simple aldehyde protecting group based on a commercial diamine which is deprotected under mind conditions. We developed a protocol for the scavenging of genotoxic aldehydes by taking advantage of our methodology and a diamine resin, as well as early studies on the development of a stimuli-responsive release system using a salycil aldehyde derived aminal. This journal is
- Afonso, Carlos A. M.,António, Jo?o P. M.,Gomes, Rafael F. A.,Mendon?a, Ricardo,Pereira, Juliana G.
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p. 7484 - 7490
(2020/11/18)
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- Design and synthesis of a versatile cooperative catalytic aerobic oxidation system with co-immobilization of palladium nanoparticles and laccase into the cavities of MCF
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We have designed a versatile reusable cooperative catalyst oxidation system, consisting of palladium nanoparticles and laccase with unprecedented reactivity. This biohybrid catalyst was synthesized by the stepwise immobilization of laccase as an enzyme and Pd as a nanometallic component into the same cavity of siliceous mesocellular foams (MCF). MCF and nanobiohybrid catalyst were characterized by BET, SAXS, SEM, EDX elemental mapping, ICP-OES, TEM, TGA, FT-IR, and XPS techniques and the stepwise immobilization of laccase enzyme and Pd onto MCF was evaluated through several compelling electrochemical studies. The present catalytic system exhibits high activity toward (i) aerobic oxidation of alcohols to the corresponding carbonyl compounds, (ii) aerobic oxidation of cyclohexanol and cyclohexanone to phenol and (iii) aerobic dehydrogenation of important N-heteocyclic compounds (tetrahydro quinazolines, quinazolonones, pyrazolines and 1,4-diydropyridines) in the presence of catalytic amount of hydroquinone (HQ) as mediator in phosphate buffer (0.1 M, pH 4.5, 4 mL)/THF (4%, 1 mL) as solvent under mild conditions. The immobilization of both oxygen-activating catalyst (laccase) and oxidizing catalyst (Pd) onto the same support makes the present catalyst system superior to other currently available heterogeneous palladium based catalytic aerobic oxidation systems.
- Moradi, Sirvan,Shokri, Zahra,Ghorashi, Nadya,Navaee, Aso,Rostami, Amin
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p. 305 - 319
(2020/01/21)
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- Decomposition of glucose with in situ deoxygenation in a low H2 pressure environment – Pt. II: Bimetallic catalysts
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Bimetallic catalysts, CoFe, NiFe, PdFe, and PtCo were studied for their ability to perform in situ deoxygenation of glucose decomposition production at 350 °C. Catalysts were prepared via co-impregnation and sequential impregnation methods on SiO2/s
- Rogers, Kyle A.,Zheng, Ying
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- Towards Improved Biorefinery Technologies: 5-Methylfurfural as a Versatile C6 Platform for Biofuels Development
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Low chemical stability and high oxygen content limit utilization of the bio-based platform chemical 5-(hydroxymethyl)furfural (HMF) in biofuels development. In this work, Lewis-acid-catalyzed conversion of renewable 6-deoxy sugars leading to formation of more stable 5-methylfurfural (MF) is carried out with high selectivity. Besides its higher stability, MF is a deoxygenated analogue of HMF with increased C/O ratio. A highly selective synthesis of the innovative liquid biofuel 2,5-dimethylfuran starting from MF under mild conditions is described. The superior synthetic utility of MF against HMF in benzoin and aldol condensation reactions leading to long-chain alkane precursors is demonstrated.
- Galkin, Konstantin I.,Ananikov, Valentine P.
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p. 185 - 189
(2018/12/05)
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- Method using biomass carbohydrate to prepare 5-methylfurfural
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The invention relates to a method using biomass carbohydrate to prepare 5-methylfurfural. The method includes: sequentially adding the biomass carbohydrate, tungsten carbide, distilled water, hydroiodic acid or iodine and an organic solvent into a reaction kettle, performing stirring reaction for 15-180 minutes in hydrogen atmosphere of 50-500psi and at the temperature of 90-200 DEG C, cooling inan ice-water bath manner, separating the reaction liquid, separating the upper-layer organic phase, and further purifying to obtain the 5-methylfurfural. The method has the advantage that the main rawmaterial for preparing the 5-methylfurfural is the renewable biomass carbohydrate; the cheap and recyclable tungsten carbide catalyst is used, the reaction is performed under mild reaction conditions, production cost is lowered, requirements on production equipment are low, and the method conforms to the principle of safety production.
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Paragraph 0028-0029
(2019/07/04)
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- Preparation of 5-methylfurfural from starch in one step by iodide mediated metal-free hydrogenolysis
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Starch is available in large quantities and at cheap price, especially that from stale rice, root and tuber crops, etc., which makes it desirable for conversion to value-added products. A metal-free approach to convert starch to 5-methylfurfural (5-MF) using hydrochloric acid, sodium iodide and hydrogen in a biphasic solvent system has been developed. 5-MF is an important fine chemical, widely used in food, medicine, pesticides, cosmetics and other industries, and is also considered to be an important bio-gasoline precursor. I- has superior nucleophilic substitution properties and high reactivity towards C-O bond cleavage, which is crucial for this transformation. Under optimal reaction conditions, 38.0% of 5-MF and 45.6% of total organic products can be obtained from starch with 22.5% levulinic acid as the main side product. Besides, 80.8% 5-MF can be directly obtained from 5-hydroxymethylfurfural (HMF) through the same process. To the best of our knowledge, this is the first reported example of a metal-free process to convert starch and HMF directly to 5-MF. The reaction mechanism was well studied. The catalyst system was proved to be stable and was recycled five times without loss of activity.
- Peng, Yang,Li, Xianghua,Gao, Tian,Li, Teng,Yang, Weiran
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p. 4169 - 4177
(2019/08/12)
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- A metal free from biomass resources of one pot process for preparing 5 - methyl furfural (by machine translation)
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The invention relates to the technical field of catalysis, in particular to a metal free from biomass resources of one pot process for preparing 5 - methyl furfural, according to the following steps: sequentially the biomass or a derivative thereof, iodide, solvent, acid is added to the high-temperature high-pressure reaction kettle, and inject a certain hydrogen, the reaction after a certain time, after the end of the collecting organic phase fractionation to obtain 5 - methyl furfural, yield is as high as 51.9%. The method through under the conditions of low temperature and low pressure, to the high expectations for production equipment, in accordance with the principles of safe production; metal free selective hydrogenolysis of biomass or its derivatives conversion 5 - methyl furfural, raw materials can be regenerated low cost, excellent performance, the process is simple, and easy separation of product and the mild condition, and to avoid the loss of the material of the intermediate steps, to achieve the optimum utilization of resources. (by machine translation)
- -
-
Paragraph 0040; 0041
(2019/07/10)
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- Insight into the hydrogenation of pure and crude HMF to furan diols using Ru/C as catalyst
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5-hydroxymethylfurfural (HMF) is one of the most important renewable platform-chemicals, a very valuable precursor for the synthesis of bio-fuels and bio-products. In this work, the hydrogenation of HMF to two furan diols, 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF), both promising renewable monomers, was investigated. Three commercial catalysts, Ru/C, Pd/C and Pt/C, were tested in the hydrogenation of aqueous HMF solutions (2–3 wt%), using a metal loading of 1 wt% respect to HMF content. By appropriate tuning of the process conditions, either BHMF or BHMTHF were obtained in good yields, and Ru/C resulted the best catalyst for this purpose, allowing us to obtain BHMF or BHMTHF yields up to 93.0 and 95.3 mol%, respectively. This catalyst was also tested for in the hydrogenation of a crude HMF-rich hydrolyzate, obtained by one-pot the dehydration of fructose. The influence of each component of this hydrolyzate on the hydrogenation efficiency was investigated, including unconverted fructose, rehydration acids and humins, in order to improve the yields towards each furan diol. Moreover, ICP-OES and TEM analysis showed that the catalyst was not subjected to important leaching and sintering phenomena, as further confirmed by catalyst recycling study.
- Fulignati, Sara,Antonetti, Claudia,Licursi, Domenico,Pieraccioni, Matteo,Wilbers, Erwin,Heeres, Hero Jan,Raspolli Galletti, Anna Maria
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p. 122 - 133
(2019/04/17)
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- Methods for producing nylon 7
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Nylon 7 may be produced from biomass derived 6-carbon hydroxymethyl furan compounds as the raw material. The hydroxymethyl furan compounds may be homologated to form an aldehyde that may be aminated to produce an amino carbonyl compound. Hydrogenation/hydro-deoxygenation of the amino-carbonyl compound provides nylon 7.
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Page/Page column 6
(2018/06/08)
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- Ruthenium on carbonaceous materials for the selective hydrogenation of HMF
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We report the use of Ru catalysts supported in the activated carbon (AC) and carbon nanofibers (CNFs) for the selective production of liquid fuel dimethylfuran (DMF) and fuel additives alkoxymethyl furfurals (AMF). Parameters such as the reaction temperature and hydrogen pressure were firstly investigated in order to optimise the synthesis of the desired products. Simply by using a different support, the selectivity of the reaction drastically changed. DMF was produced with AC as support, while a high amount of AMF was produced when CNFs were employed. Moreover, the reusability of the catalysts was tested and deactivation phenomena were identified and properly addressed. Further studies need to be performed in order to optimise the stability of the catalysts.
- Cattaneo, Stefano,Naslhajian, Hadi,Somodi, Ferenc,Evangelisti, Claudio,Villa, Alberto,Prati, Laura
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- Toward an Integrated Conversion of 5-Hydroxymethylfurfural and Ethylene for the Production of Renewable p-Xylene
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The use of biomass as a solution to satisfy the pressing needs for a fully sustainable biocommodity industry has been explored for a long time. However, limited success has been obtained. In this study, a highly effective two-stage procedure for the direct preparation of para-xylene (PX) from 5-hydroxymethylfurfural (HMF) and formic acid in one pot is described; these chemicals are two of the major bio-based feedstocks that offer the potential to address urgent needs for the green, sustainable production of drop-in chemical entities. The use of a robust, efficient heterogeneous catalyst, namely, bimetallic Pd-decorated Au clusters anchored on tetragonal-phase zirconia, is crucial to the success of this strategy. This multifunctional catalytic system can not only facilitate a low-energy-barrier H2-free pathway for the rapid, nearly exclusive formation of 2,5-dimethylfuran (DMF) from HMF but also enable the subsequent ultraselective production of PX by the dehydrative aromatization of the resultant DMF with ethylene. With increasing pressure around the world to move toward a bio-based economy, it is essential that industrially important commodity chemicals can be readily accessed from biomass resources. Para-xylene (PX) synthesis is one such target that is being actively pursued through the development of several biorefinery schemes based on integrated biomass processing. Significant progress has recently been achieved either in the selective synthesis of biorenewable PX from Diels-Alder-like coupling of ethylene with 2,5-dimethylfuran (DMF) or making DMF from 5-hydroxymethylfurfural (HMF) using hydrogen as the terminal reductant. However, a green and direct conversion of HMF, an essential feedstock source for future biorefinery schemes, into PX has yet to be developed. We have established an integrated process that directly converts HMF to PX in a highly compact and hydrogen-independent manner, thereby providing a new perspective on the potential of advanced biorefinery technologies. Cao and colleagues describe an alternative strategy for producing para-xylene through a more sustainable method than the current bio-based approaches. The strategy relies on an integrated conversion of 5-hydroxymethylfurfural with formic acid and ethylene, made possible by the use of a single multifunctional catalyst based on bimetallic Pd-decorated Au deposited on tetragonal-phase zirconia. The proposed process is particularly appealing because it is fully fossil independent, implying a viable and greener biorefinery scheme.
- Tao, Lei,Yan, Tian-Hao,Li, Wenqin,Zhao, Yi,Zhang, Qi,Liu, Yong-Mei,Wright, Mark M.,Li, Zhen-Hua,He, He-Yong,Cao, Yong
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supporting information
p. 2212 - 2227
(2018/10/02)
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- Palladium-metalated porous organic polymers as recyclable catalysts for chemoselective decarbonylation of aldehydes
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A novel palladium nanoparticle (NP)-metalated porous organic ligand (Pd NPs/POL-xantphos) has been prepared for the chemoselective decarbonylation of aldehydes. This heterogenous catalyst not only has excellent catalytic activity and chemoselectivity, but also holds high activity after 10 runs of reuse. The effective usage of this method is demonstrated through the synthesis of biofuels such as furfuryl alcohol (FFA) via the highly chemoselective decarbonylation of biomass-derived 5-hydroxy-methylfurfural (HMF) with a TON up to 1540. More importantly, 9-fluorenone could be obtained in one step through the decarbonylation of 2-bromobenzaldehyde by using this heterogeneous catalyst.
- Li, Wen-Hao,Li, Cun-Yao,Li, Yan,Tang, Hai-Tao,Wang, Heng-Shan,Pan, Ying-Ming,Ding, Yun-Jie
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p. 8446 - 8449
(2018/08/28)
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- Method for preparing N-(5-methylfurfuryl)aniline and derivatives from biomass carbohydrate
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The invention discloses a method for preparing N-(5-methylfurfuryl)aniline and derivatives from biomass carbohydrate. The method comprises the following steps: sequentially adding biomass carbohydrate, phosphorous acid, distilled water, hydrogen iodide and an organic solvent to a reaction container; stirring at a normal pressure and a temperature of 30-120 DEG C; reacting for 0.2-5 h; separating atwo-phase solvent; successively extracting and washing an organic layer with sodium sulfite, sodium hydroxide and a saturated salt solution for multiple times; collecting an organic phase to be dewatered by anhydrous magnesium sulfate; sequentially adding a multiphase hydrogenation catalyst, the additional solvent, aniline or aniline derivatives; stirring in a hydrogen atmosphere of normal pressure to 2.0 MPa and at a temperature of normal temperature to 100 DEG C; reacting for 0.2-3.0 h; and separating products. The method provided by the invention mainly uses renewable biomass carbohydrateas the raw material, is completed by two steps so as to be simple to operate and avoid loss of materials caused by intermediate steps, is performed under normal pressure and mild conditions without noble metal catalyst so as to reduce production costs, and has low requirements on equipment.
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Paragraph 0022; 0027-0029
(2018/07/30)
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- Impact of Support Oxide Acidity in Pt-Catalyzed HMF Hydrogenation in Alcoholic Medium
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Abstract: Silica and three mixed silica oxides (silica–alumina, silica–niobia, and silica–zirconia) with nominally 5 wt% of the added element (Al, Nb and Zr) were prepared and used as supports for dispersing monometallic Pt-nanoparticles. The presence of the second oxide component on the silica surface influenced some properties of the final samples, like surface area and acidity. The samples acidity was measured in a recirculation adsorption line with 2-phenylethylamine probe, by performing the titrations both in cyclohexane and in methanol to gather the intrinsic and effective acidity, respectively. The acid site density of silica–alumina was the highest compared with the other oxides; in general, an important decrease of acid sites density was determined in methanol. The order of the effective acidity in methanol was different from that determined in cyclohexane only for silica–zirconia and silica–niobia, confirming the peculiar acidity of Nb-oxide compounds in polar liquids: Colloidal spherical platinum nanoparticles were synthesized and then deposited (1 wt%) on the oxide supports. The obtained metallic nanophases were studied in the reduction of 5-hydroxymethylfurfural (HMF) to valuable chemicals such as dimethylfuran, dimethyltetrahydro-furan, 2-hexanol. In particular, this study focused on the impact of the acidity of the oxide supports on reaction selectivity when 2-butanol is used as solvent. When Pt is not present, Nb-doped silica is the most effective catalyst to di-hydroxymethyl furan diether (DHMFDE) derived from Meerwein–Ponndorf–Verley reaction, maintaining its Lewis character also in protic medium. In the presence of Pt, Nb-doped silica, however, presents the higher selectivity to hydrogenolysis products, 5-methyl furan (5-MF). Graphical Abstract: [Figure not available: see fulltext.]
- Ly, Nhu,Al-Shamery, Katharina,Chan-Thaw, Carine E.,Prati, Laura,Carniti, Paolo,Gervasini, Antonella
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p. 345 - 359
(2017/02/18)
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- A Novel Consecutive Approach for the Preparation of Cu–MgO Catalysts with High Activity for Hydrogenation of Furfural to Furfuryl Alcohol
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Abstract: A consecutive approach is introduced and tested for the first time to synthesize copper-magnesia catalysts with different (Cr, Ca, and Co) promoters for the catalytic hydrogenation of furfural. The comparison of the activity of these catalysts with that prepared via conventional co-precipitation indicated the superior activity of the former. A stable conversion of furfural (up to 91%) to furfuryl alcohol was achieved over the thus-prepared Cu–MgO and CaCu–MgO catalysts. However, both CoCu–MgO and CaCu–MgO demonstrated higher selectivities (about 99%) than the other two samples (Cu–MgO and CrCu–MgO). No direct interconnection was established between the catalytic activity and structural features of the catalysts, however. Graphical Abstract: [Figure not available: see fulltext.]
- Ghashghaee, Mohammad,Sadjadi, Samahe,Shirvani, Samira,Farzaneh, Vahid
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p. 318 - 327
(2017/02/18)
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- The furfural or furfural derivative (by machine translation)
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[Problem] furfuryl alcohol or furfuryl derivative is oxidized, furfural or furfural derivative method selectively in high yield. [Solution] the oxygen as the oxidizing agent, in the presence of a catalyst, or furfuryl alcohol furfural and furfuryl alcohol furfural derivatives or oxidized derivative produced in the method, the catalyst, a ruthenium catalyst on alumina is used, furfural or furfural derivatives can be obtained in high yield with high selectivity. [Drawing] no (by machine translation)
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-
Paragraph 0033
(2017/08/05)
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- Selective Hydrodeoxygenation of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Heterogeneous Iron Catalysts
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This work provided the first example of selective hydrodeoxygenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) over heterogeneous Fe catalysts. A catalyst prepared by the pyrolysis of an Fe-phenanthroline complex on activated carbon at 800 °C was demonstrated to be the most active heterogeneous Fe catalyst. Under the optimal reaction conditions, complete conversion of HMF was achieved with 86.2 % selectivity to DMF. The reaction pathway was investigated thoroughly, and the hydrogenation of the C=O bond in HMF was demonstrated to be the rate-determining step during the hydrodeoxygenation, which could be accelerated greatly by using alcohol solvents as additional H-donors. The excellent stability of the Fe catalyst, which was probably a result of the well-preserved active species and the pore structure of the Fe catalyst in the presence of H2, was demonstrated in batch and continuous flow fixed-bed reactors.
- Li, Jiang,Liu, Jun-Ling,Liu, He-Yang,Xu, Guang-Yue,Zhang, Jun-Jie,Liu, Jia-Xing,Zhou, Guang-Lin,Li, Qin,Xu, Zhi-Hao,Fu, Yao
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p. 1436 - 1447
(2017/04/14)
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- A Pd-Catalyzed in situ domino process for mild and quantitative production of 2,5-dimethylfuran directly from carbohydrates
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An in situ domino process has been developed to be highly efficient for direct and mild conversion of various hexose sugars to the biofuel 2,5-dimethylfuran in almost quantitative yields, without separation of unstable intermediates at 120 °C in n-butanol, by using polymethylhydrosiloxane and hydrophobic Pd/C as a H-donor and a bifunctional catalyst, respectively. Among the cascade reactions, the hydrosilylation process was confirmed by deuterium-labeling and kinetic studies to be favorable for sugar dehydration and exclusively acts on deoxygenation of in situ formed intermediates including furanic alcohols and aldehydes to DMF via a hydride transfer process that was facilitated by an alcoholic solvent. The catalytic system is more selective than the H2- participated counterpart, and could be scaled up with only 0.04 mol% catalyst loading, giving DMF in a comparable yield of 85%. Moreover, Pd(0) was demonstrated to be the active species for deoxygenation, and the heterogeneous catalyst exhibited good recyclability with little elemental leaching.
- Li, Hu,Zhao, Wenfeng,Riisager, Anders,Saravanamurugan, Shunmugavel,Wang, Zhongwei,Fang, Zhen,Yang, Song
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supporting information
p. 2101 - 2106
(2017/07/22)
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- Dehydrogenation of 5-hydroxymethylfurfural to diformylfuran in compressed carbon dioxide: An oxidant free approach
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The dehydrogenation of biomass-based 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) was achieved utilizing an activated carbon supported rhodium (Rh/C) catalyst under mild reaction conditions. The developed method successfully afforded complete conversion and the highest selectivity of DFF (>99%) without any additive, conventional hydrogen acceptor and oxidant. The efficiency of the method is achieved by the addition of compressed carbon dioxide (scCO2) and the synergistic effect of scCO2 and Rh/C, where scCO2 plays a pivotal role in accelerating the reaction by removing hydrogen, and consequently shifting the equilibrium to the forward direction. Optimization of different reaction parameters ensures the achievement of high conversion and selectivity. Characterization of the catalyst using different spectroscopic techniques suggests an interaction between the substrate and the catalyst and provides an indication of the possible reaction pathway, thus a mechanism would be outlined. The rate determining step of the reaction was calculated through mechanistic investigations involving theoretical calculations together with experimental analysis. One of the most attractive features of the method developed in this study is the reverse reaction of DFF, which can be achieved in one-pot without the addition of any external hydrogen. This process has successful application to the dehydrogenation of a variety of alcohols with different substituents.
- Chatterjee, Maya,Ishizaka, Takayuki,Chatterjee, Abhijit,Kawanami, Hajime
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p. 1315 - 1326
(2017/08/15)
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- Effect of promoter on selective hydrogenation of furfural over Cu-Cr/TiO2 catalyst
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Cu-based TiO2-supported catalysts were prepared to study their performance in the selective gas-phase hydrogenation of furfural (FF). The catalytic performance was assessed over 4 hr of run length under atmospheric pressure at the H2-to-hydrocarbon ration of 10.6 and 453 K. The effect of Cr as a promoter was also assessed. An extremely poor performance was observed for the non-promoted catalyst due to the lack of Cu species on the surface of the catalyst. When Cr was applied as a promoter, the dispersion of the Cu species was improved, and, as a result, the Cu-Cr/TiO2 catalyst showed high FF conversion and high furfuryl alcohol yield.
- Ghashghaee, Mohammad,Shirvani, Samira,Farzaneh, Vahid
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p. 304 - 309
(2017/06/06)
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- Role of lewis and Br?nsted acidity in metal chloride catalysis in organic media: Reductive etherification of furanics
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Metal chlorides are demonstrated to behave as bifunctional acid catalysts in organic media in the one-pot reductive etherification of 5-hydroxymethylfurfural (HMF) in 2-propanol toward production of biodiesel. Two competing reaction pathways, direct etherification to 5-(isopropoxymethyl)furfural and reductive etherification to 2,5-bis-(isopropoxymethyl)furan, are proposed with the selectivity depending on the metal ion. Furfural and furfuryl alcohol are used as model compounds to investigate each pathway individually. The roles of Lewis/Br?nsted acidity of metal chlorides solution are elucidated by kinetic studies in conjunction with salt speciation using electrospray soft ionization mass spectrometer. Br?nsted acidic species, generated from alcoholysis of the metal chlorides, are the predominant catalytically active species in etherification. On the other hand, partially hydrolyzed metal cations produced by alcoholysis/hydrolysis are responsible Lewis acid centers for furfural reduction to furfuryl alcohol. Isotopic labeling experiments, in combination with GCMS and 1H NMR analysis, reveal an intermolecular hydrogen transfer from the a-C of 2-propanol to the a-C of furfural as the rate-limiting step of furfural hydrogenation.
- Nguyen, Hannah,Xiao, Nicholas,Daniels, Sean,Marcella, Nicholas,Timoshenko, Janis,Frenkel, Anatoly,Vlachos, Dionisios G.
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p. 7363 - 7370
(2017/11/09)
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- Direct one-pot conversion of monosaccharides into high-yield 2,5-dimethylfuran over a multifunctional Pd/Zr-based metal-organic framework@sulfonated graphene oxide catalyst
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A one-pot conversion of monosaccharides (fructose and glucose) into high-yield 2,5-dimethylfuran (2,5-DMF) is demonstrated over a multifunctional catalyst obtained by loading Pd on a Zr-based metal-organic framework (UiO-66) that is deposited on sulfonated graphene oxide (Pd/UiO-66@SGO). The Br?nsted acidity associated with UiO-66@SGO activates the fructose dehydration to form 5-hydroxymethylfurfural (5-HMF), while the Pd nanoparticles further convert 5-HMF to 2,5-DMF by hydrogenolysis and hydrogenation. The results show that under the optimized reaction conditions of 160 °C and 1 MPa H2 in tetrahydrofuran for 3 h, the yield of 2,5-DMF is as high as 70.5 mol%. This value is higher than the previously reported values, and the direct conversion of fructose can be achieved without additional purification of 5-HMF from the reaction mixture. In addition, for the first time, glucose is converted to 2,5-DMF with a high yield of 45.3 mol%. A recyclability test suggests that the 4.8 wt% Pd loaded on the UiO-66@SGO catalyst can be re-used up to five times.
- Insyani, Rizki,Verma, Deepak,Kim, Seung Min,Kim, Jaehoon
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p. 2482 - 2490
(2017/07/17)
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- Selective hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran on Ru-MoOx/C catalysts
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Selective hydrogenation of 5-hydroxymethylfurfural (HMF) has potential application in high quality biofuels. Herein, the catalytic hydrodeoxygenation (HDO) of HMF to 2,5-dimethylfuran (DMF) was investigated using bi-functional Ru-MoOx/C catalyst prepared by initial wetness impregnation. The high dispersion and electronic transfer between Ru and MoOx were demonstrated by a series of characterization techniques. During this HDO process, the synergy effect between metallic Ru and acidic MoOx species in the Ru-MoOx/C catalyst plays an essential role in obtaining maximized target product DMF (79.4%) via effective aldehyde group hydrogenation by Ru followed by dehydration over MoOx. This work also elucidated that DMF production proceeded through two distinct pathways: the 2,5-hydroxymethyl furan intermediate was preferable by the aldehyde group hydrogenation of HMF over the Ru-MoOx/C catalyst. Over MoOx/C catalyst, comparatively, 5-methyl furfural was the key intermediate by direct hydrogenolysis of the hydroxyl group in HMF. This kind of catalyst is stable for the first two runs by maintaining the target product yield. After the third run, the catalyst showed deactivation gradually but could be almost completely recovered after regeneration by H2 reduction.
- Yang, Yue,Liu, Qiying,Li, Dan,Tan, Jin,Zhang, Qi,Wang, Chenguang,Ma, Longlong
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p. 16311 - 16318
(2017/03/24)
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- Influence of supports for selective production of 2,5-dimethylfuran via bimetallic copper-cobalt catalyzed 5-hydroxymethylfurfural hydrogenolysis
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The hydrogenolysis of carbon–oxygen bonds is an important model reaction in upgrading biomass-derived furanic compounds to transportation fuels. One of these model reactions, namely conversion of 5-hydroxymethylfurfural (HMF) to the gasoline additive 2,5-dimethylfuran (DMF), is especially attractive. In this study, bimetallic Cu-Co catalysts supported on CeO2, ZrO2, and Al2O3 were used for the selective hydrogenolysis of HMF to DMF. The structures of the fresh and used catalysts were studied using X-ray diffraction, the Brunauer-Emmett-Teller method, transmission electron microscopy, temperature-programmed reduction by H2, temperature-programmed desorption of NH3, and CHNS analysis. The structures were correlated with the catalytic activities. The Cu-Co/CeO2 catalyst produced mainly 2,5-bis(hydroxymethyl)furan via reduction of C=O bonds on large Cu particles. The Cu-Co/Al2O3 catalyst gave the best selectivity for DMF, as a result of a combination of highly dispersed Cu, mixed copper–cobalt oxides, and suitable weak acidic sites. Cu-Co/ZrO2 had low selectivity for DMF and produced a combination of various over-hydrogenolysis products, including 2,5-dimethyltetrahydrofuran and 5,5-oxybis(methylene)-bis(2-methylfuran), because of the presence of strong acidic sites. The reaction pathways and effects of various operating parameters, namely temperature, H2 pressure, and time, were studied to enable optimization of the selective conversion of HMF to DMF over the Cu-Co/Al2O3 catalyst.
- Srivastava, Sanjay,Jadeja,Parikh, Jigisha
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p. 699 - 709
(2017/04/24)
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- Towards sustainable hydrogenation of 5-(hydroxymethyl)furfural: A two-stage continuous process in aqueous media over RANEY catalysts
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The hydrogenation of 5-(hydroxymethyl)furfural (HMF) to 2,5-bis(hydroxymethyl)tetrahydrofuran (DHMTHF) in aqueous media under relatively mild reaction conditions has been investigated over heterogeneous RANEY Cu and Ni catalysts using a continuous-flow hydrogenation reactor. These RANEY catalysts were selected following a screening of several catalysts including precious metals supported on carbon for the hydrogenation of HMF. A single-stage versus a two-stage process for the hydrogenation of HMF into DHMTHF, i.e. via 2,5-dihydroxymethylfuran (DHMF) has been evaluated. The best result with an average selectivity of 98% for DHMTHF was obtained using a two-stage process; RANEY Cu was used as a catalyst for the highly selective hydrogenation of HMF to DHMF (92 mol%) in the first stage and this product was used without further purification for in a second-stage selective hydrogenation of DHMF into DHMTHF using RANEY Ni as a catalyst. The influence of the HMF concentration in the feeding solution (1-3 wt%), flow rate (0.05-0.25 mL min-1) and total pressure (20-90 bar) were investigated for the first-stage hydrogenation of HMF into DHMF over RANEY Cu. HMF was found to exert an inhibiting effect on the conversion due to strong adsorption. The RANEY Ni catalyst used in the second stage gradually deactivated. A procedure for in situ regeneration of the partially deactivated RANEY Ni catalyst using acetic acid washing was investigated with limited success.
- Lima, Sérgio,Chadwick, David,Hellgardt, Klaus
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p. 31404 - 31407
(2017/07/10)
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- Role of alkali earth metals over Pd/Al2O3 for decarbonylation of 5-hydroxymethylfurfural
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A series of Pd/Al2O3 catalysts with different alkali earth metals (Mg, Ca, Sr, Ba) and varying Sr loadings (1.8, 3.5, 5.3, 7 and 8.8 wt%) were investigated for 5-hydroxymethylfurfural (HMF) decarbonylation. The alkali earth metal and content were demonstrated to have profound influences on the metal dispersion, electron density of the metal, acid-base properties of the catalyst, and catalytic performance. The Pd3Sr/Al2O3 catalyst exhibited the highest initial activity and furfuryl alcohol selectivity, achieving a yield of 92%. The key to high decarbonylation selectivity is the suppression of hydrogenolysis and etherification side reactions through the attenuation of the acidity of catalysts. Successful catalytic activity not only lies in the increased metallic surface area, but is also affected by the adsorption properties of the carbonyl group and the poisoning CO produced. The catalytic activity is linearly correlated to the surface metallic area at low modifier loading over PdM/Al2O3 catalysts. But along with further increased metallic surface area over PdXSr/Al2O3, HMF conversion initially increased, reaching a plateau over Pd3Sr/Al2O3 and then decreased with increasing Sr loading. A synergistic effect between the Sr species and metallic Pd was proposed, which promoted the migration of carbonyl adsorption from the support to the surface Pd through the electron donation of Sr species to Al2O3 and metallic Pd.
- Meng, Qingwei,Qiu, Chengwu,Ding, Guoqiang,Cui, Jinglei,Zhu, Yulei,Li, Yongwang
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p. 4377 - 4388
(2016/07/06)
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- METHODS OF PRODUCING ALKYLFURANS
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Provided herein are methods of producing dialkylfurans, such as 2,5-dimethylfuran, and other alkyl furans, such as 2-methylfuran. For example, 2,5-dimethylfuran may be produced by hydrogenation of (5-methylfuran-2-yl) methanol or 2-(chloromethyl)-5-methylfuran in the presence of a solid supported metal catalyst having an excess of either basic or acidic sites (as determined by chemisorption of CO2 or NH3). The process could further include a urea reagent (TMU, DMPU, TMI) and an alkyl benzene.
- -
-
Paragraph 0303; 0304
(2016/02/29)
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- Palladium catalyzed hydrogenation of biomass derived halogenated furfurals
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The formation of valuable products and especially fuel candidates from lignocellulosic biomass is highly desirable. Lignocellulose derived halogenated furfurals formation was reported as highly efficient in comparison to the current existing methods of lignocellulose transformation. However, halogenated furfurals are platform chemicals and not end use chemicals, certainly not for fuels. Therefore, transformation methods of halogenated furfurals into fuels, fuels additives, or other valuable compounds are desirable. In this work we present the hydrogenation of halogenated furfurals over carbon supported palladium catalysts. Palladium catalysts showed better performance in the formation of 5-methyl furfural (MF) from halogenated furfurals compared to other catalysts. The reaction products were identified using GC-MS, FT-IR and NMR, and they were quantified using GC analysis. Catalysts were characterized with SEM, BET and pH meter. The role of catalysts properties and reaction parameters in MF preparation, and their effect on MF yields and selectivity were examined. In addition, the catalysts recovery and reuse in subsequent cycles was examined together with the recovery of hydrochloric acid or hydrobromic acid, formed as by products in halogenated furfurals hydrogenation.
- Meller, Elad,Sasson, Yoel,Aizenshtat, Zeev
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p. 103149 - 103159
(2016/11/13)
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- Preparation method for 5-methyl-2-furfural
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The invention provides a preparation method for 5-methyl-2-furfural. The method comprises the following steps: 1) reacting bis(trichloromethyl) carbonate with a mixture of 2-methylfuran and DMF so as to produce 5-methyl-2-furfural-CH=N(CH3)2Cl, thereby producing a Vilsmeier compound; and 2) adding liquid alkali into the compound obtained in the step 1) for hydrolysis so as to eventually obtain 5-methyl-2-furfural. Since bis(trichloromethyl) carbonate (triphosgene) is used as a raw material, so the preparation method provided by the invention is high in output, and links like production, storage and transportation are safer and more convenient.
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Paragraph 0022; 0023; 0024
(2016/12/01)
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- PROCESS FOR THE PREPARATION OF 2, 5-DIMETHYLEFURAN AND FURFURYL ALCOHOL OVER RUTHENIUM SUPPORTED CATALYSTS
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The present invention relates to an improved process for the preparation of 2.5-dimethylfuran and furfuryl alcohol over ruthenium supported catalysts. Further, the present invention disclosed a process for the selective hydrogenolysis of biomass derived 5-hydroxymethylfurfural (HMF) into 2.5-dimethylfuran (DMF) using Ru nanoparticles supported on NaY zeolite as a catalyst.
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Paragraph 0073
(2016/12/16)
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