- Recognizing soft templates as stimulators in multivariate modulation of tin phosphate and its application in catalysis for alkyl levulinate synthesis
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Catalyst synthesis is an art where an inefficient material can be remarkably converted into a highly active and selective catalyst by adopting a suitable synthetic strategy to tune its properties during synthesis. The underlying principle of the strategy presented here is the integration of tailoring the structural and chemical behavior of tin phosphates with tuned catalytic active centers directed by employing different structure directing agents (SDAs) and the attempt to understand this in detail. It is demonstrated how soft templates can be effectively used for their so far unknown utilization of tuning the active sites in phosphate containing catalysts. We found that, by using an appropriate synthesis strategy, it is possible to tune and control explicitly both the catalyst morphology and the nature of active sites at the same time. The 31P MAS NMR study revealed that employing SDAs in the synthesis strongly influenced the nature and amount of phosphate species in addition to porosity. The resultant different nanostructured SnPO catalysts were investigated for one-pot synthesis of alkyl levulinates via alcoholysis of furfuryl alcohol. Among the catalysts, SnPO-P123 exhibited greater butyl levulinate yield via alcoholysis of furfuryl alcohol with n-butanol and the study was extended to synthesize different alkyl levulinates. Importantly, the active sites in the SnPO-P123 catalyst responsible for the reaction were elucidated by a study using 2,6-lutidine as a basic probe molecule. This study therefore provides an avenue for rational design and construction of highly efficient and robust nanostructured SnPO catalysts to produce alkyl levulinates selectively. This journal is
- Manjunathan, Pandian,Shanbhag, Dhanush Y.,Vinu, Ajayan,Shanbhag, Ganapati V.
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p. 272 - 282
(2021/01/28)
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- AQUIVION perfluorosulfonic acid resin for butyl levulinate production from furfuryl alcohol
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This study reports the sustainable production of butyl levulinate (BL) from furfuryl alcohol (FA), a highly abundant biomass derived platform obtained from C5 sugars in hemicellulose. FA upgrading is performed adopting a robust and easily recyclable commercial perfluorosulfonic acid resin, Aquivion P87S, used as cylinder shaped pellets. This approach avoids the use of corrosive and harmful mineral acids allowing a simple separation of the catalyst from the reaction mixture, reducing the cost of equipment materials and disposal or neutralization issues, also resulting in reduced solvent dehydration. Moreover, FA alcoholysis to BL involves butanol as a sustainable reaction medium, also readily obtained from biomass. The catalyst remains stable up to 6 recycles. Furthermore, the absence of heavy by-products and the stability of the catalyst allowed us to perform successive additions of the substrate to the reaction medium to increase the BL concentrations up to 0.66 M (13 wt%).
- Bernal, Hilda Gómez,Oldani, Claudio,Funaioli, Tiziana,Raspolli Galletti, Anna Maria
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p. 14694 - 14700
(2019/09/30)
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- Hydrothermal carbon enriched with sulfonic and carboxyl groups as an efficient solid acid catalyst for butanolysis of furfuryl alcohol
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Carbonaceous material (GC-PTSA-AC) functionalized with both high density of SO3H and COOH groups was prepared by one-step hydrothermal carbonization of glucose with p-toluenesulfonic acid and acrylic acid. This novel carbon could be used directly for the alcoholysis of furfuryl alcohol and n-butanol without any post-modification, and it was found to be more efficient than the monofunctional hydrothermal carbon only decorated with SO3H or COOH groups. The reason was attributed to the larger amount of COOH groups on GC-PTSA-AC, cooperating with the SO3H active sites to facilitate the butanolysis reaction.
- Yang, Jinfan,Zhang, Hongyu,Ao, Zhifeng,Zhang, Sufeng
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p. 109 - 113
(2019/07/02)
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- Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol by using Ultrasmall Rh Nanoparticles Embedded on Diamine-Functionalized KIT-6
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A Rh/ED-KIT-6 catalyst comprised of Rh nanoparticles embedded on mesoporous silica (KIT-6) functionalized with N1-[3-(trimethoxysilyl)propyl]ethane-1,2-diamine was synthesized by Rh3+ adsorption and chemical reduction in the liquid phase. The structure of ED-KIT-6 and textural properties of the pristine and supported Rh catalysts, as well as particle size and chemical state of the Rh species were examined by various analytical methods. The homogeneous dispersion of ultrasmall Rh nanoparticles, approximately 1.2 nm in size, stabilized by the grafted diamine (ED) species was confirmed. Rh/ED-KIT-6 was applied to the transfer hydrogenation of furfural (FFR) to furfuryl alcohol (FAL) by using formic acid (FA) as the hydrogen source. The effect of the solvent and reaction parameters, such as temperature, reaction time, and FA/FFR ratio, were investigated. The Rh-embedded catalyst exhibited a significantly high turnover frequency (TOF≈204 h?1) to that of Ru, Pd, or Ni-based catalysts on KIT-6. A plausible reaction mechanism was proposed after examining an independent FA decomposition reaction over the same Rh-ED-KIT-6 catalyst. The heterogeneity of the catalyst was verified by a hot filtration experiment. The Rh/ED-KIT-6 could be reused for up to three cycles without any decrease in catalytic activity and selectivity, but the slow oxidation of Rh species was detected.
- Neeli, Chinna Krishna Prasad,Chung, Young-Min,Ahn, Wha-Seung
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p. 4570 - 4579
(2017/11/29)
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- Alcoholysis of Furfuryl Alcohol into n-Butyl Levulinate Over SBA-16 Supported Heteropoly Acid Catalyst
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Abstract: In this work, n-butyl levulinate a potential renewable chemical in the energy sector and in the field of fine chemical synthesis has been synthesized via alcoholysis of furfuryl alcohol in batch process at atmospheric pressure over SBA-16 supported tungstophosphoric acid (TPA) catalyst. In order to characterize and correlate the catalytic activity, the wet impregnated TPA/SBA-16 catalysts were subjected to the physico chemical characterization techniques such as X-ray diffraction, N2-physisorption, SEM, TEM, FT-IR, NH3-TPD and pyridine adsorbed FT-IR analysis. The retention of 3D mesoporous structure and TPA structure even after impregnation was confirmed by XRD and N2-physisorption. The impregnation of TPA over SBA-16 creates the more number of available active acidic sites for the reactants. 25?wt% TPA/SBA-16 offers 97% selectivity to n-butyl levulinate with complete conversion of furfuryl alcohol in 3?h. Various reaction parameters were optimized to achieve the best catalytic activity. These results imply that the conversion of furfuryl alcohol to n-butyl levulinate go on with the formation of the intermediate 2-butoxymethylfuran. The recyclability of the catalyst and characterization of the spent catalyst was also studied. Graphical Abstract: [Figure not available: see fulltext.] SBA-16 supported TPA catalyst is effective in the conversion of furfuryl alcohol to n-butyl levulinate at atmospheric pressure.
- Siva Sankar, Enumula,Saidulu Reddy,Jyothi, Yadagiri,David Raju, Burri,Rama Rao, Kamaraju Seetha
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p. 2807 - 2816
(2017/09/14)
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- Indium(III) triflate promoted synthesis of alkyl levulinates from furyl alcohols and furyl aldehydes
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A facile protocol for the alcoholysis of furfuryl alcohol into levulinate esters has been developed employing low catalyst loadings of indium(III) triflate. This method provides a rapid and efficient route for the synthesis of these useful materials. The alcoholysis reactions of 5-hydroxymethylfurfural (HMF), furfural and furfural dimethylacetal were also investigated under these reaction conditions.
- Kean, Jacqueline R.,Graham, Andrew E.
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p. 175 - 179
(2015/02/19)
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- Antiknock properties of furfural derivatives
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Preparative amounts of furfuryl alcohol ethers and furfural acetals were prepared from renewable vegetable raw materials. The blending reseach octane numbers of mixing of furan derivatives in straight-run gasoline were estimated: butyl furfuryl ether, 97.8 ± 7; propyl furfuryl ether, 112 ± 6; furfural diethyl acetal, 105 ± 6, furfural ethylene glycol acetal, 108 ± 7; furfurylamine, 194 ± 4. These results demonstrate prospects for using furan derivatives as available biofuels.
- Tarabanko,Chernyak,Simakova,Kaigorodov,Bezborodov,Orlovskaya
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p. 1778 - 1782
(2016/03/05)
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- CATALYST AND CATALYTIC PROCESS FOR THE ETHERIFICATION/REDUCTION OF FURFURYL DERIVATIVES TO TETRAHYDROFURFURYL ETHERS
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The invention relates to a method for producing tetrahydrofurfuryl ethers, characterised in that it involves carrying out consecutive etherification/reduction reactions based on a compound containing at least one furan ring, in the presence of at least one alcohol and at least one catalyst, optionally in the presence of H2. The catalytic process can be carried out in a cascade reaction ("one-pot"), operating under soft reaction conditions and without a solvent.
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Paragraph 0094
(2015/11/16)
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- Action of boron trifluoride etherate and stannic chloride on heterocyclic aromatic acetals
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Twelve heterocyclic aromatic acetals (1a-12a) have been synthesised and their reactions with Lewis acids, viz. boron trifluoride etherate (BTE) and stannic chloride (STC) have been studied.The acetals yield ethers, esters and aldehydes with BTE, but only esters and aldehydes with STC.Interestingly, pyridine-2-aldehyde acetal (12a), yields aldehyde alone, that too in low yield.Probable mechanisms have been suggested for the product formation.
- Raja, S.,Xavier, N.,Arulraj, S. J.
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p. 687 - 689
(2007/10/02)
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