539-88-8Relevant articles and documents
Esterification of levulinic acid with ethanol catalyzed by sulfonated carbon catalysts: Promotional effects of additional functional groups
Ogino, Isao,Suzuki, Yukei,Mukai, Shin R.
, p. 62 - 69 (2018)
Analysis of literature data on acid-catalyzed esterification reaction of levulinic acid (LA) with ethanol (EtOH) has suggested that some sulfonated carbon catalysts exhibit higher active-site performance than other solid acid catalysts such as macroreticular resins bearing sulfonic acid groups, zeolites, mesoporous silica functionalized with alkyl- and arene-sulfonic acid groups. To elucidate factors that enable the higher performance of sulfonated carbon catalysts, a series of sulfonated carbon catalysts was synthesized by sulfonating various carbon materials whose concentrations of surface oxygen-containing functional groups, porous structure, and swelling ability differ significantly. The catalysts were tested not only in the liquid-phase esterification reaction of LA with EtOH but also in the reaction of acetic acid (AcA) with EtOH because the latter reaction serves as a test reaction to probe the performance of –SO3H sites with minimal influence by mass transfer limitation and to provide an insight into a role of γ-keto group of LA in catalysis. The results show that all catalysts exhibit nearly the same turnover frequency per –SO3H site in the esterification reaction of AcA with EtOH despite widely different structural properties. In contrast, the data indicate that neighboring functional groups such as –COOH and –OH facilitate the reaction of LA with EtOH presumably through hydrogen-bonding interaction between these surface functional groups and γ-keto group of LA. These results suggest a general design strategy to improve the performance of solid acid catalysts further by precisely tuning the distance between –SO3H sites and neighboring functional groups.
Ethane-Bridged Organosilica Nanotubes Functionalized with Arenesulfonic Acid and Phenyl Groups for the Efficient Conversion of Levulinic Acid or Furfuryl Alcohol to Ethyl Levulinate
Song, Daiyu,An, Sai,Sun, Yingnan,Zhang, Panpan,Guo, Yihang,Zhou, Dandan
, p. 2037 - 2048 (2016)
A series of ethane-bridged organosilica nanotubes functionalized with arenesulfonic acid and phenyl groups (ArSO3H-Si(Et)Si-Ph-NTs) was fabricated successfully by a P123-directed sol–gel co-condensation route combined with hydrothermal treatment with a carefully adjusted P123-to-bis-silylated organic precursor-to-HCl molar ratio in the starting system. The morphological characteristics, textural properties, Br?nsted acidity, surface hydrophobicity, and structural integrity of the carbon/silica framework were characterized. The ArSO3H-Si(Et)Si-Ph-NTs materials were applied in the synthesis of ethyl levulinate from the esterification of levulinic acid and the ethanolysis of furfuryl alcohol, and the excellent catalytic activity was explained in terms of the strong Br?nsted acidity, unique hollow nanotube morphology, and enhanced surface hydrophobicity. Reusability tests confirmed that ArSO3H-Si(Et)Si-Ph-NTs can be reused for three or five times without a significant loss of activity.
Efficient solid acid catalysts based on sulfated tin oxides for liquid phase esterification of levulinic acid with ethanol
Popova, Margarita,Shestakova, Pavletta,Lazarova, Hristina,Dimitrov, Momtchil,Kovacheva, Daniela,Szegedi, Agnes,Mali, Gregor,Dasireddy, Venkata,Likozar, Bla?,Wilde, Nicole,Gl?ser, Roger
, p. 119 - 131 (2018)
Tin oxide nanomaterials prepared by hydrothermal synthesis at 100 °C or 140 °C with or without template and further calcination step were modified with sulfate groups by post synthesis treatment. The catalysts were characterized by X-ray powder diffraction (XRD), N2 physisorption, UV Vis spectroscopy, TG analysis, XPS and solid state NMR spectroscopy. The acidity of the materials was characterized by temperature programmed desorption (TPD) of ammonia. The catalytic performance of nanosized SnO2 catalysts and their sulfated analogues was studied in levulinic acid (LA) esterification with ethanol. Sulfated materials show significantly higher activity compared to non-sulfated ones. It was found that the synthesis parameters (temperature, template) for preparation of the parent SnO2 nanoparticles influence significantly their textural properties and have a pronounced effect on the structural characteristics of the obtained sulfated tin oxide based materials and their catalytic performance in levulinic acid esterification. Skipping the calcination step during the preparation of parent SnO2 samples synthesized without template resulted in the formation of new, highly crystalline phase based on hydrated tin(IV) sulfate [Sn(SO4)2.xH2O], tin(IV) bisulfate [Sn(HSO4)4.xH2O] and/or tin(IV) pyrosulfate [Sn(S2O7).xH2O] species in the sulfated nanomaterials with superior catalytic performance. The formation of this new and catalytically very active phase not reported so far in the literature for sulfated tin oxide-based materials is discussed. The catalytically active sites for esterification of levulinic acid with ethanol is suggested to result from the formation of strong Br?nsted and Lewis acid sites with high density in the newly registered phase. The results indicate that the chemical structure and catalytic performance of the obtained sulfated tin oxide based materials strongly depend on the treatment of the SnO2 nanoparticles before the sulfation procedure.
The selective conversion of furfuryl alcohol to ethyl levulinate over Zr-modified tungstophosphoric acid supported on β-zeolites
Yogita,Rao, B. Srinivasa,Subrahmanyam, Ch.,Lingaiah
, p. 3224 - 3233 (2021)
Catalysts of zirconium-exchanged proton-containing tungstophosphoric acid (TPA) supported on β-zeolites were prepared by an impregnation method for the selective alcoholysis of furfuryl alcohol into ethyl levulinate. The prepared catalysts were characterized by different spectroscopic techniques. The results indicated the existence of a Keggin ion structure of TPA after its modification with Zr ions and successive dispersion on β-zeolites. The introduction of Zr in TPA generated Lewis acidic sites in the catalyst. Pyridine-adsorbed FT-IR confirmed the presence of both Br?nsted and Lewis acidic sites in catalysts. The catalytic activity for the alcoholysis of furfuryl alcohol depends on the strength of both Br?nsted and Lewis acids of the catalyst. Among these catalysts, 20%Zr0.75TPA/β-zeolite was active for the alcoholysis of furfuryl alcohol with a 96% yield of ethyl levulinate. Optimal conditions were established to obtain maximum yield. A plausible reaction mechanism was also proposed. The catalyst was reused without any appreciable loss of activity.
Esterification of levulinic acid to ethyl levulinate over bimodal micro-mesoporous H/BEA zeolite derivatives
Patil,Niphadkar,Bokade,Joshi
, p. 188 - 191 (2014)
A series of bimodal micro-mesoporous H/BEA zeolite derivatives were prepared by the post-synthesis modification of H/BEA zeolite by NaOH (0.05 M-1.2 M) treatment. Samples were characterized by powder XRD, low temperature nitrogen adsorption/desorption, temperature programmed desorption of ammonia and ICP. The mesopore formation was found to play a crucial role in liquid phase esterification of levulinic acid with ethanol. The enhanced catalytic activity of a bimodal micro-mesoporous H/BEA zeolite derivative (H/BEA0.10) prepared by treatment with 0.1 M NaOH can be mainly attributed to the high mesoporosity coupled with better preserved crystallinity and acidic properties.
Conversion of furfuryl alcohol into ethyl levulinate over glucose-derived carbon-based solid acid in ethanol
Zhao, Geng,Liu, Ming,Xia, Xinkui,Li, Li,Xu, Bayin
, (2019)
In this study, a carbon-based solid acid was created through the sulfonation of carbon obtained from the hydrothermal pretreatment of glucose. Additionally, ethyl levulinate, a viable liquid biofuel, was produced from furfuryl alcohol using the environmentally benign and low-cost catalyst in ethanol. Studies for optimizing the reaction conditions, such as reaction time, temperature, and catalyst loading, were performed. Under the optimal conditions, a maximum ethyl levulinate yield of 67.1% was obtained. The recovered catalyst activity (Ethyl levulinate yield 57.3%) remained high after being used four times, and it was easily regenerated with a simple sulfonation process. Moreover, the catalyst was characterized using FT-IR, XRD, SEM, elemental analysis, and acid-base titration techniques.
Synthesis of hierarchical ZSM-12 nanolayers for levulinic acid esterification with ethanol to ethyl levulinate
Dugkhuntod, Pannida,Imyen, Thidarat,Wannapakdee, Wannaruedee,Yutthalekha, Thittaya,Salakhum, Saros,Wattanakit, Chularat
, p. 18087 - 18097 (2019)
Hierarchical ZSM-12 nanolayers have been successfully synthesized via a one-pot hydrothermal process using dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (TPOAC) as a secondary organic structure-directing agent (OSDA). The as-synthesized ZSM-12 samples were characterized by means of XRD, SEM, TEM, N2 physisorption, and NH3-TPD. This clearly demonstrates that the TPOAC content and the crystallization time are crucial parameters for the formation of nanolayered structures. The presence of such a structure significantly improves the mesoporosity of ZSM-12 by generating interstitial mesopores between nanolayers, eventually resulting in enhancing external surface areas and mesopore volumes, and subsequently promoting the molecular diffusion inside a zeolite framework. To illustrate its advantages as a heterogeneous catalyst, hierarchical ZSM-12 nanolayers were applied in the catalytic application of an esterification of levulinic acid with ethanol to ethyl levulinate. Interestingly, hierarchical ZSM-12 nanolayers exhibit an improvement of catalytic activity in terms of levulinic acid conversion (78.5%) and ethyl levulinate selectivity (98.7%) compared with other frameworks of hierarchical zeolite nanosheets, such as ZSM-5 and FAU. The example reported herein demonstrates an efficient way to synthesize a unidimensional pore zeolite with hierarchical nanolayered structure via a dual template method and also opens up perspectives for the application of different hierarchical porous systems of zeolites in the bulky-molecule reactions such as in the case of levulinic acid esterification with ethanol.
Sulphonic Acid-Functionalized Benzimidazolium Based Poly Ionic Liquid Catalyzed Esterification of Levulinic Acid
Khiratkar, Avinash Ganesh,Balinge, Kamlesh Rudreshwar,Krishnamurthy, Manikandan,Cheralathan,Patle, Dipesh S.,Singh, Vishal,Arora, Sanyam,Bhagat, Pundlik Rambhau
, p. 680 - 690 (2018)
Abstract: Esters of levulinic acid (LA) are bio-based compounds having widespread applications and have the remarkable potential to be blended with commercial diesel or gasoline. In this study, a sulphonic acid-functionalized benzimidazolium based poly ionic liquid (SAFBPIL) catalyst was prepared and characterized by NMR, FT-IR, elemental analysis (C, H, N, S), TGA and BET surface area. Br?nsted acidity was determined by anion-exchange/neutralization titration method and was found to be 5.55?mmol/g. The heterogeneous ionic liquid catalyst showed an excellent thermal stability up to 270?°C. Experiments were carried at different temperatures, LA to ethanol molar ratios, catalyst loadings and duration of the reaction in a batch reactor. The highest conversion was obtained at 70?°C using an initial LA:ethanol molar ratio of 1:10 and a catalyst loading of 15?wt% in 9?h. It was observed that ethyl levulinate (EL) could be effectively obtained over SAFBPIL with a selectivity higher than 99.5%. This is due to more acidic sites exhibited on SAFBPIL catalyst under optimized conditions. Herein, we are reporting for the first time an esterification of LA to EL using a new SAFBPIL as a catalyst. The catalyst was recycled for five runs without significant loss of catalytic activity.
Niobium pentachloride-mediated novel homologation reactions using α-trialkylstannylmethyl-β-keto esters
Yamamoto, Makoto,Nakazawa, Misako,Kishikawa, Keiki,Kohmoto, Shigeo
, p. 2353 - 2354 (1996)
In the presence of niobium pentachloride (NbCl5), an α-trialkylstannylmethyl-β-keto ester is homologated to the corresponding γ-keto ester in good yield; the reaction mechanism is discussed.
Selective conversion of biomass-derived levulinic acid to ethyl levulinate catalyzed by metal organic framework (MOF)-supported polyoxometalates
Guo, Tianmeng,Qiu, Mo,Qi, Xinhua
, p. 168 - 175 (2019)
The esterification of levulinic acid (LA) and ethanol into ethyl levulinate is an attractive biomass conversion process since the product EL has wide applications as food additive, fragrance and fuel. Herein, a metal-organic framework (MOF)-supported phosphomolybdic acid [Cu-BTC][HPM] was synthesized with 1,3,5-Benzenetricarboxylic acid, copper nitrate and phosphomolybdic acid in a one-step process at ambient temperature. The synthesized [Cu-BTC][HPM] was used for the catalytic esterification of levulinic acid to EL in ethanol, and showed excellent activity with a high EL yield close to 100% at 120 °C for 6 h, which should be ascribed to the uniform dispersion of HPM embedded in the MOF. The [Cu-BTC][HPM] catalyst could keep stable crystal structure and active component contents, and thus exhibited good stability in recycling process.
Magnetically separable sulfated zirconia as highly active acidic catalysts for selective synthesis of ethyl levulinate from furfuryl alcohol
Tiwari, Manishkumar S.,Gawade, Anil B.,Yadav, Ganapati D.
, p. 963 - 976 (2017)
Magnetically separable sulfated zirconia catalysts were prepared by a two-step approach. Coating of zirconia around the particles helps to increase the number of sites needed for sulfate ion loading and hence enhances the acidity of the catalyst. Different molar concentrations of chlorosulfonic acid were used for sulfonation. The prepared catalysts were used for selective synthesis of ethyl levulinate using renewable substrates: furfuryl alcohol and ethanol. Ethyl levulinate has many applications in different industries including as a potential blending component in biodiesel. The catalyst could be easily separated by the use of a magnet. The influence of different parameters was investigated to reach the optimum yield of ethyl levulinate. Detailed kinetics were established for scaling up purposes. The catalyst is robust and reusable.
Esterification of levulinic acid with ethanol over sulfated mesoporouszirconosilicates: Influences of the preparation conditions on thestructural properties and catalytic performances
Kuwahara, Yasutaka,Fujitani, Tadahiro,Yamashita, Hiromi
, p. 18 - 28 (2014)
Levulinic acid is considered one of the most important biomass-derived chemicals owing to its poten-tial as a versatile building block to synthesize valuable fuels and chemicals. Levulinate esters, such asmethyl levulinate and ethyl levulinate obtained via esterification of levulinic acid with alcohols, can inparticular be used as fuel additives and plasticizers, and thus have a potential to replace a significantamount of petroleum-derived chemical feedstocks. In this article, sulfated zirconosilicates having P6mmhexagonal mesoporous structure were applied as solid acid catalysts to the esterification of levulinic acidwith ethanol to produce ethyl levulinate, and the influences of preparation conditions on the structuralproperties and catalytic performances were investigated. A distinct correlation was observed betweenthe catalytic activity and the density of acid sites, showing that dispersibility of the acid sites and theassociated accessibility of the organic reactants play an important role in determining the overall activ-ity. Among the catalysts tested, sulfated Zr-SBA-15 with optimum Zr content (Si/Zr ratio of 10.7) wasfound to be the best catalyst, the activity of which was far superior to that of conventional sulfated ZrO2.In addition, direct conversion of cellulosic sugars (glucose and fructose) into levulinate esters was alsoexamined.
Chemoselective Coupling of α-Bromo Aldehydes with a Tin Enolate Derived from the Ring Opening of Diketene by Bis(tributyltin) Oxide
Yasuda, Makoto,Nishio, Masahiro,Shibata, Ikuya,Baba, Akio,Matsuda, Haruo
, p. 486 - 487 (1994)
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Catalytic upgrading of levulinic acid to ethyl levulinate using reusable silica-included Wells-Dawson heteropolyacid as catalyst
Pasquale, Gustavo,Vázquez, Patricia,Romanelli, Gustavo,Baronetti, Graciela
, p. 115 - 120 (2012)
In this paper we report, for the first time, the direct incorporation of a heteropolyacid (HPA) with Wells-Dawson structure during the synthesis of silica by the sol-gel technique, in acidic media, using tetraethyl orthosilicate. The catalyst characterization was carried out by 31P MAS-NMR, FT-IR, XRD, N2 adsorption-desorption measurements, and the acidic properties were determined through potentiometric titration with n-butylamine. The synthesized catalysts were used in the esterification of levulinic acid with ethanol, at 78 °C, to obtain ethyl levulinate. The synthesis of silica-included HPAs was satisfactory, and the samples kept their HPA structure intact after synthesis. The catalytic tests for the esterification reaction between levulinic acid and ethanol to produce ethyl levulinate have shown that the silica-included Wells-Dawson HPA is an active and selective catalyst for this reaction. It must be noted that silica-included HPAs also kept their structure and catalytic activity after three consecutive reaction cycles. These results indicated that these solid acids are promissory catalysts for the esterification reaction of levulinic acid and ethanol to ethyl levulinate.
Sulfonated porous biomass-derived carbon with superior recyclability for synthesizing ethyl levulinate biofuel
Zhang, Xiao-Li,Li, Ning,Qin, Zao,Zheng, Xiu-Cheng
, p. 5325 - 5343 (2020)
The synthesis of ethyl levulinate (EL) via esterification of levulinic acid (LA) with ethanol, which can be derived from biomass, has become an attractive topic since EL can be applied in many fields, such as fuel additives for petroleum and biodiesel, food additives and fragrance. Herein, the sulfonated porous carbon catalysts derived from the rinds of corn stalk biomass wastes were prepared by using sulfuric acid and phosphoric acid as the sulfonating agent and activator, respectively. The preparation parameters were optimized based on the catalytic activity for LA esterification with ethanol and the acid density of the corresponding catalysts. Also, various reaction factors were optimized to improve the catalytic efficiency over the optimal sulfonated corn stalk-derived carbon (s-CSC). Under the conditions of reaction temperature 80?°C, catalyst dosage 5?wt%, ethanol-to-LA molar ratio 5.0:1 and reaction time 8?h, the LA conversion reached 94% and 93% catalyzed by s-CSC and the optimal porous catalyst (s-p-CSC), respectively. Noticeably, benefitting from the hierarchical porous structure with large surface area, s-p-CSC exhibited much better recyclability than s-CSC. This work offers a highly effective solid acid catalyst for the synthesis of biofuel.
Ethanolysis of selected catalysis by functionalized acidic ionic liquids: An unexpected effect of ILs structural functionalization on selectivity phenomena
Nowakowska-Bogdan, Ewa,Nowicki, Janusz
, p. 1857 - 1866 (2022/02/05)
A series of functionalized hydrogen sulfate imidazolium ILs were synthesized and applied as catalysts in the reaction of glucose, xylose and fructose with ethanol. In this research, an unexpected selectivity phenomenon was observed. It showed that in this reaction functionalized ILs should be considered as a special type of catalyst. Functionalization of alkyl imidazolium ILs, especially the addition of electronegative OH groups, causes a clear and unexpected effect manifested via visible changes in the selectivity of the reaction studied. In the case of fructose, an increase in the number of OH groups affects an increase in the selectivity towards ethyl levulinate from 14.2% for [bmim]HSO4 to 20.1% for [glymim]HSO4 with an additional increase in selectivity to 5-hydroxymethyfurfural. In turn, for xylose, the introduction of OH groups to the alkyl chain was manifested by a decrease in selectivity to furfural as its ethyl acetal and an increase in selectivity to ethylxylosides. This journal is
