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.
Conversion of levulinic acid to ethyl levulinate using tin modified silicotungstic acid supported on Ta2O5
Ganji, Parameswaram,Roy, Sounak
, (2020)
Tin modified silicotungstic acid (STA) deposited on Ta2O5 was explored as suitable catalyst for the conversion of levulinic acid to ethyl levulinate. The microwave synthesized catalysts of varying amounts of STA were characterised by N2 adsorption, powder XRD, FT-IR, FE-SEM, XPS, pyridine-FT-IR, TGA-DTA and NH3-TPD. Among the synthesized catalysts, 50% Sn2STA/Ta2O5 catalyst exhibited excellent catalytic activity for the esterification of levulinic acid providing 78% of ethyl levulinate yield and stable recyclability up to three cycles. The rate of esterification was 6.6 × 10?3 mol/g/min, which is significantly higher compared to reported values in the open literature. Mechanistic investigations revealed that the high catalytic activity was influenced by the presence of appropriate Br?nsted acid sites, surface area and porosity.
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.
Zr-DBS with Sulfonic Group: A Green and Highly Efficient Catalyst for Alcoholysis of Furfuryl Alcohol to Ethyl Levulinate
Li, Xiaoning,Li, Yehui,Wang, Xiang,Peng, Qingrui,Hui, Wei,Hu, Aiyun,Wang, Haijun
, p. 2622 - 2630 (2021)
The alcoholysis of furfuryl alcohol (FA) produce ethyl levulinate (EL) plays a crucial role in the field of biomass conversion. In this work, a novel Zr-base catalyst with sulfonic groups in its structure was prepared by the co-precipitation of sodium dodecyl benzene sulfonate and ZrOCl2 (Zr-DBS) under non-toxic conditions. It was found that Zr-DBS has an excellent catalytic performance for this reaction and an EL yield of 95.27% could be achieved. Besides, Zr-DBS could be easily separated from the reaction system and reused at least four times without a significantly decrease in activity. Meanwhile, Zr-DBS was characterized by Fourier transform infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption–desorption, inductively coupled plasma optical emission spectroscopy (ICP-OES) and Temperature-programmed desorption of ammonia (NH3-TPD). The main reason for the high catalytic activity of the Zr-DBS was that the synergetic effects of Lewis and Br?nsted acid sites and appropriate textural properties. Graphic Abstract: [Figure not available: see fulltext.]
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.
Tuning the Catalytic Activity of UiO-66 via Modulated Synthesis: Esterification of Levulinic Acid as a Test Reaction
Fan, Jingdeng,Gao, Lijing,Hu, Feng,Qu, Xumin,Wei, Ruiping,Wu, Yuanfeng,Xiao, Guomin,Zhang, Zongqi
, (2020)
Due to their high stabilities and tunable defects, zirconium terephthalate UiO-66 type metal organic frameworks (MOFs) have been promising catalysts in many catalytic reactions. The catalytic activity of UiO-66 MOFs is significantly affected by the density of defects and hydroxyl groups bonded to Zr6 nodes, which can be tuned by modulators. In this work, a series of defective UiO-66 were synthesized via tuning the ratio of H2BDC/Zr and adding monocarboxylic acids with different chain length as modulators. The synthesized UiO-66 MOFs were characterized by powder X-ray diffraction, N2 physisorption, IR and 1H NMR spectroscopy, scanning and transmission electron microscopy. Esterification of levulinic acid with ethanol was selected to reveal the influence of modulators, defects and hydroxyl groups. The results showed that UiO-66 with 0.5 of H2BDC/Zr ratio and lauric acid as the modulator owned excellent catalytic activity. The cooperative effects, between the Lewis acid sites offered by unsaturated Zr6 nodes and Br?nsted acid sites supplied by OH, has been revealed to have a significant influence on the catalytic activity.
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.
One pot conversion of glucose to ethyl levulinate over a porous hydrothermal acid catalyst in green solvents
Bosilj, Monika,Schmidt, Johannes,Fischer, Anna,White, Robin J.
, p. 20341 - 20344 (2019)
The one-pot conversion of glucose to ethyl levulinate over an acid-functionalised hydrothermal catalyst (derived from glucose) provides high initial yields up to 37 mol%, comparable to the homogeneous H2SO4 catalyst, whilst catalyst performance is strongly influenced by green solvent choice.
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.
Fabrication of propylsulfonic acid functionalized SiO2 core/PMO shell structured PrSO3H-SiO2@Si(R)Si nanospheres for the effective conversion of D-fructose into ethyl levulinate
Song, Daiyu,Sun, Yingnan,Zhang, Qingqing,Zhang, Panpan,Guo, Yihang,Leng, Jiyan
, p. 36 - 46 (2017)
Propylsulfonic acid functionalized SiO2 core/alkyl- or phenyl-bridged organosilica shell structured PrSO3H-SiO2@Si(R)Si (R = –C2H4–, –C6H4– or –C6H4–C6H4–) nanospheres are facilely prepared by a CTAB-directed one-pot two-step condensation strategy. The morphological characteristics, textural properties, Br?nsted acid nature and structure of the PrSO3H-SiO2@Si(R)Si nanospheres are well characterized. The materials are successfully applied in the catalytic transformation of D-fructose into the important organic chemical, ethyl levulinate, in the presence of ethanol as both reactant and solvent. The catalytic activity of the PrSO3H-SiO2@Si(R)Si nanospheres outperform commercially available Amberlyst-15, HY zeolite and HCl, mainly attributing to their strong Br?nsted acid nature; additionally, unique core-shell structure with excellent porosity properties and well-adjusted hydrophilicity/hydrophobicity also give the positive influence on the ethanolysis activity, which can improve the accessibility of the reactants to the PrSO3H sites and facilitate the multi-step ethanolysis reaction proceeding to the formation of the final product. The PrSO3H-SiO2@Si(R)Si nanospheres can be reused three times without obvious activity loss, contributed from covalent bonding of the PrSO3H groups with the silica and organosilica framework as well as hydrophobic PrSO3H-functionalized organosilica shell.
