2052-15-5Relevant articles and documents
Highly Efficient Conversion of Renewable Levulinic Acid to?n-Butyl Levulinate Catalyzed by Sulfonated Magnetic Titanium Dioxide Nanotubes
Mao, Fei-Feng,Zhao, Wenguang,Tao, Duan-Jian,Liu, Xianxiang
, p. 2709 - 2715 (2020)
Abstract: A new solid acid catalyst Fe3O4@TNTs-SO3H was successfully prepared, characterized, and applied for efficient conversion of renewable levulinic acid to n-butyl levulinate, serving as a promising liquid fuel additive. This catalyst was demonstrated to show high catalytic activity and afford n-butyl levulinate with a yield of 94.6% under optimum conditions. Graphic Abstract: [Figure not available: see fulltext.]
Esterification of levulinic acid to n-butyl levulinate over various acidic zeolites
Maheria, Kalpana C.,Kozinski, Janusz,Dalai, Ajay
, p. 1220 - 1225 (2013)
Levulinic acid (LA) has been recognized as a versatile building block for the synthesis of various organic chemicals as it contains ketone and carboxylic functional groups. Levulinate esters are important chemical feedstocks having potential applications either in flavouring and fragrance industries or biodiesel as blending component. The present work focuses on the synthesis of n-butyl levulinate by esterification of LA with n-butanol using various small and large pore zeolites. The preferential order to yield n-butyl levulinate was found to be: H-BEA > H-Y > H-ZSM-5 > H-MOR. Further, a study for optimizing the reaction conditions such as acid to n-butanol molar ratio, reaction time and catalyst concentration has been described. Under optimized reaction conditions, zeolite H-BEA has been found as most efficient catalyst with 82.2 % LA conversion and 100 % selectivity of n-butyl levulinate. Graphical Abstract: [Figure not available: see fulltext.] Scheme: Zeolite catalyzed esterification of levulinic acid
Highly efficient metal salt catalyst for the esterification of biomass derived levulinic acid under microwave irradiation
Huang, Yao-Bing,Yang, Tao,Cai, Bo,Chang, Xin,Pan, Hui
, p. 2106 - 2111 (2016)
The esterification of levulinic acid (LA) to alkyl levulinates has been investigated in the presence of various metal salt catalysts under microwave irradiation. The reaction obtained 99.4% yield of methyl levulinate (ML) in the presence of Al2(SO4)3 catalyst in methanol solution under microwave conditions. The optimized reaction conditions were 110 °C and 10 minutes with a 20 mol% catalyst loading. Alcohols with longer carbon chains showed lower reactivities in the microwave electromagnetic field due to their poorer abilities to absorb and transmit microwave energy. Moreover, microwave irradiation provided a significantly higher reaction rate compared to conventional oil bath heating. LA aqueous solution was also converted to ML with high yields. The Al2(SO4)3 catalyst was successfully applied to the esterification of other biomass derived organic acids to their corresponding esters in high yields. Finally, the catalyst was recycled 5 times without much decrease in activity.
Carbon nanotube/PTFE as a hybrid platform for lipase B fromCandida antarcticain transformation of α-angelica lactone into alkyl levulinates
Boncel, Slawomir,Chrobok, Anna,Jurczyk, Sebastian,Kolanowska, Anna,Latos, Piotr,Szelwicka, Anna
, p. 3255 - 3264 (2020)
In this work an enzymatic method for the synthesis of alkyl levulinates from α-angelica lactone has been reported for the first time. Lipase B fromCandida antarcticawas immobilizedviainterfacial activation on the surface of a hybrid support, consisting of commercially available multi-walled carbon nanotubes (MWCNTs) and polytetrafluoroethylene (PTFE). Among the biocatalysts with various contents of PTFE in the support, the CALB/MWCNT-PTFE (0.10 wt%) biocatalyst with 22.5 wt% CALB loading was determined as the most active one in the model synthesis of then-butyl levulinate in toluene.n-Butyl levulinate was obtained quantitively after 120 min of the reaction under the selected reaction conditions (2-fold molar excess ofn-butanol, 0.150 g of biocatalyst per 1 mmol of α-angelica lactone, 20 °C). The yield ofn-butyl levulinate was found to be higher than that in the presence of accurate amounts of sulfuric acid or Novozyme-435. Additionally, the unique stability of the developed biocatalyst was demonstrated over 6 reaction cycles at 20 °C. The biocatalyst remained stable over 3 reaction cycles at 60 °C as well. The essence of the proposed approach lies in the possibility to overcome the equilibrium limitations occurring in the conventional Fisher esterification. The activity of the elaborated hybrid biocatalyst in the reactions non-specific for lipases is a clear proof of the versatility of the novel system.
Direct conversion of furfuryl alcohol to butyl levulinate using tin exchanged tungstophosphoric acid catalysts
Dicks, Jennifer Sarah,Keogh, John,Manyar, Haresh G.,Ranade, Vivek V.,Tiwari, Manishkumar S.
, (2020)
To decrease the dependence on crude oil, biomass derived liquid transportation fuels are highly desirable. Butyl levulinate is a potential cellulose-derived biofuel additive with properties similar to diesel and low water solubility. Herein we report a direct one-pot production of levulinic acid ester, butyl levulinate, from furfuryl alcohol by alcoholysis using n-butanol. The partial tin exchanged tungstophosphoric acid (TPA) supported on montmorillonite K-10 catalysts showed facile alcoholysis of furfuryl alcohol to levulinate ester under mild temperature conditions. Partially exchanging the H+ ion of TPA with Sn (x = 1) resulted in enhanced acidity of the catalyst and showed an increase in the catalytic activity as compared to TPA/K-10 catalyst. A series of tin exchanged tungstophosphoric acid (20 % w/w) supported on montmorillonite K-10 clay (Snx-TPA/K-10, where x = 0.5–1.5) were synthesized and thoroughly characterized by using XRD, FT-IR, UV-VIS, titration and SEM techniques. Among various catalysts, Sn1-TPA/K-10 was found to be the most active catalyst for butyl levulinate synthesis. Two different clay supports and varying tin loadings were used to study the effects on surface acidity as well as catalytic activity in butyl levulinate synthesis. Effects of different reaction parameters were studied and optimized to get high yields of butyl levulinate. Under mild reaction conditions at 110 °C, complete conversion of furfuryl alcohol with 98 % selectivity to butyl levulinate was achieved. The prepared catalyst could be recycled at least five times without significant loss of activity. The overall process is green and clean.
Solvent-free transesterification of methyl levulinate and esterification of levulinic acid catalyzed by a homogeneous iron(III) dimer complex
Melchiorre, Massimo,Amendola, Raffaele,Benessere, Vincenzo,Cucciolito, Maria E.,Ruffo, Francesco,Esposito, Roberto
, (2020)
Levulinic acid esters MeC(O)CH2CH2CO2R (LAE) are emerging bio-based chemicals used as solvents, additives and plasticizers. In this work a variety of levulinates (R= n-butyl, n-hexyl, n-octyl, 2-ethylhexyl, geranyl, 2-ethoxyethyl, benzyl, 2-octyl, cyclohexyl, menthyl) is obtained from the solvent-free transesterification of methyl levulinate (ML) and esterification of levulinic acid (LA), catalyzed by a dimeric complex of iron(III). The results are competitive with the few related reports of literature mainly based on heterogeneous catalysis. This first systematic study based on a homogeneous catalytic system therefore represents a significant extension within the field of biomass valorization.
Production of n-butyl levulinate over modified KIT-6 catalysts: comparison of the activity of KIT-SO3H and Al-KIT-6 catalysts
Najafi Chermahini, Alireza,Assar, Matin
, p. 2045 - 2053 (2019)
The catalytic activity of propylsulfonic acid-functionalized mesoporous silica (KIT-SO3H) was compared to the performance of alumina-incorporated KIT-6 (Al-KIT-6) in the esterification reaction of the biomass-derived levulinic acid with n-butanol. The catalysts were prepared by functionalization of the silica support with propylsulfonic acid (Pr-SO3H) by post-synthesis grafting using 3-mercaptopropyltrimethoxysilane as a propyl-thiol precursor followed by oxidation. In addition, Al-KIT-6 was synthesized according to in situ synthesis. Catalysts were characterized using various techniques such as XRD, nitrogen adsorption/desorption, SEM, TGA, ICP-OES, FT-IR and elemental analysis. It is evident that increases in catalyst loading, butyl alcohol-to-levulinic acid ratio and reaction temperature significantly enhance the butyl levulinate yield. The reusability and stability of catalysts were evaluated, and it was found that while esterification reaction by KIT-SO3H compound catalyzed under milder conditions, the stability of Al-KIT-6 catalyst was better.
Continuous Synthesis of Fuel Additives Alkyl Levulinates via Alcoholysis of Furfuryl Alcohol over Silica Supported Metal Oxides
Chada, Raji Reddy,Koppadi, Kumara Swamy,Enumula, Siva Sankar,Kondeboina, Murali,Kamaraju, Seetha Rama Rao,Burri, David Raju
, p. 1731 - 1738 (2018)
Abstract: Aiming at synthesizing alkyl levulinates via alcoholysis of furfuryl alcohol in continuous mode for the first time an attempt is made using cheapest and eco-friendly solid acid catalysts. Different silica supported solid acid catalysts containing the oxides of aluminium, tungsten, zirconium and titanium have been prepared. The nature, number and strength of surface acidic sites were evaluated by DRIFT spectroscopy with pyridine adsorption and NH3-TPD and also structural and textural features of the catalysts have been investigated by XRD and BET surface area techniques. Al2O3/SiO2 catalyst exhibited better activity with 100% conversion of furfuryl alcohol and 92.8% selectivity of methyl levulinate, which may be due to more number of surface acidic sites with large number of weak Lewis acidic sites. The catalytic activity of these solid acid catalysts is as follows: Al2O3/SiO2 > ZrO2/SiO2 > WO3/SiO2 > TiO2/SiO2. This is well correlated with the number of surface acidic sites. The stable catalytic activity during the 10?h time-on-stream study confirmed the sturdiness of Al2O3/SiO2 catalyst and also it is active for the selective formation of ethyl, n-propyl, n-butyl levulinates.
Zirconium Exchanged Phosphotungstic Acid Catalysts for Esterification of Levulinic Acid to Ethyl Levulinate
Pasha, Nayeem,Lingaiah,Shiva, Raj
, p. 2500 - 2507 (2019)
Abstract: Zirconium exchanged phosphotungstic acid catalysts were prepared and studied for esterification of levulinic acid with ethanol. The catalysts were characterized by powder XRD, BET surface area, Raman spectroscopy, FT-infrared spectroscopy, Temperature programmed desorption of NH3 and Pyridine adsorbed FT-IR analysis. The presence of Zr resulted in the generation of strong Lewis acidic sites. Among all the catalysts the catalyst with partially exchanged Zr (Zr0.75TPA) showed higher activity due to the present of stronger Br?nsted and Lewis acidic sites. The Zr0.75TPA catalyst exhibits amazing reusability with constant activity. Graphic Abstract: Zr exchanged TPA is active in the esterification of levulinic acid into ethyl levulinate.[Figure not available: see fulltext.].
Catalytic upgrading of α-angelica lactone to levulinic acid esters under mild conditions over heterogeneous catalysts
Al-Shaal, Mohammad G.,Ciptonugroho, Wirawan,Holzh?user, Fabian J.,Mensah, Joel B.,Hausoul, Peter J. C.,Palkovits, Regina
, p. 5168 - 5173 (2015)
Butyl levulinate was prepared starting from α-angelica lactone and butanol over Amberlyst 36. Different reaction conditions were optimized, which resulted in full conversion and 94% selectivity toward the ester at 75°C. A reaction network analysis reveals pseudo-butyl levulinate and levulinic acid as intermediates in the preparation of butyl levulinate. The mild protocol was successfully applied for different alcohols and compared with the esterification of levulinic acid. Overall, this study identifies α-angelica lactone as a better candidate than levulinic acid for the heterogeneously catalysed preparation of levulinic acid esters. A catalyst screening shows that also zeolites and zirconia-based catalysts are able to catalyse the reaction. However, the transformation of the intermediate pseudo-butyl levulinate into butyl levulinate requires acid sites of sufficient strength to proceed.
